USOO9682868B2

(12) United States Patent (10) Patent No.: US 9,682,868 B2

Hasinoff et al. (45) Date of Patent: *Jun. 20, 2017
(54) PARTIALLY CONTINUOUS (2013.01); COIP 2002/60 (2013.01); COIP
COUNTERCURRENT PROCESS FOR 2004/61 (2013.01); COIP 2006/80 (2013.01)
CONVERTING GYPSUM TO AMMONUM (58) Field of Classification Search
SULFATE AND CALCUM CARBONATE CPC ....................................................... CO1F 11 F18
See application file for complete search history.
(71) Applicant: Sparstane Technologies LLC,
Brimingham, AL (US) (56) References Cited
(72) Inventors: Murray P. Hasinoff, Birmingham, AL U.S. PATENT DOCUMENTS
(US); Taylor Pursell, Mountain Brook,
AL (US); Joseph A. Saiia, 3,004,827 A * 10/1961 Schaus .................... CO1B 25/22
Birmingham, AL (US); Arthur R. 423.316
3,552,919 A 1/1971 Roberts
Shirley, Jr., Florence, AL (US); Keith 3,615.253 A 10, 1971 Warzel
D. Cochran, Killen, AL (US); Timothy 3,687,620 A 8, 1972 Witts et al.
G. Holt, Florence, AL (US); Joseph M. 8,758,719 B2 * 6/2014 Hasinoff ................. C22B 26/20
Miller, Killen, AL (US); Melissa C. 423 (420
Hayes, Florence, AL (US) 2014/0044619 A1 2/2014 Hasinoff et al.

(73) Assignee: SPARSTANE TECHNOLOGIES FOREIGN PATENT DOCUMENTS

LLC, Birmingham, AL (US) WO WO2O16115386 A T 2016
WO WO2O16115393 A T 2016
(*) Notice: Subject to any disclaimer, the term of this WO WO2O16115396 A T 2016
patent is extended or adjusted under 35 WO WO2O16115398 A T 2016
U.S.C. 154(b) by 0 days. WO WO2O16137597 A 9, 2016
This patent is Subject to a terminal dis * cited by examiner
claimer.
Primary Examiner — Stuart Hendrickson
(21) Appl. No.: 15/005,851 (74) Attorney, Agent, or Firm — Paul E. White, Jr.;
Manelli Selter PLLC
(22) Filed: Jan. 25, 2016
(57) ABSTRACT
(65) Prior Publication Data
The present invention includes a partially continuous coun
US 2016/0221834 A1 Aug. 4, 2016 tercurrent process for converting gypsum, by reaction with
Related U.S. Application Data ammonium carbonate, to products of ammonium Sulfate and
calcium carbonate by introducing the reactants into reactors,
(60) Provisional application No. 62/109,988, filed on Jan. mixing the reactants for a predetermined amount of time,
30, 2015. employing a novel combination of countercurrent flows
coupled with the reactors operated in a batch manner with
(51) Int. C. process recycle of liquids, removing materials from the
GOIF II/8 (2006.01) reactor and separating Solids from solutions wherein no
COIF II/I-8 (2006.01) reactants are added during the removal process and thus the
C30B 7/4 (2006.01) reactants have sufficient time to react and ensure the desired
C3OB 29/10 (2006.01) degree of reaction, yield and purity of product calcium
COIC I/244 (2006.01) carbonate and ammonium sulfate while minimizing the
(52) U.S. C. reaction time.
CPC .............. COIF II/18 (2013.01); COIC I/244
(2013.01); C30B 7/14 (2013.01); C30B 29/10 28 Claims, 25 Drawing Sheets
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FGURE 3
Product Calcium Carbonate Crystals: SEM image at 12,000x
U.S. Patent US 9,682,868 B2
 US 9,682,868 B2
1. 2
PARTIALLY CONTINUOUS The phosphate rock is typically treated with sulfuric acid
COUNTERCURRENT PROCESS FOR according to the following reaction:
CONVERTING GYPSUM TO AMMONUM
SULFATE AND CALCUM CARBONATE

BACKGROUND OF THE INVENTION

Tri-calcium phosphate reacts with sulfuric acid to form
phosphoric acid and calcium Sulfate (gypsum).
Phosphate rock may also be treated with nitric acid to
This invention relates to the efficient, low cost production yield phosphoric acid and calcium nitrate. The calcium
of high purity ammonium Sulfate and calcium carbonate 10 nitrate is then reacted with ammonium sulfate to yield
from gypsum. The gypsum may be from any source, whether ammonium nitrate and gypsum as shown in the following
mined from natural deposits or produced synthetically by a reactions:
variety of means including that obtained as a byproduct from
flue gas desulfurization (FGD gypsum) systems located at
electric power plants, the manufacture of phosphoric acid 15
(phosphogypsum), the production of nitrogen-phosphorus Whether the phosphate rock is treated with sulfuric acid,
potassium (NPK) fertilizers (nitrogypsum), the production nitric acid or another acid, the less soluble gypsum can be
of titanium dioxide by the Sulfate process (titanogypsum), separated from the product phosphoric acid by filtration. The
the manufacture of purified citric acid (citrogypsum), and resulting phosphogypsum is usually a hemihydrate or a
the production of hydrofluoric acid (fluoroanhydrite (an dihydrate, depending on process parameters and reactant
anhydrous form of gypsum). concentrations.
While synthetic gypsum provides a cheap source of Titanium dioxide is an important white pigment which is
gypsum as byproducts, the physical structure of the gypsum manufactured in large quantities wherein about half is pro
crystalline particles may have characteristics that make it duced by the sulfate process. The sulfate process results in
difficult to react with other chemicals. The process of the 25 byproduct calcium sulfate (titanogypsum).
present invention overcomes this problem and other diffi Large quantities of citric acid are used in the food,
culties to result in an economically viable method to produce pharmaceutical and detergent industries which is produced
ammonium sulfate and calcium carbonate of high purity and by mycological fermentation of crude Sugar Solutions such
yield and further resulting in selectable polymorphs of as molasses. In order to eliminate impurities from the citric
calcium carbonate including the crystal structure of Vaterite 30 acid, Such as proteins and Sugars, it is precipitated with lime
and calcium carbonate crystals down to nano proportions. (calcium oxide) to form calcium citrate. Pure citric acid is
Further, the process provides for multiple concurrent cal produced by acidification with sulfuric acid and byproduct
cium carbonate crystal sizes and crystal shapes to be pro calcium Sulfate (citrogypsum) is removed.
duced simultaneously. In the production of hydrofluoric acid the mineral fluor
FGD gypsum is a synthetic product resulting from Sulfur
35 spar or fluorite is heated with sulfuric acid. This results in the
production of hydrofluoric acid and calcium sulfate in the
dioxide (SO) gas emission control systems used at fossil anhydrous form of anhydrite (fluoroanhydrite).
fuel and particularly, coal combustion power plants to Synthetically produced gypsum results from precipitation
remove sulfur from the combustion gases using “scrubber' processes and consists of Small, fine, crystalline particles
devices. The sulfur dioxide is derived from sulfur containing 40 that are chemically nearly identical to mined natural gyp
compounds in the fuels. A wet scrubber uses lime (calcium Sum, but physically may be of Smaller particle size and have
oxide or calcium hydroxide) or more typically, limestone different crystal structure.
(calcium carbonate) to react with Sulfur dioxide gas to For example, FGD gypsum produced at different power
remove the sulfur in a solid form. The reaction in wet
plants may differ slightly in chemical composition and in
scrubbing uses a limestone (CaCO)—water slurry to pro 45 crystalline structure. Most chemical differences are due to
duce calcium Sulfite (CaSO) according to the following impurities from the employed fuel. Structurally, however,
chemical reaction: Some FGD gypsum may be composed of crystalline particles
that have less Surface area and are thus less reactive than
CaCO (solid)+SO(gas)->CaSO(solid)+CO(gas) other FGD gypsum crystalline particles. FGD crystals that
To partially offset the cost of the FGD installation, the 50 are thicker and more spherical have less reactive Surface
CaSO (calcium sulfite) may be further oxidized (known as area. Thus, a process that employs FGD gypsum as a starting
forced oxidation) to produce CaSO4.2H2O (FGD gypsum) material, must be able to accommodate the less reactive
according to the following chemical reaction: FGD gypsum particles as well as FGD gypsum crystalline
particles resulting from other FGD installations that produce
55 particles having flatter, more disc like structure with greater
reactive Surface area.
The above discussion of the relation of crystal size and
Large quantities of phosphoric acid are used in the pro shape to reactivity is also true for other types of gypsum,
duction of fertilizers and detergents. Phosphoric acid is Such as, for example, phosphogypsum, titanogypsum, citro
obtained by processes based on the decomposition of phos 60 gypsum and fluoroanhydrite.
phate minerals, such as phosphate rock (e.g. apatite or A further consideration of the process that results in the
phosphorite) with an acid. Such as Sulfuric acid or nitric acid. production of synthetic gypsum is the purity of the reactants
Phosphogypsum is a byproduct of producing phosphoric and process operations which affect purity of the gypsum
acid by treating phosphate rock with an acid. Often, the byproduct.
phosphate rock contains one or more radioactive elements 65 The process of the present invention employs a chemical
Such as uranium and thorium and these elements may be reaction of FGD gypsum with ammonium carbonate
present in the phosphogypsum. ((NH4)2CO) to produce ammonium sulfate ((NH4)2SO)
 US 9,682,868 B2
3 4
and calcium carbonate (CaCO). Both the ammonium Sul alkaline or acid-free papermaking for several decades. Pre
fate and calcium carbonate products are commercially valu cipitated calcium carbonate is especially useful compared to
able materials and are produced by the present process in ground calcium carbonate because of having a very fine and
high purity and high yield. controlled particle size, on the order of 2 micrometers in
Ammonium sulfate (21-0-0-24S) is used most commonly diameter, which is of particular utility in producing coatings
as a chemical fertilizer for alkaline soils. When applied to for paper.
damp soil, an ammonium ion is released which creates a The calcium carbonate produced by the process of the
small amount of acid, that lowers the pH balance of the soil. present invention has been characterized as having a high
In the soil, the ammonium ions are converted to nitrate by proportion of the Vaterite polymorph. Calcite, aragonite, and
soil bacteria which contributes nitrogen to the soil and aids 10 Vaterite are the three anhydrous polymorphs of calcium
in plant growth. Ammonium sulfate dissolves relatively carbonate, in order of decreasing stability. Among the poly
slowly (ammonium sulfate 74.4 g/100 mL at 20° C. (68° morph modifications of calcium carbonate, the metastable
F.), urea—107.9 g/100 mL at 20° C., ammonium nitrate— Vaterite is the most practically important. Vaterite particles
150 g/100 mL at 20°C.), which makes for more efficient use are applied in regenerative medicine, drug delivery and a
and thus reduces cost compared to some other artificial 15 broad range of personal care products. Vaterite-type calcium
fertilizers. For example, the relatively slow aqueous disso carbonate particles have unique properties Such as high
lution of ammonium sulfate affords a slow release fertilizer hydrophilicity, large Surface areas, and hierarchical struc
providing environmental benefits of less runoff of fertilizer tures consisting of primary Vaterite particles in comparison
unused by plants to streams and less leaching of fertilizer with calcite or aragonite-type polymorphs. Synthesized and
unused by plants to groundwater. natural calcium carbonates have been widely used as fillers,
Common nitrogen fertilizers include anhydrous ammonia pigments and other functional materials for paper, foods,
(82% N), urea (46% N), urea and ammonium nitrate solu cosmetics, medical materials and commodities produced at
tions (28-32% N), ammonium sulfate (21% N) and ammo industrial level. Of the three polymorphs of calcium carbon
nium nitrate (34% N). Ammonium sulfate (21%) is a nitro ate, Vaterite-type calcium carbonate particles are meta
gen source with little or no surface volatilization loss when 25 stable, and have secondary spheres consisting of primary
applied to most soils. It is easy to store and is not as particles approximately 100 nm in diameter. Thus, Vaterite
hygroscopic as ammonium nitrate. Ammonium Sulfate is a particles have large specific Surface areas with porous struc
good source of sulfur when it is needed to correct or prevent tures and are more hydrophilic than other two polymorphs.
a sulfur deficiency. In areas with high pH soils, the sulfur in These properties of Vaterite particles are significant as
ammonium sulfate helps lower soil pH levels. 30 coatings for high-grade ink-jet papers, because rapid absorp
In addition to use as fertilizer, ammonium Sulfate is used tion of extremely small and water-based ink droplets into the
as an agricultural spray adjuvant for water soluble insecti coated layer without spreading to the in-plane direction is
cides, herbicides and fungicides. In this capacity, it functions the most significant for photograde ink-jet printing.
to bind iron and calcium cations that are present in both well In the oil industry, calcium carbonate is added to drilling
water and plant cells. It is particularly effective as an 35 fluids as a formation-bridging and filter cake sealing agent
adjuvant for 2,4-D (amine), glyphosate, and glufosinate and can also be used as a weighting material to increase the
herbicides. density of drilling fluids to control the down-hole pressure.
Ammonium sulfate is used in flame retardant materials The process of the present invention further employs a
because it lowers the combustion temperature and increases chemical reaction of gypsum resulting from acid treatment
the production of residues or chars. 40 of phosphate rock with ammonium carbonate ((NH4)2CO)
In biochemistry, ammonium Sulfate precipitation is a to produce ammonium sulfate ((NH4)2SO4) and calcium
common method for purifying proteins by precipitation. As carbonate (CaCO). Both the ammonium sulfate and cal
Such, ammonium Sulfate is also listed as an ingredient in cium carbonate products are commercially valuable mate
many vaccines used in the United States. The DTap vaccine, rials and are produced by the present process in high purity,
which protects children from diphtheria, tetanus, and 45 depending upon the composition of the phosphate rock, and
whooping cough, uses ammonium sulfate for this purpose. high yield.
Fine calcium carbonate results as precipitated particles
from the process of the present invention and is useful in SUMMARY OF THE INVENTION
many industries.
High purity calcium carbonate is used as dietary calcium 50 While the present partially continuous countercurrent
Supplement to help ensure healthy bones and teeth. Calcium process can employ gypsum from any source without limi
carbonate Supplement is effective to treat certain medical tation, the examples used in the present application
disorders related to calcium deficiency such as osteoporosis employed FGD gypsum (CaSO 2H2O) from coal fired
and to reduce acid in the stomach and relieve indigestion and electric power plants and gypsum (CaSO4.2H2O) from acid
heartburn. For irritable bowel syndrome, a calcium carbon 55 treatment of phosphate rock Such as phosphogypsum, and
ate Supplement may be taken to reduce or relieve diarrhea. Successfully converted the gypsum to calcium carbonate
Calcium carbonate is used in the production of toothpaste (CaCOs) and ammonium Sulfate ((NH4)2SO) at conversion
and as an inert Substance in pharmaceutical or dietary rates of 100% and at least of 98 to 100% using the process
Supplement tablets. of the present invention. Such high conversion rates were
Fine calcium carbonate is the most preferred mineral in 60 achieved despite some of the employed gypsum crystalline
the paper industry, used for filling and coating paper. It helps particles having a physical structure that provided poor
in production of the best quality printing papers. Precipitated reactivity.
calcium carbonate is used as a filler in paper because it is The process of the present invention is characterized by a
cheaper than wood fiber wherein printing and writing paper unique combination of countercurrent flows coupled with
can contain 10-20% calcium carbonate. In North America, 65 reactors operated in a batch manner and thus partially
calcium carbonate has begun to replace kaolin in the pro continuous, with internal recycle of liquids to maximize the
duction of glossy paper. Europe has been practicing this as yield and purity of reaction products while minimizing the
 US 9,682,868 B2
5 6
reaction time. If the present process was a fully continuous Alternatively, the ammonium carbonate could be pro
process, then material would be constantly fed into and out duced directly, according to the above reaction, in process
of the reactors. Where mixing occurs in the reactors then the reactors while the gypsum conversion reaction is occurring
material does not enter and exit on a first-in-first-out basis. by using carbon dioxide removed from the flue gas or
For this reason, Some material may be last-in-first-out and directly using flue gas (containing carbon dioxide) and
exit the reactor before the contents completely react. With adding ammonia with it in the reactor.
respect to the reaction of gypsum and ammonium carbonate The process further enables control over the size, size
in a fully continuous process, then some ammonium car distribution, polymorphs, and Stability of polymorphs of
bonate would exit with the product ammonium sulfate and calcium carbonate product crystals by providing flexibility
Some gypsum would exit with the product calcium carbon 10
in control of reactions times, reaction temperatures, reaction
ate, and the desired conversion to calcium carbonate and pH, and reactant ratios in each reactor. The mixtures of
ammonium sulfate would not be achieved.
However, unlike a fully continuous countercurrent pro ammonium carbonate and ammonium bicarbonate also may
cess, the present process is a partially continuous counter be used efficiently for this process as shown in the examples
current process for converting gypsum by reaction with 15
below.
ammonium carbonate to ammonium sulfate and calcium FGD gypsum is produced at different power plants in the
carbonate. The partially continuous countercurrent process form of crystalline particles that have different physical
of the present invention overcomes the above noted ineffi characteristics. The present process achieves a high product
ciencies and problem of incomplete reactions by introducing yield even employing fairly unreactive FGD gypsum crys
the reactants into the reactor, mixing the reactants for a tals. Such gypsum crystals are thicker and have less Surface
predetermined amount of time and then removing materials area compared to the flatter, more disc like crystals produced
from the reactor and separating Solids from Solutions. No at other power plants.
reactants are added during the removal process and thus the Accordingly, the present process can accommodate the
reactants have sufficient time to react and ensure the desired less reactive FGD gypsum particles due to their large size
degree of reaction and product yield. 25 and thickness and decreased surface area, as well as FGD
While reference has been made to converting gypsum, the gypsum crystalline particles resulting from other FGD
dihydrate form of calcium sulfate (CaSO4.2H2O), the pro installations that produce particles having flatter, more disc
cess of the present invention also converts the hemihydrate like structure with greater reactive surface area. Testing of
and anhydrous forms of calcium Sulfate to the products, FGD gypsum and the resulting product purities indicate that
calcium carbonate and ammonium sulfate. 30 other forms of gypsum that are not FGD gypsum may easily
The process of the present invention employs FGD gyp be used in the process. This assertion is further validated by
sum or gypsum from acid treated phosphate rock, to com the tests described herein, employing gypsum originating
bine with ammonium carbonate ((NH)CO) or alterna from acid treatment of phosphate rock.
tively, ammonium bicarbonate (NHHCO) to undergo a The present partially continuous countercurrent process
chemical reaction to produce ammonium sulfate Solution 35 achieved a conversion efficiency to ammonium sulfate and
((NH4)2SO) and calcium carbonate (CaCO) by the fol calcium carbonate of 97 to approximately 100% and higher
lowing reaction: conversion yields were also obtained of 98% to approxi
mately 100%, 99% to approximately 100% and an achieved
yield of approximately 100% conversion by employing two
The process achieves a conversion efficiency to ammo 40 or more reactors in a multistage, partially continuous coun
nium sulfate and calcium carbonate of 100% and at least 97 tercurrent flow process.
to 100% by employing two or more reactors in a partially BRIEF DESCRIPTION OF THE DRAWINGS
continuous countercurrent flow process. The process of the
present invention obtains a high yield while maintaining low
reaction retention time, low excess use of reactants, mod 45 FIG. 1 shows a schematic of the two stage, two reactor
erate temperature and less mixing action. gypsum conversion, partially continuous countercurrent
The process of the present invention makes maximum use flow process of the invention.
of recycled materials such as the previously mentioned FGD FIG. 2 shows a schematic of the two stage, four reactor
gypsum and gypsum from acid treatment of phosphate rock. gypsum conversion, partially continuous countercurrent
Additionally, with respect to the above described production 50 flow process of the invention.
of carbon dioxide by scrubbing the flue gas which ultimately FIG. 3 shows Plant Gorgas FGD gypsum crystals, Scan
produces FGD gypsum, the ammonium carbonate used in ning Electron Microscope (SEM) Image at 500x.
the process of the present invention is preferably produced FIG. 4 shows Plant Miller FGD gypsum crystals, SEM
by removing the carbon dioxide created by the reaction of Image at 500x.
sulfur dioxide and calcium carbonate in the flue gas scrubber 55 FIG. 5 shows Plant Bowen FGD gypsum crystals, SEM
or from the burning of coal, and reacting the carbon dioxide Image at 100x.
with ammonia in a separate reactor and process to produce FIG. 6 shows Plant Crist FGD gypsum crystals, SEM
the ammonium carbonate according to the following reac Image at 100x.
tion: FIG. 7 shows Plant Wansley FGD gypsum crystals, SEM
60 Image at 100x.
FIGS. 8A and 8B together show a schematic of the two
Thus, a complete recycle of the scrubber carbon dioxide reaction stage gypsum conversion, partially continuous
can be achieved by employing it in the form of ammonium countercurrent flow process of the invention using three
carbonate to feed back into the process of the present reactors acting in parallel within each stage (six total reac
invention. This would help lead to compliance with air 65 tors).
quality regulations and possibly lead to less atmospheric FIGS. 9A, 9B and 9C together show a schematic of the
greenhouse effect. three or more reaction stage, gypsum conversion, partially
 US 9,682,868 B2
7 8
continuous countercurrent flow process of the invention countercurrent process, the present process is a partially
using two reactors acting in parallel within each stage (six or continuous countercurrent process for converting gypsum to
more total reactors). ammonium Sulfate and calcium carbonate. As shown in FIG.
FIGS. 10A, 10B and 10C together show a process 1, for example, reactants are fed to Reactor No. 1 or Reactor
sequencing diagram for the two stage, two reactor process No. 2; the feed is then shut off, and the reaction is allowed
shown in FIG. 1. to occur for a period of time after which the materials are
FIGS. 11A, 11B and 11C together show a process discharged. At the time that materials are drawn from the
sequencing diagram for the two stage, four reactor process reactor, there are no reactants added to the reactors. Further
shown in FIG. 2.
referring to FIG. 1, for example, product ammonium sulfate
FIGS. 12A, 12B and 12C together show a process 10
is not drawn off as a final product until the desired degree of
sequencing diagram for the two stage, six reactor process the reaction is complete and none is recycled back into the
shown in FIG. 8.
FIG. 13 shows magnification of product calcium carbon process, e.g. into Reactor No. 1. Also, as shown in FIG. 1,
ate crystals, SEM Image at 12,000x. the calcium carbonate slurry is not removed from the final
FIG. 14 shows results of product calcium carbonate 15 reactor until the desired degree of the reaction is complete
reactivity test. and ammonium sulfatefammonium carbonate solution is
FIG. 15 shows a schematic of the two stage, two reactor then removed from the final reactor to the preceding reactor
gypsum conversion, partially continuous countercurrent before it is again Supplied with unreacted ammonium car
flow process of the invention wherein ammonium carbonate bonate and the total solids of the preceding reactor consist
and ammonium bicarbonate Solution is produced directly in ing of a mixture of unreacted gypsum and calcium carbon
the reactors. ate. Thus total control is maintained over the reaction
FIG.16 shows a schematic of the three stage, three reactor completion of the final products until the desired complete
gypsum conversion, partially continuous countercurrent ness of the reaction is obtained. In most cases, the desired
flow process of the invention. degree of reaction completeness will be 100% from ammo
DETAILED DESCRIPTION OF THE
25 nium carbonate to ammonium Sulfate and 100% from gyp
Sum to calcium carbonate. It follows that the reactors are not
INVENTION required to be totally emptied to ensure the desired com
The processes of the present invention employ two or pleteness, as long as no reactants are being added while the
reactor is emptied.
more reactors in a partially continuous countercurrent flow 30
The filters remove solids and thus enable the solids to pass
process to convert gypsum to ammonium sulfate and cal through the process without recycle while liquid flows are
cium carbonate at a yield of 100%, 99 to 100% and 97 to controlled as countercurrent flows but with internal recycle
100%. The gypsum is converted according to the following
chemical reaction: within the system of a reactor, the filter for its discharge, and
35 the pump which handles the prime filtrate of the filter.
Circulation of liquids in embodiments of the present process
may be induced by gravity, or one or more pumps, or by a
The present inventive process includes five embodiments combination of gravity and pump(s), or even by other means
that are described in detail below. The first embodiment is a for inducing circulation of liquids. By this configuration, the
two stage reaction process that employs two reactors (e.g. 40 concentration of the liquid reactants can be controlled within
See FIG. 1), the second embodiment is a two stage reaction a reactor and the Solids concentration within a reactor can be
process that employs four or more reactors wherein there are controlled. By controlling the concentration of liquid reac
two or more parallel reactors in each stage (e.g. see FIG. 2), tants, the reactors can be run with major excesses of a
the third embodiment is a three stage reaction process that particular reactant within a reactor thereby greatly influenc
employs six or more reactors wherein there are two or more 45 ing both the reaction time and reaction completeness with
parallel reactors in each stage (e.g. see FIG. 9), the fourth regard to the low concentration of another reactant. This
embodiment is a three stage reaction process that employs means of operation also allows the Solids concentration
three reactors (see e.g. FIG. 16), and the fifth embodiment is within a reactor to be controlled, which is also important in
the first, second, third or fourth embodiments wherein obtaining complete reaction of the Solids in a minimum time.
ammonium carbonate is produced directly in the reactors 50
In all of the embodiments, filtration may be by various
rather than added from an outside source (see e.g. FIG. 15). means including gravity, pressure or vacuum filtration,
However, the present invention is not limited to a two or employing filtration media Such as glass fiber and porcelain
three stage process, nor limited to employing two, three, four sieve. Filters, especially Zoned filters, may be used including
or six reactors, but may include a multiplicity of stages, of belt filters, pan filters, drum filters and plate & frame filters.
two or more and include any number of reactors of two or 55
Alternative means of separating Solids from liquids such as
more, to facilitate process control and optimize product centrifugation may be employed. If desired, agglomerates of
purity and yield depending upon the characteristics of the
gypsum feed to be converted and desired characteristics of calcium carbonate product crystals that form during the
the product ammonium sulfate and calcium carbonate. process may be broken up by using a sonifier, homogenizer,
Features Shared by all Embodiments of the Invention 60 or other traditional means used for particle size reduction.
The process for conversion of gypsum to ammonium In embodiments of the present process that employ an
Sulfate and calcium carbonate by the reaction with ammo absorber tower to recycle the product calcium carbonate
nium carbonate is by a unique combination of countercur cake wash water, the types of towers include packed bed,
rent flows coupled with reactors operated in a batch manner and spray tower absorbers. When treating gypsum, the
and thus partially continuous, with internal recycle of liquids 65 calcium carbonate cake wash water will pass through the
to maximize the purity of reaction products while minimiz absorber along with ammonia and carbon dioxide from the
ing the reaction time. However, unlike a fully continuous power plant stack gases to produce ammonium carbonate.
 US 9,682,868 B2
10
The ammonium carbonate will be recycled back into the Solution Product (19). The combination Calcium Carbonate
process for use as a process reactant. and Gypsum Cake (10) which is formed in Filter No. 1 (9)
is fed to Reactor No. 2 (11). Ammonium Carbonate Solution
Embodiment Number 1 (12), ranging from 25 to 35% and preferably 33% at a
temperature ranging from 120° F. to 60° F. and preferably
Two Stage. Two Reactor Gypsum Conversion from 110° F. to 70° F., but most preferably from 100°F. to
Partially Continuous Countercurrent Process 80° F., is metered to Reactor No. 2 (11) and is agitated by a
Mixer (20). The temperature in Reactor No. 2 (11) is
A two reactor, two stage, countercurrent process is one maintained between 41° F to 176° F., preferably 60° F. to
embodiment of the present invention. A schematic of the 10 120° F., more preferably 70° F. to 110° F and most prefer
process is shown in FIG. 1. With reference to FIG. 1, an ably 80° F. to 100°F. The gypsum reacts quickly in Reactor
ammonium carbonate solution enters the process at Reactor No. 2 (11) since there is a stoichiometric excess of ammo
No. 2 (11) and the unreacted gypsum enters the process at nium carbonate present. Ammonia (21) in the form of
Reactor No. 1 (8). The ammonium carbonate solution may ammonium hydroxide solution or ammonia gas or liquid is
be obtained from an off-site source or if treating FGD 15 added to prevent foaming and to maintain a pH of 6.8 to 9.4
gypsum, the ammonium carbonate may be prepared from and preferably 7.6 to 9.0 within the Reactors. After a
electric power plant flue gas containing carbon dioxide from retention time of 4 to 60 minutes and preferably about 10
the reaction of the carbon dioxide with ammonia to produce minutes, effluent from Reactor No. 2 (11) is sent to Filter No.
the ammonium carbonate that is introduced to the process as 2 (15) to result in a Calcium Carbonate Product Cake (14).
described above. The Calcium Carbonate Product Cake (14) is then rinsed
This introduction of reactants ensures that previously, with Water Wash (13).
partially reacted gypsum is exposed to the greatest strength When process parameters are adjusted to produce the
ammonium carbonate Solution (as may be prepared by calcium carbonate product to be the polymorph of Vaterite,
absorption tower from the CO of the flue gas, if treating then the Water Wash (13) may be bypassed in favor of no
FGD gypsum) in the Reactor No. 2 (11) resulting in excess 25 water wash or the use of a wash with ammonium sulfate to
ammonium carbonate which enables 100% conversion to stabilize Vaterite formed in the process for long term storage.
calcium carbonate. Further, in Reactor No. 1 (8), the par The Wash Water Solution To Ammonium Carbonate
tially reacted Solution of ammonium carbonate is reacted Absorber Tower (17) now contains some ammonium car
with full strength gypsum resulting in 100% conversion of bonate and ammonium sulfate that is used when making
the ammonium carbonate to ammonium sulfate. Based upon 30 Ammonium Carbonate Solution (12) for use in the process.
laboratory and pilot plant test procedures as described, for All or a portion of the Wash Water Solution (17) from
instance, in the below disclosed Examples, FIG. 1 depicts a Filter No. 2, containing some ammonium carbonate and
two stage partially continuous countercurrent process of the ammonium sulfate, may be fed to Reactor No. 1.
present invention, employing two reactors as simulated by Note that additional process control is provided by having
bench scale laboratory tests and pilot plant tests having an 35 a liquid receiver hold portions of the Ammonium Sulfate/
approximate 100 pound per hour feed of ammonium car Ammonium Carbonate Solution as is shown in FIG. 1 and
bonate. notated as Receiver (16).
Thus, a two reactor, two stage embodiment of the present The following list of process steps summarizes the above
partially continuous countercurrent process is shown in FIG. described steps of the present two reactor, multistage par
1. The displayed process entails reacting gypsum (including 40 tially continuous countercurrent flow process shown in FIG.
FGD gypsum and gypsum from other sources) with ammo 1 (where filtration is employed, other usual solids-liquids
nium carbonate to form ammonium Sulfate and calcium separation operations may be used such as centrifugation):
carbonate. This is a unique, partially continuous countercur 1. Gypsum (including FGD gypsum and gypsum from
rent process with internal recycle of liquids to maximize the other sources, such as that produced from acid treat
yield and purity of product calcium carbonate and ammo 45 ment of phosphate rock) was mixed with water and
nium sulfate and minimize water usage. sulfuric acid to form an aqueous slurry of about 25 to
With further reference to FIG. 1, Gypsum Slurry (2) is a 30% gypsum, shown as Gypsum Slurry (2), and which
slurry of gypsum previously treated with sulfuric acid which was then filtered in Filter A (5) to remove possible
is poured over Filter A (5) resulting in a residual cake. The physical contaminants in the gypsum. Note that when
Gypsum Cake (6) is then rinsed with Wash Water (3) to 50 handling FGD gypsum, a gypsum slurry may be taken
remove contaminants and the Sulfuric acid. The Gypsum directly from the sulfur oxides (SO) scrubber.
Cake (6) is fed to Reactor No. 1 (8) where it is mixed with 2. The filtered Gypsum Cake (6) from Filter A (5) was
Ammonium Sulfate/Ammonium Carbonate Solution (18) washed with water. Thus, wash water containing
from Filter No. 2 (15) and its Receiver (16). A Mixer (7) is Soluble contaminants in the gypsum was the filtrate
used to agitate the contents of the Reactor No. 1 (8). The 55 from Filter A (5).
temperature in Reactor No. 1 (8) is maintained between 41 3. The filter cake from Filter A (5) was removed and
F. to 176° F., preferably 60° F to 120° F., more preferably charged to Reactor No. 1 (8).
70° F. to 110° F. and most preferably 80° F. to 100° F. The 4. The Ammonium Sulfate/Ammonium Carbonate Solu
Ammonium Carbonate reacts quickly in Reactor No. 1 (8) tion (18) stream from Receiver (16) was mixed with
since there is a stoichiometric excess quantity of gypsum 60 Gypsum Cake (6) from Filter A (5) within Reactor No.
present. Ammonia (21) in the form of ammonium hydroxide 1 (8) and Ammonia (21) was added as needed to
Solution or ammonia gas or liquid is added as needed to maintain a pH of 6.8 to 9.4 and preferably 7.6 to 9.0 and
prevent foaming and to maintain a pH of approximately 6.8 to prevent foaming. However, it may be necessary to
to 9.4 and preferably 7.6 to 9.0 within Reactor No 1 (8). neutralize the ammonia added for control of foaming
After a retention time of 4 to 60 minutes, and preferably 65 (whether aqua ammonia or anhydrous ammonia), and
about 10 minutes, effluent from Reactor No. 1 (8) is dis thus an acid such as Sulfuric acid, may need to be added
charged to Filter No. 1 (9). The filtrate is Ammonium Sulfate to the ammonium sulfate Solution product. Retention
 US 9,682,868 B2
11 12
times in reactors of 5, 10, 15, 20, 30, and 60 minutes and then the reactor is discharged over a 10 minute period.
provided 100% conversion. A retention time of 2 min Each block of each row of the sequencing diagram as shown
utes provides 90 to 100% conversion. Using a reactor in FIGS. 10A, 10B and 10C represents a 10 minute period
retention time of 20 minutes in each reactor at 25°C., of time where the time of the operation is elapsing from left
the Stoichiometric percent ratios of gypsum reacting in 5 to right and each block vertically represent the same 10
Reactor No. 1 (8) to Reactor No. 2 (11) of 20%:80%, minute period. Each row of the sequencing diagram repre
80%:20%, 30%:70%, and 70%:30% were tested and sents the times of the operations related to the reactors in
showed a 99-100% conversion of gypsum to calcium FIG. 1 where the first row represents the time of operations
carbonate. Reducing the retention time to less than 20 for Reactor No. 1 (8) and the second row represents the time
minutes in each reactor may produce an incomplete 10 of the operations for Reactor No. 2 (11). The shading of the
reaction if a less reactive gypsum is used. The tem sequencing diagram shows the periods of time in the process
perature in Reactors No. 2 (11) and No. 1 (8) is during which the filters shown in FIG. 1, which in this case
maintained between 41°F. to 176° F., preferably 60° F. are vacuum belt filters, are turned off as labeled by the
to 120° F., more preferably 70° F. to 110° F. and most legend at the top of the diagram. A block with no shading
preferably 80° F to 100° F. 15 indicates that all of the filters are active.
5. A mixing unit operation was employed in Reactor No. The numbers 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110,
1 (8). 120, 130, 140, and 150 within the blocks represent time in
6. The Ammonium Sulfate Solution Product (19) was minutes and the labels within the blocks, 1 charge, 1
collected from Filter No. 1 (9). reaction, 1 discharge, 2 charge, 2 reaction, and 2 discharge
7. Combination product Calcium Carbonate and Gypsum designate the reactor and operation occurring during that
Cake (10) from Filter No. 1 (9) was introduced to time interval. For example, the first block in the first row of
Reactor No. 2 (11) and Ammonia (21) was added as the sequencing diagram, FIGS. 10A, 10B, and 10C, is
needed to maintain a pH of 6.8 to 9.4 and preferably 7.6 labeled “1 charge indicating that Reactor No. 1 (8) of FIG.
to 9.0 and to prevent foaming. 1 is being charged with Gypsum Slurry (2) by Filter A (5)
8. In an optional embodiment of the two reactor process, 25 over a 10 minute period. Further, the second block of the first
a Mixer (20) may be employed in Reactor No. 2 (11). row is labeled "1 reaction' indicating that the materials are
9. Ammonium Carbonate Solution (12) ranging from 25% held within Reactor No. 1 (8) for a retention time of 10
to 35% and preferably about 33% ammonium carbon minutes. The third block represents the 10 minute period of
ate solution at a temperature of 60° F. to 120° F., time during which the slurry in Reactor No. 1 (8) is
preferably of 70° F to 110° F. and most preferably of 30 discharged to Filter No. 1 (9) forming the Calcium Carbon
80° F. to 100° F. was introduced to Reactor No. 2 (11) ate and Gypsum Cake (10). Row 2 of the sequencing
for a time of reaction and the slurry of reaction products diagram is similar to row 1 but shows the charge times,
introduced to Filter No. 2 (15). retention times, and discharge times for Reactor No. 2 (11)
10. Calcium carbonate filter cake formed in Filter No. 2 labeled as 2 charge, 2 reaction, and 2 discharge respectively.
(15) was washed with water (Water Wash (13)) to result 35 By comparing all of the time intervals during which each
in Calcium Carbonate Product Cake (14), and the filter is off for the 150 minutes of operation shown in this
resulting filtrate (Wash Water Solution To Ammonium sequencing diagram of this two stage, two reactor process,
Carbonate Tower (17)) now containing some ammo it is demonstrated that the gypsum slurry Filter A (5) was off
nium carbonate and ammonium sulfate was used when line 66.7% of the time, Filter No. 1 (9) was of 61.5% of the
making Ammonium Carbonate Solution (12) for use in 40 time and Filter No. 2 (15) was off 53.8% of the time. FIGS.
the process. However, the Water Wash (13) may be 11A, 11B and 11C show a process sequencing diagram for
bypassed in favor of no water wash or the use of a wash a two stage, four reactor process of the present invention as
with ammonium sulfate to stabilize waterite formed in shown in FIG. 2, which is discussed below regarding a
the process for long term storage. second embodiment of the present invention. The rows,
11. Ammonium Sulfate Solution Product (19), which is 45 labels, and legend of FIGS. 11A, 11B, and 11C are similar
the filtrate from Filter 1 (9), is stored and used as to FIG. 10 as described above. The difference is that the
produced or it can be concentrated to a more concen parallel reactors in the first stage of FIG. 2, Reactor No. 1
trated solution or sent to a crystallizer. If stored, this (36) and Reactor No. 2 (40), are denoted on the sequencing
solution is optimally heated to 110°F. to 115°F. to keep diagram by 1a and 1b respectively and the sequencing
crystallization from occurring. If a solid ammonium 50 diagram labels 2a and 2b denote Reactor No. 3 (41) and
sulfate product is desired then a crystallizer or alterna Reactor No. 4 (42) respectively of FIG. 2. During 180
tively, an evaporator, or granulator is employed in the minutes of operation shown in FIGS. 11A, 11B, and 11C of
process of the present invention to grow ammonium this two stage, four reactor process, the gypsum slurry Filter
Sulfate crystals for separation and removal as an easier No. 1 (32) of FIG. 2 was off line 33.3% of the time, Filter
to handle, more solid product. 55 No. 2 (37) was offline 33.3% of the time, and Filter No. 3
The calcium carbonate product is shown to principally be (43) was off line 26.7% of the time. FIGS. 12A, 12B, and
very small waterite spherulites between 1L and 8L in 12C show a process sequencing diagram for a two stage, six
diameter, and by weight, 95% of the spherulite diam reactor process of the present invention as shown in FIGS.
eters were between 2L and 5L. 8A and 8B which is discussed below regarding the second
Reactor Sequencing for Exemplified Two Stage Process 60 embodiment of the present invention. This sequencing dia
Embodiments gram is again like the sequencing diagrams of FIG. 10 and
FIGS. 10A, 10B and 10C together show a process FIG. 11 described above except 1a, 1b, and 1c shown in
sequencing diagram for a two stage, two reactor process of FIGS. 12A, 12B, and 12C denote Reactor No. 1 (36),
the present invention as shown in FIG. 1. This sequencing Reactor No. 2 (40), and Reactor No. 5 (51) respectively of
diagram is for a two stage, two reactor process where the 65 FIG. 8 and the 2a, 2b, and 2c of the FIG. 12 sequencing
feed to each reactor is charged over a 10 minute period, after diagram denote Reactor No. 3 (41), Reactor No. 4 (45), and
which the materials are mixed in the reactor for 10 minutes, Reactor No. 6 (52) respectively of FIG.8. At no time during
 US 9,682,868 B2
13 14
the times shown in the sequencing diagram for this two Reactor 1 (36) or Reactor 2 (40) is fed to Filter 2 (37) where
stage, six reactor process are any of the vacuum filter belts the filtrate as Ammonium Sulfate Solution Product (46) is
off line. collected as product and the filter cake consisting of Calcium
The above discussed sequencing diagrams demonstrate Carbonate and Gypsum Cake (38) is fed to either Reactor
the efficiency benefits of running parallel reactors in each 5 No. 3 (41) or Reactor No. 4 (45), which previously has been
stage of the present process. charged or is being charged with Ammonium Carbonate
Embodiment Number 2
Solution (50) and is under mixing by the appropriate Mixer
(42 or 44). When charging is complete the reaction continues
Two Stage. Four Reactor Gypsum Conversion 10
for the time required to complete the reaction and Ammonia
Partially Continuous Countercurrent Process (58) is added to Reactor 1 (36) and Reactor 2 (40) as needed
to prevent foaming by controlling pH between 6.8 and 9.4
A second embodiment of the present invention is a two and preferably between pH 7.6 and 9.0.
stage, partially continuous countercurrent process, similar to When the reaction is complete and either Reactor 3 (41)
the two stage, two reactor embodiment, but containing four 15 or Reactor 4 (45) is empty or emptied to a desired level, the
reactors wherein two reactors are in parallel for each stage slurry formed in Reactor No. 3 (41) or Reactor No. 4 (45)
(see FIG. 2 for process schematic). An expansion of this can be fed to Filter 3 (43), Zone A to form the Ammonium
embodiment, discussed further below, is a two stage process Sulfate/Ammonium Carbonate Solution (49) to be sent to
having more than two reactors operating in parallel within the empty reactor. The filter cake has a Water Wash (46) to
each stage, such as the six reactors shown in FIGS. 8A and remove any solution of Ammonium Sulfate/Ammonium
8B. Carbonate Solution left in the filter cake so the solutions
The additional two reactors are added to ensure extremely washed from the cake can be recycled to the process by
high purity and high yield products when using gypsums using the solution to furnish Wash Water Solution To the
which contain large crystals having less Surface area or with Ammonium Carbonate Absorber Tower (48). However, the
impurities, making them less reactive. 25 Water Wash (46) may be bypassed in favor of no water wash
Further, the four reactor process provides benefits for or the use of a wash with ammonium sulfate to stabilize
commercial operation wherein good belt filter operation is Vaterite formed in the process for long term storage.
maintained. The process has two sets of reactors, but only For a smooth running process the filters are normally
one set of filters so that the filters are always filled with filled with cake. Gypsum Filter Cake (34) from Filter 1 (32)
filtration residual cake. When the filters are fed continually, 30
feeds either Reactor No. 1 (36) or Reactor No. 2 (40) as does
good filtration vacuum is maintained leading to good filtra the Ammonium Sulfate/Ammonium Carbonate Solution
tion and good washing of the filtration cakes. (49) which is fed to the same reactor. The filter cake from
In comparing the four reactor process with the two reactor
process shown in FIG. 1, the process in FIG. 1 shows two Filter 2 (37) feeds Reactor No. 3 (41) or Reactor No. 4 (45),
reactors in series and a Receiver (16) to hold Ammonium 35 with fresh Ammonium Carbonate Solution (50) feeding the
Sulfate/Ammonium Carbonate Solution (18). Embodiments same reactor. Filter No. 3 (43) discharges Calcium Carbon
of the present process shown in FIG. 2 include a four-reactor ate Product Cake (47). Additional process control is pro
process operating like two reactors in series without the use vided by having a liquid receiver to hold portions of the
of a Receiver. Additional reactors and/or receivers can be Ammonium Sulfate/Ammonium Carbonate Solution as is
added (if desired) for Smooth semi-continuous operation. 40 shown in FIG. 1 and notated as Receiver (16).
For example, in FIG. 2, a receiver can be added to hold the Expanded Embodiment Number 2 Having Multiplicity of
Ammonium Sulfate/Ammonium Carbonate Solution (49). Reactors
With reference to FIG. 2, Filter 1 (32) is used to filter As noted above, an expansion of the second embodiment
incoming Gypsum Slurry (30) made up of gypsum and water of the present invention, is a two stage process having more
which contains 1 to 5% sulfuric acid which has been added 45 than two reactors operating in parallel within each stage,
to dissolve impurities in the FGD gypsum. The belt filters such as the six reactors shown in FIGS. 8A and 8B. In this
employed in the FIG. 2 process contain a Zone A and a Zone case, there may be any number of reactors of two or more,
B. In Filter 1 (32) (Zone A) the gypsum is filtered leaving a to facilitate process control and optimize product purity and
residual cake which in Zone B has Wash Water (31) passed yield depending upon the characteristics of the gypsum feed
through it leaving a solution To Clean Up and Recycle (33). 50 to be converted and desired characteristics of the product
The Gypsum Filter Cake (34) is then fed into either Reactor ammonium Sulfate and calcium carbonate. Further, the use
No. 1 (36) or Reactor No. 2 (40) which has previously been of additional reactor sets of two improves the efficiency of
charged or is being charged with Ammonium Sulfate/Am the process by reducing or eliminating idle time for vacuum
monium Carbonate Solution (49) as discharged from Filter belt filters. The additional reactor sets also allow for more
3 (43) Zone A and coming from either Reactor No. 3 (41) or 55 flexibility of control of particle size by allowing adjustment
Reactor No. 4 (45). When Reactor No. 1 (36) or Reactor No. of retention times, temperatures, pH, and reactant ratios.
2 (40) is receiving Ammonium Sulfate/Ammonium Carbon The three reactors in each stage improve process effi
ate Solution (49) and is under mixing action from either ciency by eliminating vacuum belt idle time as seen by
Mixer (35) or Mixer (39), the Gypsum Filter Cake (34) can comparing FIGS. 10-12. This is particularly shown by FIG.
be introduced. After being filled with Gypsum Filter Cake 60 12 wherein FIGS. 12A, 12B, and 12C show a process
(34) and Ammonium Sulfate/Ammonium Carbonate Solu sequencing diagram for a two stage six reactor process for
tion (49) to the appropriate Stoichiometric proportions, mix the process shown in FIGS. 8A and 8B. At no time during
ing continues while the reaction is proceeding for the the process are any of the vacuum filter belts off line but
required time for desired completion of reaction and Ammo rather are running at capacity all the time. The sequencing
nia (58) is added as needed to prevent foaming by control 65 diagrams of FIGS. 10-12 show the efficiency benefits of
ling pH between 6.8 and 9.4 and preferably between pH 7.6 running parallel reactors in each stage of the process. The
and 9.0. After the reaction is complete, the contents of the additional reactors also allow for flexibility in residence time
 US 9,682,868 B2
15 16
in the reactors, providing control over particle size and shape a liquid receiver to hold portions of the Ammonium Sulfate/
and to ensure complete conversion of large, less reactive Ammonium Carbonate Solution as is shown in FIG. 1 and
gypsum. labeled as Receiver (16).
In FIG. 8, Filter 1 (32) is used to filter incoming Gypsum
Slurry (30) made up of gypsum and water which contains 1 5 Embodiment Number 3
to 5% sulfuric acid which has been added to dissolve
impurities in the FGD gypsum. The Filter No. 1 and Filter Three or More Stages, Six or More
No. 2 employed in the process are Zoned, containing a Zone Reactors—Gypsum Conversion Partially
Continuous Countercurrent Process
A and a Zone B. In Filter 1 (32) Zone A, the gypsum is 10
filtered leaving a residual cake which in Zone B has Wash A third embodiment of the present invention is a partially
Water (31) passed through it leaving a solution To Clean Up continuous countercurrent process, that includes a multiplic
and Recycle (33). The Gypsum Filter Cake (34) is then fed ity of stages, of two or more and includes any number of
into either Reactor No. 1 (36), Reactor No. 2 (40), or Reactor reactors of two or more, with the number of stages and
No. 5 (51) which has previously been charged or is being 15 reactors selected to facilitate process control and optimize
charged with Ammonium Sulfate/Ammonium Carbonate product purity and yield depending upon the characteristics
Solution (49) as discharged from Filter 3 (43) Zone A and of the gypsum feed to be converted and desired character
coming from either Reactor No. 3 (41), Reactor No. 4 (45), istics of the product ammonium sulfate and calcium carbon
or Reactor No. 6 (52). When Reactor No. 1 (36), Reactor No. ate (see FIGS. 9A, 9B and 9C for process schematic).
2 (40), or Reactor No. 5 (51) is receiving Ammonium The size and/or polymorphs of product calcium carbonate
Sulfate/Ammonium Carbonate Solution (49) and is under can be controlled by the performing the process of the
mixing action from either Mixer (35), Mixer (39), or Mixer present invention in more than two stages. The stability of
(53) the Gypsum Filter Cake (34) can be introduced. After the calcium carbonate polymorphs waterite and aragonite is
being filled with Gypsum Filter Cake (34) and Ammonium low, particularly the stability of Vaterite. Thus, the schematic
Sulfate/Ammonium Carbonate Solution (49) to the appro 25 of FIGS. 9A, 9B and 9C may optionally include the direct
priate Stoichiometric proportions, mixing continues while use of ammonium sulfate or recirculation of ammonium
the reaction is proceeding for the required time. Ammonia is Sulfate to keep and or delay the product calcium carbonate
added to Reactor No. 1 (36), Reactor No. 2 (40), and Reactor polymorphs such as Vaterite from changing to a more stable
No. 5 (51) as needed to prevent foaming by controlling the calcium carbonate polymorph Such as calcite. The schematic
pH to be between 6.8 and 9.4 and preferably between pH 7.6 30 of FIG.9A-C shows a process embodiment containing three
and 9.0. After the reaction is complete, the contents of the stages using three sets of two parallel reactors. While FIG.
Reactor No. 1 (36), Reactor No. 2 (40), or Reactor No. 5 (51) 9A-C shows a process comprising at least six reactors, more
is fed to Filter 2 (37) to maintain a continuous filtration reactors can be used such as the three reactors for each stage
where the filtrate as Ammonium Sulfate Solution Product shown in FIGS. 8A and 8B. More than three stages, includ
(46) is collected as product and the filter cake consisting of 35 ing a multiplicity of stages, can be employed greater than
Calcium Carbonate and Gypsum Cake (38) is fed to either three stages shown in FIGS. 9A, 9B and 9C as indicated by
Reactor No. 3 (41), Reactor No. 4 (45), or Reactor No. 6 (52) the exponent “n” bracketing two parallel reactors, Reactor
which previously has been charged or is being charged with No. 5 (51) and Reactor No. 6 (52) and their Filter 4 (53) and
Ammonium Carbonate Solution (50), and is under mixing Mixers (54 and 55).
by the appropriate Mixer (42, 44, or 54). When charging is 40 In FIG. 9, Filter 1 (32) is used to filter incoming Gypsum
complete the reaction continues for the appropriate time to Slurry (30) made up of gypsum and water which contains 1
finish the reaction and Ammonia (58) is added to Reactor to 5% sulfuric acid which has been added to dissolve
No. 3 (41), Reactor No. 4 (45), and Reactor No. 6 (52) as impurities in the FGD gypsum. The belt filters employed in
needed to prevent foaming by controlling the pH to be the process contain a Zone A and a Zone B. In Filter 1 (32)
between 6.8 and 9.4 and preferably between pH 7.6 and 9.0. 45 Zone A, the gypsum is filtered leaving a residual cake which
When the reaction is complete and either Reactor No. 1 in Zone B has Wash Water (31) passed through it leaving a
(36), Reactor No. 2 (40), or Reactor No. 5 (51) is empty, the solution To Clean Up and Recycle (33). The Gypsum Filter
slurry formed in Reactor No. 3 (41), Reactor No. 4 (45), or Cake (34) is then fed into either Reactor No. 1 (36) or
Reactor No. 6 (52) can be fed to Filter 3 (43) Zone A to Reactor No. 2 (40) which has previously been charged or is
maintain a continuous filtration to form the Ammonium 50 being charged with Ammonium Sulfate/Ammonium Car
Sulfate/Ammonium Carbonate Solution (49) to be sent to bonate Solution (57) as discharged from Filter 4 (53) and
the empty reactor. The filter cake has a Water Wash (46) to coming from either Reactor No. 5 (51) or Reactor No. 6 (52).
remove any solution of Ammonium Sulfate/Ammonium When Reactor No. 1 (36) or Reactor No. 2 (40) is receiving
Carbonate Solution (49) left in the filter cake so the solutions Ammonium Sulfate/Ammonium Carbonate Solution (57)
washed from the cake can be recycled to the process by 55 and is under mixing action from either Mixer (35) or Mixer
using the solution to furnish Wash Water Solution To the (39), the Gypsum Filter Cake (34) can be introduced. After
Ammonium Carbonate Absorber Tower (48). being filled with Gypsum Filter Cake (34) and Ammonium
For a smooth running process the filters are always filled Sulfate/Ammonium Carbonate Solution (57) to the appro
with cake. Gypsum Filter Cake (34) from Filter 1 (32) feeds priate Stoichiometric proportions, mixing continues while
either Reactor No. 1 (36), Reactor No. 2 (40), or Reactor No. 60 the reaction is proceeding for the required time and Ammo
5 (51) as does the Ammonium Sulfate/Ammonium Carbon nia (58) is added to Reactor No. 1 (36) and Reactor No. 2
ate Solution (49) which is fed to the same reactor. The filter (40) as needed to prevent foaming by controlling the pH to
cake from Filter 2 (37) feeds Reactor No. 3 (41), Reactor No. be between 6.8 and 9.4 and preferably between 7.6 and 9.0.
4 (45), or Reactor No. 6 (52), with fresh Ammonium However, it may be necessary to neutralize the ammonia by
Carbonate Solution (50) feeding the same reactor. Filter No. 65 adding an acid, such as Sulfuric acid. After the reaction is
3 (43) discharges Calcium Carbonate Product Cake (47). over, the contents of the Reactor 1 (36) or Reactor 2 (40) is
Additional process control, if desired, is provided by having fed to Filter 2 (37) where the filtrate as Ammonium Sulfate
 US 9,682,868 B2
17 18
Solution Product (46) is collected as product and the filter charges Calcium Carbonate Product Cake (47). Additional
cake consisting of Calcium Carbonate and Gypsum Cake process control is provided by having a liquid receiver to
(38) is fed to either Reactor No. 5 (51) or Reactor No. 6 (52), hold portions of the Ammonium Sulfate/Ammonium Car
which previously has been charged or is being charged with bonate Solution as is shown in FIG. 1 and labeled as
Ammonium Sulfate/Ammonium Carbonate Solution (49) Receiver (16).
and is under mixing by the appropriate Mixer (54 or 55).
When charging is complete the reaction continues for the Embodiment Number 4
appropriate time to the desired partial completion and mix
ing continues while the reaction is proceeding for the Three Stage, Three Reactor Gypsum Conversion
required time. Ammonia (58) is added to Reactor No. 1 (36), 10 Partially Continuous Countercurrent Process
Reactor No. 2 (40), Reactor No. 5 (51) and Reactor No. 6
(52) as needed to prevent foaming by controlling the pH to A three reactor, three stage, countercurrent process is an
be between 6.8 and 9.4 and preferably between 7.6 and 9.0. embodiment of the present invention. A schematic of the
When the reaction reaches the desired completion for this process is shown in FIG. 16. With reference to FIG. 16, an
stage and either Reactor No. 1 (36) or Reactor No. 2 (40) is 15 ammonium carbonate Solution (such as that, for example,
empty, the slurry formed in Reactor No. 5 (51) or Reactor prepared from ammonia and the carbon dioxide in electric
No. 6 (52) can be fed to Filter 4 (53) to form the Ammonium power plant flue gas) enters the process at Reactor No. 3 (22)
Sulfate/Ammonium Carbonate Solution (57) to be sent to and the unreacted gypsum enters the process at Reactor No.
the empty reactor. The Calcium Carbonate and Gypsum 1 (8). This introduction of reactants ensures that previously,
Cake (56) which is discharged from Filter 4 (53) is fed to partially reacted gypsum is exposed to the greatest strength
either Reactor No. 3 (41) or Reactor No. 4 (45) which ammonium carbonate solution (as prepared, for example, by
previously has been charged or is being charged with absorption tower from the CO of the flue gas) in the Reactor
Ammonium Carbonate Solution (50) and is under mixing by No. 3 (22) resulting in excess ammonium carbonate which
the appropriate Mixer (42) or (44). When charging is com enables 100% conversion to calcium carbonate. Further, in
plete the reaction continues for the appropriate time to 25 Reactor No. 1, the partially reacted solution of ammonium
complete the reactions and Ammonia (58) is added to the carbonate is reacted with full strength gypsum resulting in
Reactors No. 1 (36), No. 2 (40), No. 5 (51), No. 6 (52), No. 100% conversion of the ammonium carbonate to ammonium
3 (41), and/or No. 4 (45) as needed to prevent foaming by sulfate. Based upon laboratory procedures as described, for
controlling pH to be between 6.8 and 9.4 and preferably instance, in the below disclosed Examples, FIG. 16 depicts
between pH 7.6 and 9.0. It may be necessary to neutralize 30 a three stage partially continuous countercurrent process of
the ammonia by adding an acid, such as Sulfuric acid. the present invention, employing three reactors as simulated
When the reaction is complete and either Reactor No. 5 by bench scale laboratory tests.
(51) or Reactor No. 6 (52) is empty, the slurry formed in With reference to FIG. 16, Gypsum Slurry (2) is a slurry
Reactor No. 3 (41) or Reactor No. 4 (45) can be fed to Filter of gypsum previously treated with Sulfuric acid which is
3 (43) Zone A to form the Ammonium Sulfate/Ammonium 35 poured over Filter A (5) resulting in a residual cake. The
Carbonate Solution (49) to be sent to the empty Reactor No. Gypsum Cake (6) is then rinsed with Wash Water (3) to
5 (51) or Reactor No. 6 (52). remove contaminants and the Sulfuric acid. The Gypsum
Should the process be such that the number of interme Cake (6) is fed to Reactor No. 1 (8) where it is mixed with
diate pairs of parallel reactors (such as Reactors No. 5 (51) Ammonium Sulfate/Ammonium Carbonate Solution (18)
and No. 6 (52)) be greater than when “n” equals one, then 40 from Filter No. 2 (15) and its Receiver (16). A Mixer (7) is
their operation will entail that the filter, such as Filter 4 (53), used to agitate the contents of the Reactor No. 1 (8). The
feeds the Solid calcium carbonate and gypsum cake forward temperature in Reactor No. 1 (8) is maintained between 41
to the next pair of reactors, to further react the cake towards F. to 176° F., preferably 60° F to 120° F., more preferably
formation of calcium carbonate. The Ammonium Sulfatef 70° F to 110° F. and most preferably 80° F to 100° F. The
Ammonium Carbonate Solution will feed in the opposite 45 Ammonium Carbonate reacts quickly in Reactor No. 1 (8)
direction to the next pair of reactors toward formation of since there is a stoichiometric excess quantity of gypsum
ammonium sulfate. present. Ammonia (21) in the form of ammonium hydroxide
The filter cake has a Water Wash (46) to remove any Solution or ammonia gas or liquid is added as needed to
solution of Ammonium Sulfate/Ammonium Carbonate prevent foaming within Reactor No 1 (8). After a retention
Solution left in the filter cake so the solutions washed from 50 time of 4 to 60 minutes and preferably about 10 minutes,
the cake can be recycled to the process by using the Solution effluent from Reactor No. 1 (8) is discharged to Filter No. 1
to furnish Wash Water Solution To the Ammonium Carbon (9). The filtrate is Ammonium Sulfate Solution Product (19).
ate Absorber Tower (48). However, the Water Wash (46) However, to neutralize the ammonia, it may be necessary to
may be bypassed in favor of no water wash or the use of a add an acid, Such as Sulfuric acid. The combination Calcium
wash with ammonium sulfate to stabilize waterite formed in 55 Carbonate and Gypsum Cake (10) which is formed in Filter
the process for long term storage. No. 1 (9) is fed to Reactor No. 2 (11) where it is mixed with
For a smooth running process the filters are filled with Ammonium Sulfate/Ammonium Carbonate Solution (27)
cake, preferably to capacity. Gypsum Filter Cake (34) from from Filter No. 3 (25) and its Receiver (26). Ammonia (21)
Filter 1 (32) feeds either Reactor No. 1 (36) or Reactor No. is added to Reactor No. 1 (8), Reactor No. 2 (11), and
2 (40) as does the Ammonium Sulfate/Ammonium Carbon 60 Reactor No. 3 (51) as needed to prevent foaming by con
ate Solution (57) which is fed to the same reactor. The filter trolling the pH to be between 6.8 and 9.4 and preferably
cake from Filter 2 (37) feeds Reactor No. 5 (51) or Reactor between 7.6 and 9.0. A Mixer (20) is used to agitate the
No. 6 (52), with fresh Ammonium Sulfate/Ammonium Car contents of the Reactor No. 2 (11). The temperature in
bonate Solution (49) feeding the same reactor. The filter Reactor No. 2 (11) is maintained between 41° F to 176° F.,
cake from Filter No. 4 (53) feeds Reactor No. 3 (41) or 65 preferably 60° F. to 120° F., more preferably 70° F. to 110°
Reactor No. 4 (45) with fresh Ammonium Carbonate Solu F. and most preferably 80° F to 100°F. Ammonia (21) in the
tion (50) feeding the same reactor. Filter No. 3 (43) dis form of ammonium hydroxide solution or ammonia gas or
 US 9,682,868 B2
19 20
liquid is added as needed to prevent foaming within Reactor numbers on FIG. 15 are the same as on FIG. 1 except for the
No 2 (11). After a retention time of 4 to 60 minutes and modifications needed for the present embodiment of pro
preferably about 10 minutes, effluent from Reactor No. 2 ducing ammonium carbonate inside the process reactors.
(11) is discharged to Filter No. 2 (15) and its Receiver (16). Please refer to the previous description of FIG. 1 for an
The combination Calcium Carbonate and Gypsum Cake (24) explanation of each reference number that is common to
which is formed in Filter No. 2 (15) is fed to Reactor No. 3 both FIG. 1 and FIG. 15. Different in FIG. 15, is Ammonia
(22). Ammonium Carbonate Solution (12), ranging from 25 (21) being fed to both Reactor No. 1 (8) and Reactor No. 2
to 35% and preferably 33% at a temperature ranging from (11). Carbon Dioxide (12) is also fed to both Reactor No. 1
120° F to 60° F. and preferably from 110° F. to 70° F., but (8) and Reactor No. 2 (11), where ammonia and carbon
most preferably from 100°F. to 80° F., is metered to Reactor 10
dioxide react to produce ammonium carbonate, an initial
No. 3 (22) and is agitated by a Mixer (23). The temperature reactant in the present process. The Vent To Scrubber (22)
in Reactor No. 3 (22) is maintained between 41° F to 176° provides for removing excess Ammonia and Carbon Diox
F., preferably 60° F. to 120° F., more preferably 70° F. to ide. The Rinse Water (17) of the process is recycled to
110° F. and most preferably 80° F. to 100° F. The gypsum Reactor No. 2 (11) and may be supplemented with additional
reacts quickly in Reactor No. 3 (22) since there is a 15
water if needed for adequate reaction.
Stoichiometric excess of ammonium carbonate present. The operation of this embodiment and testing are
Ammonia (21) in the form of ammonium hydroxide Solution
or ammonia gas or liquid is added to prevent foaming within described in the below Examples as well as for the afore
the Reactors. After a retention time of 4 to 60 minutes and mentioned embodiments of the present invention, which
preferably about 10 minutes, effluent from Reactor No. 3 demonstrate that the production of ammonium carbonate
(22) is sent to Filter No. 3 (25) to result in a Calcium was successful and there was 100% conversion of gypsum
Carbonate Cake. The Calcium Carbonate Cake is then rinsed to calcium carbonate and ammonium sulfate. Direct addition
with Water Wash (13) producing a Calcium Carbonate of ammonia and carbon dioxide to the reactors avoids some
Product Cake (14). However, the Water Wash (13) may be of the water that dilutes the ammonium sulfate product.
bypassed in favor of no water wash or the use of a wash with 25 Non-Limiting Summary of Embodiments
ammonium sulfate to stabilize waterite formed in the process 1. A partially continuous countercurrent flow process for
for long term storage. The Wash Water Solution To Ammo converting gypsum to ammonium sulfate and calcium
nium Carbonate Absorber Tower (17) now contains some carbonate comprising the following steps:
ammonium carbonate and ammonium sulfate that is used separating an aqueous slurry of gypsum to result in a
when making Ammonium Carbonate Solution (12) for use in 30
gypsum liquid residue and a gypsum cake;
the process. Note that additional process control is provided feeding a flow of reactants being the gypsum cake and a
by having a liquid receiver hold portions of the Ammonium Solution of ammonium sulfate and ammonium carbon
Sulfate/Ammonium Carbonate Solutions as is shown in FIG.
ate into a first reactor for chemical reaction;
16 and notated as Receivers (16 & 26). stopping the flow of reactants into the first reactor for a
35
Embodiment Number 5 retention time selected to achieve a preselected degree
of chemical reaction to form an ammonium sulfate
Multi-Stage, Multi-Reactor Gypsum Conversion Solution containing a first precipitate calcium carbonate
Partially Continuous Countercurrent Process with and a gypsum remnant;
Ammonium Carbonate-Ammonium Bicarbonate 40 discharging the ammonium sulfate Solution containing a
Solution Produced in Reactors first precipitate calcium carbonate and a gypsum rem
nant,
All embodiments of the present invention employ the resuming the flow of reactants into the first reactor;
partially continuous countercurrent flow process of the separating the first precipitate calcium carbonate and
invention whereby gypsum is reacted with ammonium car 45 gypsum remnant from the ammonium Sulfate Solution
bonate to produce calcium carbonate and ammonium Sul to result in a product ammonium sulfate solution and a
fate. The previously described embodiments of the present remnant cake of first precipitate calcium carbonate and
invention use the reactant, ammonium carbonate, which has gypsum,
been produced outside of the reactors of the present process. retaining the product ammonium Sulfate Solution;
One method of producing ammonium carbonate is to react 50 feeding a flow of reactants being the remnant cake of first
carbon dioxide with ammonia. If FGD gypsum is being precipitate calcium carbonate and gypsum and ammo
treated as the process starting material then the ammonium nium carbonate solution into a second reactor for
carbonate may be conveniently, environmentally and eco chemical reaction;
nomically produced by reacting electric power plant flue gas stopping the flow of reactants into the second reactor for
(containing carbon dioxide) directly with ammonia or react 55 a retention time selected to achieve a predetermined
ing the carbon dioxide removed from flue gas with ammo degree of chemical reaction to form a second precipi
nia. tate calcium carbonate and a solution of ammonium
The present embodiment of the present invention employs Sulfate and ammonium carbonate;
the process of the invention wherein ammonium carbonate discharging the first and second precipitate calcium car
is produced inside the reactors of the process. Thus, this 60 bonate and a solution of ammonium Sulfate and ammo
embodiment encompasses the present multi stage, multi nium carbonate;
reactor, partially continuous countercurrent flow processes. resuming the flow of reactants into the second reactor,
A schematic of the present embodiment is shown in FIG. separating the first and second precipitate calcium car
15, which is a modified version of the two stage, two reactor bonate from the solution of ammonium Sulfate and
process of the first embodiment shown in FIG. 1. A two 65 ammonium carbonate to result in a product calcium
stage, two reactor embodiment was selected to illustrate the carbonate cake and a residue solution of ammonium
present fifth embodiment due to its simplicity. The reference Sulfate and ammonium carbonate;
 US 9,682,868 B2
21 22
retaining the product calcium carbonate cake; and 10. The process of 1), wherein the process is conducted at
adding the residue solution of ammonium sulfate and temperatures of 41 to 176° F.
ammonium carbonate to the first reactor. 11. The process of 1), further including mixing within the
. The process of 1), wherein the step of separating the first reactor and the second reactor by a mixer selected
aqueous slurry of gypsum to result in first and second 5 from the group consisting of impeller mixer, paddle
gypsum liquid residues and a gypsum cake is accom mixer, ultrasonic mixer and homogenizer.
plished by steps comprising: 12. The process of 1), wherein the separating steps are
filtering an aqueous slurry of gypsum on a filter having accomplished by a device selected from the group con
two Zones, Zone A and Zone B, wherein Zone A the 10
sisting of belt filter, pan filter, drum filter and centrifuge.
gypsum slurry is filtered resulting in a first gypsum 13. The process of 1), wherein contaminants are removed
liquid residue and a residual gypsum cake; and from the gypsum by an acid rinse process comprising the
transporting the residual gypsum cake on the filter to Zone steps of
B in which the residual gypsum cake is washed with separating the aqueous slurry of gypsum to result in a
water to result in a second gypsum liquid residue. 15 gypsum liquid residue and a gypsum cake;
. The process of 1), wherein the step of separating the first rinsing the gypsum cake with an aqueous solution con
and second precipitate calcium carbonate from the solu taining sulfuric acid from 0.01 to 10% concentration to
tion of ammonium Sulfate and ammonium carbonate is result in a purified gypsum cake; and
accomplished by steps comprising: rinsing the purified gypsum cake with water to remove
filtering the first and second precipitate calcium carbonate residual Sulfuric acid solution to result in a final puri
from the solution of ammonium sulfate and ammonium fied gypsum cake.
carbonate on a filter having two Zones, Zone A and Zone 14. The process of 13), wherein the gypsum is a phospho
B, wherein Zone A the solution of ammonium sulfate gypsum and a contaminant is uranium wherein uranium is
and ammonium carbonate is filtered resulting in a removed from the gypsum cake to result in a 40 to 75%
calcium carbonate cake and a residue solution of 25 reduction of uranium in the gypsum cake.
ammonium Sulfate and ammonium carbonate; 15. The process of 1), wherein the aqueous slurry of gypsum
adding the residue solution of ammonium sulfate and is directly from a SO, scrubber.
ammonium carbonate to one or both of the first and 16. A partially continuous countercurrent flow process for
second reactors; converting gypsum to ammonium sulfate and calcium
transporting the calcium carbonate cake on the filter to 30 carbonate comprising the following steps:
Zone B in which the calcium carbonate cake is washed separating an aqueous slurry of gypsum to result in a
with water to result in a product calcium carbonate cake gypsum liquid residue and a gypsum cake:
and a wash water Solution of ammonium Sulfate and feeding a flow of reactants being the gypsum cake and a
ammonium carbonate; Solution of ammonium sulfate and ammonium carbon
retaining the product calcium carbonate cake; and 35 ate, selectively into one or both of a first reactor and a
feeding the wash water Solution of ammonium sulfate and second reactor, for chemical reaction;
ammonium carbonate to an ammonium carbonate stopping the flow of reactants into one or both of the first
absorber to retain ammonium carbonate. reactor and second reactor for a first reactor retention
. The process of 1) further comprising the following steps: time and a second reactor retention time both selected
washing the product calcium carbonate cake with water to 40 to achieve a predetermined degree of chemical reaction
result in a wash residue solution of ammonium Sulfate in one or both first reactor and second reactor to form
and ammonium carbonate; and an ammonium sulfate solution containing a first pre
adding the wash residue solution of ammonium Sulfate cipitate calcium carbonate and a gypsum remnant in
and ammonium carbonate to the first reactor. one or both first reactor and second reactor;
. The process of 1) further comprising the following steps: 45 discharging the ammonium sulfate Solution containing a
washing the product calcium carbonate cake with water to first precipitate calcium carbonate and a gypsum rem
result in a wash residue solution of ammonium Sulfate nant from one or both first reactor and second reactor;
and ammonium carbonate; and resuming the flow of reactants into one or both first
feeding the wash residue solution of ammonium Sulfate reactor and second reactor;
and ammonium carbonate to an ammonium carbonate 50 separating the first precipitate calcium carbonate and
absorption column. gypsum remnant from the ammonium Sulfate Solution
. The process of 1) further comprising the following step: to result in a product ammonium sulfate solution and a
adding ammonia or ammonium hydroxide to the first remnant cake of precipitated calcium carbonate and
reactor and second reactor to reduce foaming. gypsum,
. The process of 1), wherein the product ammonium Sulfate 55 retaining the product ammonium Sulfate Solution;
Solution contains ammonium Sulfate and the product feeding a flow of reactants being the remnant cake of first
calcium carbonate cake contains calcium carbonate, with precipitate calcium carbonate and gypsum and ammo
ammonium sulfate in a yield of 97 to 100% and calcium nium carbonate solution, selectively into one or both of
carbonate in a yield of 97 to 100%. a third reactor and a fourth reactor, for chemical reac
. The process of 1), wherein the product ammonium Sulfate 60 tion;
Solution contains ammonium Sulfate and the product stopping the flow of reactants into one or both of the third
calcium carbonate cake contains calcium carbonate, with reactor and fourth reactor for a third reactor retention
both ammonium sulfate in a yield of 100% and calcium time and a fourth reactor retention time both selected to
carbonate in a yield of 100%. achieve a predetermined degree of chemical reaction in
. The process of 1), wherein the process has a total retention 65 one or both third reactor and fourth reactor to form a
time of 4 to 60 minutes for 100% yield of product calcium second precipitate calcium carbonate and a solution of
carbonate and product ammonium Sulfate. ammonium Sulfate and ammonium carbonate;
 US 9,682,868 B2
23 24
discharging the first and second precipitate calcium car discharging the ammonium sulfate Solution containing a
bonate and a solution of ammonium Sulfate and ammo first precipitate calcium carbonate and a gypsum rem
nium carbonate from one or both third reactor and nant from one or both first reactor and second reactor;
fourth reactor; resuming the flow of reactants into one or both first
resuming the flow of reactants into one or both third reactor and second reactor;
reactor and fourth reactor; separating the first precipitate calcium carbonate and
separating the first and second precipitate calcium car gypsum remnant from the ammonium Sulfate Solution
bonate from the solution of ammonium sulfate and to result in a product ammonium sulfate solution and a
ammonium carbonate to result in a product calcium 10
first precipitate calcium carbonate and gypsum remnant
carbonate cake and a residue solution of ammonium cake;
Sulfate and ammonium carbonate; retaining the product ammonium Sulfate Solution;
retaining the product calcium carbonate cake; and feeding a flow of reactants being the second precipitate
adding the residue solution of ammonium sulfate and calcium carbonate and gypsum remnant cake and an
ammonium carbonate to one or both first reactor and 15 ammonium carbonate solution, selectively into one or
second reactor. both of a third reactor and a fourth reactor for chemical
17. The process of 16), wherein the step of separating the reaction;
aqueous slurry of gypsum to result in first and second stopping the flow of reactants into one or both of the third
gypsum liquid residues and a gypsum cake is accom reactor and fourth reactor for a third reactor retention
plished by steps comprising: time and a fourth reactor retention time both selected to
filtering an aqueous slurry of gypsum on a filter having achieve a predetermined degree of chemical reaction in
two Zones, Zone A and Zone B, wherein Zone A the one or both third reactor and fourth reactor to form a
gypsum slurry is filtered resulting in a first gypsum third precipitate calcium carbonate and a first Solution
liquid residue and a residual gypsum cake; and of ammonium sulfate and ammonium carbonate in one
transporting the residual gypsum cake on the filter to Zone 25 or both third reactor and fourth reactor;
B in which the residual gypsum cake is washed with discharging the third precipitate calcium carbonate and a
water to result in a second gypsum liquid residue. first Solution of ammonium sulfate and ammonium
18. The process of 16), wherein the step of separating the carbonate from one or both third reactor and fourth
first and second precipitate calcium carbonate from the reactor,
Solution of ammonium sulfate and ammonium carbonate 30
is accomplished by steps comprising: resuming the flow of reactants into one or both third
filtering the first and second precipitate calcium carbonate reactor and fourth reactor;
from the solution of ammonium sulfate and ammonium separating the first, second, and third precipitate calcium
carbonate from the first solution of ammonium sulfate
carbonate on a filter having two Zones, Zone A and Zone and ammonium carbonate to result in a product calcium
B, wherein Zone A the solution of ammonium sulfate 35
carbonate cake and a first residue solution of ammo
and ammonium carbonate is filtered resulting in a
calcium carbonate cake and a residue solution of nium sulfate and ammonium carbonate;
ammonium Sulfate and ammonium carbonate; retaining the product calcium carbonate cake;
adding the residue solution of ammonium sulfate and feeding a flow of reactants being the first residue solution
ammonium carbonate to one or both of the first and 40 of ammonium sulfate and ammonium carbonate and
second reactors; first precipitate calcium carbonate and gypsum remnant
transporting the calcium carbonate cake on the filter to cake, selectively into one or both of a fifth reactor and
Zone B in which the calcium carbonate cake is washed a sixth reactor, for chemical reaction;
with water to result in a product calcium carbonate cake stopping the flow of reactants into one or both of the fifth
and a wash water Solution of ammonium Sulfate and 45 reactor and sixth reactor for a fifth reactor retention
ammonium carbonate; time and a sixth reactor retention time both selected to
retaining the product calcium carbonate cake; and achieve a predetermined degree of chemical reaction in
feeding the wash water Solution of ammonium sulfate and one or both fifth reactor and sixth reactor to form a
ammonium carbonate to an ammonium carbonate second solution of ammonium Sulfate and ammonium
absorber to retain ammonium carbonate. 50 carbonate and second precipitate calcium carbonate
19. A partially continuous countercurrent flow process for and gypsum remnant in one of both fifth reactor and
converting gypsum to ammonium sulfate and calcium sixth reactor;
carbonate comprising the following steps: discharging the first and second solution of ammonium
separating an aqueous slurry of gypsum to result in a Sulfate and ammonium carbonate and second precipi
gypsum liquid residue and a residual gypsum cake; 55 tate calcium carbonate and gypsum remnant from one
feeding a flow of reactants being the residual gypsum or both fifth reactor and sixth reactor;
cake and a second solution of ammonium sulfate and resuming the flow of reactants into one or both fifth
ammonium carbonate, selectively into one or both of a reactor and sixth reactor;
first reactor and a second reactor, for chemical reaction; separating the second precipitate calcium carbonate and
stopping the flow of reactants into one or both of the first 60 gypsum remnant from the second solution of ammo
reactor and second reactor for a first reactor retention nium Sulfate and ammonium carbonate to result in the
time and a second reactor retention time both selected second residue solution of ammonium Sulfate and
to achieve a predetermined degree of chemical reaction ammonium carbonate and the second precipitate cal
in one or both first reactor and second reactor to form cium carbonate and gypsum remnant cake;
an ammonium sulfate solution containing a first pre 65 feeding the second residue solution of ammonium sulfate
cipitate calcium carbonate and a gypsum remnant in and ammonium carbonate to the first reactor and Sec
one or both first reactor and second reactor; ond reactor, and
 US 9,682,868 B2
25 26
feeding the second precipitate calcium carbonate and ammonium carbonate Solution, selectively into a third
gypsum remnant cake to the third reactor and fourth reactor for chemical reaction;
reactOr. stopping the flow of reactants into the third reactor for a
20. The process of 19), wherein the step of separating the third reactor retention time selected to achieve a pre
aqueous slurry of gypsum to result in first and second determined degree of chemical reaction in the third
gypsum liquid residues and a gypsum cake is accom reactor to form a third precipitate calcium carbonate
plished by steps comprising: and a first Solution of ammonium sulfate and ammo
filtering an aqueous slurry of gypsum on a filter having nium carbonate in the third reactor;
two Zones, Zone A and Zone B, wherein Zone A the discharging the third precipitate calcium carbonate and a
10 first Solution of ammonium sulfate and ammonium
gypsum slurry is filtered resulting in a first gypsum
liquid residue and a residual gypsum cake; and carbonate from the third reactor;
transporting the residual gypsum cake on the filter to Zone resuming the flow of reactants into the third reactor;
separating the first, second, and third precipitate calcium
B in which the residual gypsum cake is washed with carbonate from the first solution of ammonium sulfate
water to result in a second gypsum liquid residue. 15 and ammonium carbonate to result in a product calcium
21. The process of 19), wherein the step of separating the carbonate cake and a first residue solution of ammo
first, second, third, fourth, fifth and sixth precipitate nium sulfate and ammonium carbonate;
calcium carbonate from the first solution of ammonium retaining the product calcium carbonate cake;
Sulfate and ammonium carbonate is accomplished by feeding a flow of reactants being the first residue solution
steps comprising: of ammonium sulfate and ammonium carbonate and
filtering the first, second, third, fourth, fifth and sixth first precipitate calcium carbonate and gypsum remnant
precipitate calcium carbonate from the Solution of cake, into a second reactor, for chemical reaction;
ammonium Sulfate and ammonium carbonate on a filter stopping the flow of reactants into the second reactor for
having two Zones, Zone A and Zone B, wherein Zone A a second reactor retention time selected to achieve a
the Solution of ammonium sulfate and ammonium 25 predetermined degree of chemical reaction in the sec
carbonate is filtered resulting in a calcium carbonate ond reactor to form a second solution of ammonium
cake and a residue solution of ammonium sulfate and Sulfate and ammonium carbonate and second precipi
ammonium carbonate; tate calcium carbonate and gypsum remnant in the
adding the residue solution of ammonium sulfate and second reactor,
ammonium carbonate to any one or all of the first, 30 discharging the first and second solution of ammonium
second, third, fourth, fifth and sixth reactors; Sulfate and ammonium carbonate and second precipi
transporting the calcium carbonate cake on the filter to tate calcium carbonate and gypsum remnant from the
Zone B in which the calcium carbonate cake is washed second reactor,
with water to result in a product calcium carbonate cake resuming the flow of reactants into the second reactor,
and a wash water Solution of ammonium Sulfate and 35 separating the second precipitate calcium carbonate and
ammonium carbonate; gypsum remnant from the second solution of ammo
retaining the product calcium carbonate cake; and nium Sulfate and ammonium carbonate to result in the
feeding the wash water Solution of ammonium sulfate and second residue solution of ammonium Sulfate and
ammonium carbonate to an ammonium carbonate ammonium carbonate and the second precipitate cal
absorber to retain ammonium carbonate. 40 cium carbonate and gypsum remnant cake;
22. A partially continuous countercurrent flow process for feeding the second residue solution of ammonium sulfate
converting gypsum to ammonium sulfate and calcium and ammonium carbonate to the first reactor, and
carbonate comprising the following steps: feeding the second precipitate calcium carbonate and
separating an aqueous slurry of gypsum to result in a gypsum remnant cake to the third reactor.
gypsum liquid residue and a residual gypsum cake; 45 23. The process of 22), wherein the step of separating the
feeding a flow of reactants being the residual gypsum aqueous slurry of gypsum to result in first and second
cake and a second solution of ammonium sulfate and gypsum liquid residues and a gypsum cake is accom
ammonium carbonate, into a first reactor, for chemical plished by steps comprising:
reaction; filtering an aqueous slurry of gypsum on a filter having
stopping the flow of reactants into the first reactor for a 50 two Zones, Zone A and Zone B, wherein Zone A the
first reactor retention time selected to achieve a prede gypsum slurry is filtered resulting in a first gypsum
termined degree of chemical reaction in the first reactor liquid residue and a residual gypsum cake; and
to form an ammonium Sulfate solution containing a first transporting the residual gypsum cake on the filter to Zone
precipitate calcium carbonate and a gypsum remnant in B in which the residual gypsum cake is washed with
the first reactor; 55 water to result in a second gypsum liquid residue.
discharging the ammonium Sulfate Solution containing a 24. The process of 22), wherein the step of separating the
first precipitate calcium carbonate and a gypsum rem second precipitate calcium carbonate and gypsum rem
nant from the first reactor; nant from the second solution of ammonium sulfate and
resuming the flow of reactants into the first reactor; ammonium carbonate is accomplished by Steps compris
separating the first precipitate calcium carbonate and 60 ing:
gypsum remnant from the ammonium Sulfate Solution filtering the first and second precipitate calcium carbonate
to result in a product ammonium sulfate solution and a from the Solution of ammonium sulfate and ammonium
first precipitate calcium carbonate and gypsum remnant carbonate on a filter having two Zones, Zone A and Zone
cake; B, wherein Zone A the solution of ammonium sulfate
retaining the product ammonium Sulfate solution; 65 and ammonium carbonate is filtered resulting in a
feeding a flow of reactants being the second precipitate calcium carbonate cake and a residue solution of
calcium carbonate and gypsum remnant cake and an ammonium Sulfate and ammonium carbonate;
 US 9,682,868 B2
27 28
adding the residue solution of ammonium sulfate and transporting the residual gypsum cake on the filter to Zone
ammonium carbonate to any one or all of the first, B in which the residual gypsum cake is washed with
second, and third reactors; water to result in a second gypsum liquid residue.
transporting the calcium carbonate cake on the filter to 27. The process of 25), wherein the step of separating the
Zone B in which the calcium carbonate cake is washed 5 first and second precipitate calcium carbonate from the
with water to result in a product calcium carbonate cake Solution of ammonium sulfate and ammonium carbonate
and a wash water Solution of ammonium Sulfate and is accomplished by steps comprising:
ammonium carbonate; filtering the first and second precipitate calcium carbonate
retaining the product calcium carbonate cake; and from the Solution of ammonium sulfate and ammonium
feeding the wash water Solution of ammonium sulfate and 10
carbonate on a filter having two Zones, Zone A and Zone
ammonium carbonate to an ammonium carbonate
absorber to retain ammonium carbonate. B, wherein Zone A the solution of ammonium sulfate
25. A partially continuous countercurrent flow process for and ammonium carbonate is filtered resulting in a
calcium carbonate cake and a residue solution of
converting gypsum to ammonium sulfate and calcium
carbonate comprising the following steps: 15 ammonium Sulfate and ammonium carbonate;
separating an aqueous slurry of gypsum to result in a adding the residue solution of ammonium Sulfate and
gypsum liquid residue and a gypsum cake; ammonium carbonate to one or both of the first and
feeding a flow of reactants being ammonia, carbon diox second reactors;
ide, the gypsum cake, and a solution of ammonium transporting the calcium carbonate cake on the filter to
Sulfate and ammonium carbonate into a first reactor for Zone B in which the calcium carbonate cake is washed
chemical reaction; with water to result in a product calcium carbonate cake
stopping the flow of reactants into the first reactor for a and a wash water Solution of ammonium Sulfate and
retention time selected to achieve a predetermined ammonium carbonate;
degree of chemical reaction to form an ammonium retaining the product calcium carbonate cake; and
Sulfate solution containing a first precipitate calcium 25 feeding the wash water Solution of ammonium sulfate and
carbonate and a gypsum remnant; ammonium carbonate to an ammonium carbonate
discharging the ammonium Sulfate Solution containing a absorber to retain ammonium carbonate.
first precipitate calcium carbonate and a gypsum rem 28. A partially continuous countercurrent flow process for
nant, converting gypsum to ammonium sulfate and calcium
resuming the flow of reactants into the first reactor; 30 carbonate comprising the following steps:
separating the first precipitate calcium carbonate and separating an aqueous slurry of gypsum to result in a
gypsum remnant from the ammonium sulfate solution gypsum liquid residue and a gypsum cake:
to result in a product ammonium sulfate solution and a feeding a flow of reactants being the gypsum cake and a
remnant cake of first precipitate calcium carbonate and Solution of ammonium sulfate and ammonium carbon
gypsum, 35 ate, selectively into one or all reactors of a plurality of
retaining the product ammonium Sulfate solution; reactors, for chemical reaction;
feeding a flow of reactants being ammonia, carbon diox stopping the flow of reactants into one or all reactors of
ide, the remnant cake of first precipitate calcium car the plurality of reactors for a reactor retention time
bonate and gypsum and ammonium carbonate Solution selected for any one or all reactors of the plurality of
into a second reactor for chemical reaction; 40 reactors, wherein the retention time for a particular one
stopping the flow of reactants into the second reactor for reactor is selected to achieve a predetermined degree of
a retention time selected to achieve a predetermined chemical reaction in the particular one reactor to form
degree of chemical reaction to form a second precipi an ammonium sulfate solution containing a first pre
tate calcium carbonate and a solution of ammonium cipitate calcium carbonate and a gypsum remnant in
Sulfate and ammonium carbonate; 45 one or all reactors of the plurality of reactors;
discharging the first and second precipitate calcium car discharging the ammonium sulfate Solution containing a
bonate and a solution of ammonium Sulfate and ammo first precipitate calcium carbonate and a gypsum rem
nium carbonate; nant from one or all reactors of the plurality of reactors;
resuming the flow of reactants into the second reactor, resuming the flow of reactants into one or all reactors of
venting excess carbon dioxide and ammonia from the first 50 the plurality of reactors;
reactor and the second reactor, separating the first precipitate calcium carbonate and
separating the first and second precipitate calcium car gypsum remnant from the ammonium Sulfate Solution
bonate from the solution of ammonium sulfate and to result in a product ammonium sulfate solution and a
ammonium carbonate to result in a product calcium remnant cake of precipitated calcium carbonate and
carbonate cake and a residue solution of ammonium 55 gypsum,
Sulfate and ammonium carbonate; retaining the product ammonium Sulfate Solution;
retaining the product calcium carbonate cake; and feeding a flow of reactants being the remnant cake of first
adding the residue solution of ammonium sulfate and precipitate calcium carbonate and gypsum and ammo
ammonium carbonate to the first reactor. nium carbonate solution, selectively into one or all
26. The process of 25), wherein the step of separating the 60 reactors of the plurality of reactors, for chemical reac
aqueous slurry of gypsum to result in first and second tion;
gypsum liquid residues and a gypsum cake is accom stopping the flow of reactants into one or all reactors of
plished by steps comprising: the plurality of reactors for a reactor retention time
filtering an aqueous slurry of gypsum on a filter having selected for any one or all reactors of the plurality of
two Zones, Zone A and Zone B, wherein Zone A the 65 reactors, wherein the retention time for a particular one
gypsum slurry is filtered resulting in a first gypsum reactor is selected to achieve a predetermined degree of
liquid residue and a residual gypsum cake; and chemical reaction in the particular one reactor to form
 US 9,682,868 B2
29 30
a second precipitate calcium carbonate and a solution 8. The residual cake from the Reactor 1 filtration was
of ammonium sulfate and ammonium carbonate; added to the beaker serving as Reactor 2. Fresh 33%
discharging the first and second precipitate calcium car ammonium carbonate Solution containing 100% stoi
bonate and a solution of ammonium Sulfate and ammo chiometric requirement of ammonium carbonate was
nium carbonate from one or all reactors of the plurality added to the cake.
of reactors; 9. The resulting slurry was mixed on a stir plate for 10 or
resuming the flow of reactants into one or all reactors of 20 minutes (usually 10 minutes). Any foaming was
the plurality of reactors; dissipated by spraying aqua ammonia into the reactor.
separating the first and second precipitate calcium car 10. The slurry was filtered and the resulting cake was
bonate from the solution of ammonium sulfate and 10
washed with 300 mL of Grade I water. The Reactor 2
ammonium carbonate to result in a product calcium filtrate was kept for possible recycling to Reactor 1 in
carbonate cake and a residue solution of ammonium the next test.
Sulfate and ammonium carbonate; 11. The resulting cake was dried overnight in an oven at
retaining the product calcium carbonate cake; and 60° C. to drive off any free moisture and was then
adding the residue solution of ammonium sulfate and 15
analyzed by LECOR) quantitative instruments (nitrogen
ammonium carbonate to one or all reactors of the
plurality of reactors. analyzer was a LECO Model FP-528; carbon/sulfur
The present invention is demonstrated with reference to analyzer was a LECO Model SC-144DR) for percent
the following examples, which are of an illustrative nature carbon, percent Sulfur, and percent nitrogen content. A
only and which are to be construed as non-limiting. quick carbon, Sulfur, and nitrogen analytical result can
be obtained by drying a sample in the moisture balance
EXAMPLES before analysis is performed using the LECOR instru
mentS.
Example 1
25 Example 2
The two reactor embodiment of the present multistage,
partially continuous countercurrent process was tested by Lab Tests Showing Effect of Process Washing on
performing laboratory tests and tests in a pilot plant to Control of Product Crystal Size and Morphology
simulate the process of the present invention as illustrated in
FIG. 1. The laboratory procedures and equipment are 30
Lab Scale Test Using Anhydrous Ammonia and Delayed
described below. Water Wash of Product
Laboratory Gypsum Conversion Partially Continuous This test was performed in the two stage, two reactor
Countercurrent Process Equipment and Procedure embodiment of the invention, such as shown in FIG. 1, to
Equipment: achieve approximately 50% conversion of gypsum (in this
2 liter beakers 35
2 liter Erlenmeyer flask case, FGD gypsum) to calcium carbonate in each reactor
5/4." ID Buchner funnel while producing a substantially pure, calcium carbonate
Busch laboratory vacuum pump product. The test employed ammonium carbonate Solution
41 cfm, polyester filter cloth (same as reactor filters used that had been stored, and over time had developed a high
in Pilot Plant tests described below) 40 concentration of ammonium bicarbonate. To change the
Laboratory hot/stir plate ammonium bicarbonate back to ammonium carbonate,
Procedure: anhydrous ammonia was sparged into each reactor. This
1. A 1% or 5% (usually 1%) by volume sulfuric acid adjustment was needed to prevent carbon dioxide gas for
Solution in water was prepared in a beaker. mation.
2. The gypsum to be tested was weighed out to make a 45 The FGD gypsum (175 g) was washed with 1% by
slurry containing about 30% solids. Volume (including the water in the gypsum) Sulfuric acid for
3. The slurry was mixed on a stir plate with a magnetic stir twenty minutes and then filtered and washed with water.
bar for a minimum of 20 minutes. This gypsum was fed to Reactor No. 1 where it was mixed
4. The slurry was filtered by adding it to a Buchner funnel with a solution containing 186.7 g of 36% ammonium
holding the filter cloth and a vacuum was pulled 50 sulfate solution and 267.86 g of ammonium carbonate/
through by the vacuum pump. All filtrate was captured bicarbonate solution. The ammonium carbonate/bicarbonate
in the Erlenmeyer flask. The resulting cake was washed Solution was made weeks earlier and analyzed at the time of
with 300 mL of Grade I water. this test as 2.7% C and 6.2% N. It is assumed that during the
5. The washed gypsum was added to the beaker serving as storage time, large amounts of bicarbonate formed as ammo
Reactor 1. Either fresh 33% ammonium carbonate 55 nia volatilized. To obtain 50% conversion in the Reactor No.
solution and 36% ammonium sulfate solution or filtrate 1, anhydrous ammonia was added at a rate of 1.9 cfm for 11
recycled from the previous test's Reactor 2 filtration seconds to convert ammonium bicarbonate to ammonium
was added containing 50% stoichiometric requirements carbonate in Reactor No. 1 while the solution and gypsum
of ammonium carbonate and ammonium Sulfate. The were mixing. The reactants were mixed for twenty minutes
fresh Solutions were made from adding reagent grade 60 and the resulting slurry was filtered. The product as a filter
ammonium carbonate and feed grade ammonium Sul cake was added to Reactor No. 2 with 535.71 g of ammo
fate to Grade I water. nium carbonate/bicarbonate Solution, the amount needed to
6. The slurry was mixed on a stir plate for 10 or 20 ensure full conversion to product calcium carbonate. Anhy
minutes (usually 10 minutes). Any foaming was dissi drous ammonia was added to the mixture after the start of
pated by spraying aqua ammonia into the reactor. 65 mixing at a rate of 1.9 cfm for 22 seconds, and the mixing
7. The slurry was filtered. The filtrate was the ammonium was performed for twenty minutes. After the final product
Sulfate product solution. was filtered and dried overnight at 100 degrees C., it was
 US 9,682,868 B2
31 32
found to be 11.324% Carbon. Four days later, the product sizes of the product were up to 3 microns with the Vaterite
was washed and dried overnight again and analyzed, giving forming porous agglomerates up to 50 microns across. The
11636% C. calcite was single prismatic crystals 2 microns in size, the
Reacting the product with hydrochloric acid showed that size being controlled by the reaction times and the propor
the calcium carbonate product contained 1.05% unreactive 5 tion of reactants in each reactor.
material which by X-ray diffraction showed chlorite, kaolin The above three tests demonstrate that:
ite, k-feldspar, mica, plagioclase, pyrite, quartz, and amor 1. The use of ammonium bicarbonate with ammonia
phous material of mostly barium sulfate. X-ray diffraction addition during the reaction can substitute for the use of
also showed that the calcium carbonate crystalline forms ammonium carbonate.
present in the product were calcite and Vaterite, the latter 10
2. Adjustment of process parameters controls product
being a metastable form of calcium carbonate. Analysis by particle (crystal) size distribution and specific particle
polarized light microscopy after storage of the sample for 31 size.
weeks showed the bulk of the sample to be Vaterite with a 3. Adjustment of process parameters controls production
crystal size of up to 1x1x4 microns and a minor portion of of specific types of calcium carbonate polymorphs
the sample to be calcite with a crystal size of up to 3x3x7 15
microns. including calcite, Vaterite and aragonite.
Lab Scale Test Using Anhydrous Ammonia Without 4. The ammonium Sulfate (and in particular the Sulfate
Water Wash of Final Product anion) is capable of keeping the Vaterite polymorph of
To test the effects of no water wash step in the present two product calcium carbonate to be stable during the
stage, two reactor process on the particle size and formation process. Thus, the process of the present invention
of the calcium carbonate product, 175g of FGD gypsum was optionally includes the direct use of ammonium sulfate
washed with 1% sulfuric acid solution by mixing for twenty or recycle of ammonium sulfate to keep the product
minutes. The mixture was filtered, washed with water, and Vaterite from changing to another calcium carbonate
filtered again. The FGD gypsum cake was then mixed in polymorph Such as aragonite or calcite. This poly
Reactor No. 1 with 186.7 g of 36% ammonium sulfate 25 morph stabilization Subprocess may be integrated into
solution and 267.86 g of 33% ammonium carbonate solu the processes of the present invention as shown in
tion. After the initial mixing started, anhydrous ammonia FIGS. 1, 2, 8A-B, and 9 A-C.
was sparged in at a rate of 1.9 cfm for 11 seconds, and the
mixing continued for a total of twenty minutes. The product Example 3
calcium carbonate was filtered without additional water 30
wash and the filter cake was added to Reactor No. 2 with Pilot Plant Gypsum Conversion Partially
535.71 g of ammonium carbonate solution while stirring. Continuous Countercurrent Process Equipment and
Ammonia was added with a sparger at a rate of 1.9 cfm for Procedure
thirty seconds. The reactants were mixed for twenty min
utes, and then filtered and dried overnight at 130 degrees 35 This pilot plant was a two stage, two reactor system, Such
Fahrenheit without any water wash prior to drying. as in embodiment number 1 and shown in FIG. 1.
Polarized light microscopy of the final calcium carbonate Equipment:
product showed approximately 75 to 95% waterite and 5 to Ammonium Carbonate Column—30" diameter stainless
25% calcite present with no unreacted gypsum. The crystals steel column with pall ring packing and mist eliminator
sizes of the product were up to 3 microns with the Vaterite 40 pad, 80 gallon bottom tank
forming porous agglomerates up to 50 microns across. The Ammonium Carbonate Column Pump Durco 5 HP cen
calcite comprised single prismatic crystals, 2-3 microns in trifugal pump
size, the size being controlled by the reaction times and the Ammonium Carbonate Solution Tank 3.5" diameterx
reaction percentages in each reactor. 4.67" tall with dished bottom, approximately 350 gal
Lab Scale Test Using Anhydrous Ammonia With Imme 45 lons, stainless Steel with steam coil
diate Water Wash of Final Product Ammonium Carbonate Solution Tank Agitator—1 HP,
To show the effects of employing a water washing step in stainless steel
the present two stage, two reactor process, the final calcium Ammonium Carbonate Solution Pump /2" air dia
carbonate product, 175 g of FGD gypsum was washed with phragm pump
1% sulfuric acid solution by mixing for twenty minutes. The 50 Gypsum Acid Wash Tank 275 gallon polypropylene
mixture was filtered, washed with water, and filtered again. tote, 48"x40"X46"
The FGD gypsum cake was then mixed in Reactor No. 1 Gypsum Acid Wash Tank Agitator /2 HP, stainless steel
with 186.7 g of 36% ammonium sulfate solution and 267.86 Sulfuric Acid Tank—55 gallon polypropylene drum
g of 33% ammonium carbonate solution. After the initial Sulfuric Acid Pump-120 volt drum pump
mixing started, anhydrous ammonia was sparged in at a rate 55 Gypsum Acid Wash Pump-1/2"x72", 0.5 HP. Seepex
of 1.9 cfm for 11 seconds, and the mixing continued for a progressive cavity pump
total of twenty minutes. The product was filtered and washed Gypsum Acid Wash Belt Filter National Filter Media
with 500 mL of water and filtered again. The filter cake was unit with a 19"x36" filter section (4.75 ft), a 19"x48"
added to Reactor No. 2 with 535.71 g of ammonium wash section (6.33 ft), 80 cfm polypropylene filter
carbonate Solution while stirring. Ammonia was added with 60 cloth, variable speed drive, two vacuum pumps and
a sparger at a rate of 1.9 cfm for thirty seconds. The reactants receivers, two centrifugal filtrate transfer pumps
mixed for twenty minutes. The product calcium carbonate Acid Solution Tank 275 gallon polypropylene tote, 48"x
was filtered, washed with 500 mL of water, filtered again and 40"X46"
dried overnight at 130 degrees Fahrenheit. Reactor 1–2" diameterx2.5" tall with cone bottom,
Polarized light microscopy of the final calcium carbonate 65 approximately 35 gallons, stainless steel with Steam
product showed approximately 75 to 95% waterite and 5 to coil
25% calcite present with no unreacted gypsum. The crystals Reactor 1 Agitator—1 HP stainless steel
 US 9,682,868 B2
33 34
Reactor 1 Pump-1/2"x134", 0.75 HP. Seepex progres 5. Reactor 1 was charged with stoichiometric amounts of
sive cavity pump ammonium carbonate and ammonium sulfate to achieve
Reactor 1 Belt Filter 9/2"x42" (2.77 ft) filter area, 41 the desired amount of conversion in Reactor 1 (usually
cfm polyester filter cloth, one vacuum pump and 50%). In some tests, fresh ammonium carbonate solution
receiver, /2" air diaphragm filtrate transfer pump was used from the Ammonium Carbonate Solution Tank
Ammonium Sulfate Solution Tank 275 gallon polypro and 36% ammonium sulfate solution was used which was
pylene tote, 48"x40"x46" made by dissolving feed grade ammonium sulfate in
Ammonium Sulfate Solution Tank Agitator—/2" HP, water. In other tests, the filtrate from the Reactor 2 Belt
stainless steel 10
Filter's filtration Zone, containing ammonium carbonate
and ammonium Sulfate, was recycled to Reactor 1. This
Reactor 2–2 diameterx2.5" tall with cone bottom, Solution mixture is present in Reactor 1 before gypsum is
approximately 35 gallons, stainless steel with Steam added.
coil
6. The filtered, washed gypsum was charged to Reactor 1
Reactor 2 Agitator—1 HP stainless steel 15 and mixed with the solution by the Reactor 1 Agitator for
Reactor 2 Pump-1/2"x1'4", 0.75 HP. Seepex progres 10 or 20 minutes (usually 10 minutes). The slurry was also
sive cavity pump recirculated by the Reactor 1 Pump during the mixing.
Reactor 2 Belt Filter Eimco unit with a 6"x24" filter Any foaming was dissipated by spraying aqua ammonia
section (1 ft), a 6"x18" wash section (0.75 ft), 41 cm from the Aqua Ammonia Tank into the reactor using the
polyester filter cloth, one vacuum pump with two Aqua Ammonia Pump and a wide angle spray nozzle
receivers, two /2 "air diaphragm filtrate transfer pumps mounted over the reactor. An excess of gypsum was
Water Wash Tank 275 gallon polypropylene tote, 48"x present in Reactor 1 leading to complete conversion of the
40"X46" solution to Ammonium Sulfate.
Ammonium Carbonate Wash Pump 1"x72", 120 volt 7. The slurry was pumped by the Reactor 1 Pump to the
SeepeX progressive cavity pump 25 Reactor 1 Belt Filter. The partially converted cake was
vacuum filtered to remove pure ammonium Sulfate solu
Aqua Ammonia Tank—55 gallon polypropylene drum tion as the filtrate. This solution was pumped by the
Aqua Ammonia Pump—/2" air diaphragm pump filtrate pump to the Ammonium Sulfate Tank for storage.
Ammonia Scrubber Stainless steel with tower pre 30
8. Reactor 2 was charged with 100% stoichiometric require
Scrubber and candle wicking sections, includes cen ments of ammonium carbonate from the Ammonium
trifugal recirculation pump and centrifugal exhaust Carbonate Solution Tank using the Ammonium Carbonate
blower Solution Pump. This solution was present in Reactor 2
Procedure: before the partially converted cake was introduced.
1. With reference to the above Equipment list, the Ammo 35 9. The filtered, partially converted cake of gypsum and
nium Carbonate Column was charged with 29% aqua calcium carbonate was charged to Reactor 2 and mixed by
ammonia and the appropriate amount of wash water from the Reactor 2 Agitator for 10 or 20 minutes (usually 10
the Reactor 2 Belt Filter was added in order to make minutes). The slurry was also recirculated by the Reactor
approximately 33% ammonium carbonate Solution by 2 Pump during the mixing. Any foaming was dissipated
weight. Carbon dioxide from Dewar cylinders (contain 40 by spraying aqua ammonia from the Aqua Ammonia Tank
ers) was sparged in until the proper pH and specific into the reactor using the Aqua Ammonia Pump and a
gravity was reached and analysis by LECOR instrumen wide angle spray nozzle mounted over the reactor. The
tation showed approximately 33% ammonium carbonate excess ammonium carbonate present in Reactor 2 led to
Solution was achieved. complete conversion of the cake to calcium carbonate.
2. The solution was pumped by the Ammonium Carbonate 45 10. The slurry was pumped by the Reactor 2 Pump to the
Column Pump to the Ammonium Carbonate Solution Reactor 2 Belt Filter. The slurry was filtered and then
Tank for storage. The solution was mixed by the Ammo washed using tap water by employing an overflow weir to
nium Carbonate Solution Tank Agitator and recirculated remove any remaining ammonium carbonate and ammo
by The Ammonium Carbonate Solution Pump until the nium sulfate. Filtrate from the filtration Zone was captured
Solution was pumped to and used in the conversion 50 in a receiver for recycle back to Reactor 1. The wash
process. water from the wash Zone was captured in a separate
receiver and pumped to the Water Wash Tank so that it
3. The Gypsum Acid Wash Tank was charged with tap water could later be recycled and used to make ammonium
and 93% sulfuric acid was pumped from the Sulfuric Acid carbonate solution in the Ammonium Carbonate Column.
Tank by the Sulfuric Acid Pump to make a 1% or 5% 55 Filtered, cleaned calcium carbonate cake was discharged
sulfuric acid solution by volume. off of the belt filter into a super sack for storage.
4. FGD gypsum was hand fed into the Gypsum Acid Wash 11. The ammonia scrubber was used to pull vents on the
Tank until the slurry contained about 30% gypsum. The Ammonium Carbonate Column and various process
gypsum was allowed to mix with the acid solution for a points to remove ammonia vapor and wash it out of the air
minimum of 20 minutes. Foaming can occur during 60 through contact with water in the pre-scrubber and candle
mixing but is dissipated through the use of an organic wicking sections. The cleaned air was exhausted outside
defoamer. After mixing, the slurry was metered by the of the pilot plant area.
Gypsum Acid Wash Pump and load cells on the tank to the 12. Process samples were taken of the ammonium sulfate
Gypsum Acid Wash Belt Filter. The slurry was filtered and solution, Reactor 1 Belt Filter cake, and Reactor 2 Belt
then washed with tap water by using an overflow weir to 65 Filter cake to test and analyze by LECOR instruments for
remove metal impurities and the sulfuric acid. The filtrate purity of the products and conversion levels in each
was pumped to the Acid Solution Tank for storage. reactOr.
 US 9,682,868 B2
35 36
Example 4 14) Final product cake was analyzed for conversion to
calcium carbonate. Analysis of the calcium carbonate
Pilot Plant Tests For Two Stage, Two Reactor using LECOR) analytical instrumentation showed
Partially Continuous Countercurrent Process 100% conversion; microscope examination showed
that product cake consisted of homogenous single
This pilot plant was a two stage, two reactor System, Such crystals of calcium carbonate with size of 1 to 4
as in embodiment number 1 and shown in FIG. 1. microns in diameter; by X-ray diffraction, the calcium
carbonate content was determined to be 98.8% and acid
Pilot Plant Test on Apr. 24, 2014–50% Conversion insolubles were determined to be 1.24%.
in Reactor 1 10
Pilot Plant Test on Oct. 3, 2014
Test objective: to produce 100% pure calcium carbonate
(and thus stoichiometrically, 100% pure ammonium sulfate) 50%. Conversion in Both Reactors 1 and 2 Using
with 50% conversion in each reactor. Plant Miller Stack Gas with Acid Wash (Metals
1) Mixed 1,000 pounds of water, 23 pounds of 93.2% 15 Analysis)
sulfuric acid, and 535 pounds of FGD gypsum from the
Miller Electric Generating Plant, Alabama (Plant Test objective: To achieve 50% conversion in Reactor 1
Miller), in a tote with an agitator. This resulted in a 1% and Reactor 2 using ammonium carbonate Solution made
acid solution by volume. The slurry had been mixing from Plant Miller's stack (flue) gas.
for several days at time of test at ambient temperature: 1) Wash large sample of raw FGD gypsum from Plant
accounting for water in the gypsum, '% Miller with 1% acid, filter the washed gypsum and
solids—approximately 29.7%. retain gypsum cake.
2) In the absence of an effective method of measuring 2) Mixed 500 pounds of water, 11.5 pounds of 93.2%
ammonium carbonate content in Solution at this time, sulfuric acid, and 267.5 pounds of Plant Miller gypsum
an ammonium carbonate column was used until the 25 cake which had been washed with 1% acid, in a tote
solution had a pH of 9.2 and a specific gravity of about with an agitator in addition to heel (residual slurry
1.11; these conditions were approximately the same as remaining from previous filtration operation) already
ammonium carbonate Solution use in the lab when mixed at same percentages; this calculates to a 1% acid
100% conversion was achieved. solution by volume; heel had been mixing for several
3) Pumped 219 pounds of gypsum slurry to gypsum acid 30 days at time of run at ambient condition; accounting for
wash belt filter at a rate of 18 pounds/minute; this water in the gypsum, 96 solids—approximately 29.7%.
equates to about 65 pounds of gypsum or 0.378 moles. 3) Ammonium carbonate solution used in test had been
4) About a 3/4" cake was formed on the belt. The cake was made at Plant Miller from Jun. 16-Jun. 27, 2014 by
very Soupy and wet. bubbling Stack (flue) gas through a drum of ammonium
5) The cake was washed with tap water on the belt by 35 hydroxide; because of the time lapse between produc
hand with a sprayer. tion of the solution and the present test, the solution
6) The cake was introduced offend of belt to Reactor 1. measured low in % nitrogen (6.903%) and % carbon
7) Filtrate had been recycled from Reactor 2 belt filter to (2.627%); experience with the process shows that con
Reactor 1; by material balance this equaled 25 pounds version is difficult to achieve with such a weak solution;
of ammonium sulfate, 21.6 pounds of ammonium car 40 the solution was added back to the ammonium carbon
bonate, and 136.4 pounds of water; this met the 50% ate column and sparged with anhydrous ammonia and
Stoichiometric requirements for both ammonium Sul CO, to raise the analysis back to % N=9.637 and %
fate and ammonium carbonate. C=4.242 (N/C-2.27); pure ammonium carbonate has
8) The acid washed gypsum cake was mixed in Reactor 1 N/C ratio of 2.33; solution is slightly nitrogen limited
by agitator for 10 minutes at ambient conditions; no 45 with excess carbon; % ammonium carbonate solu
external heat was applied; the temperature remained tion=33.0.
around 65 to 70 degrees F.; the pH decreased from 4) Pumped 219 pounds of gypsum slurry to gypsum acid
approximately 9 to 8.1 over the course of 10 minutes: wash belt filter at a rate of 21.3 pounds/minute; this
there was minimal foaming. equates to about 65 pounds of gypsum or 0.378 moles.
9) The slurry was then pumped to the Reactor 1 filter belt 50 5) There was about 4" of Hg vacuum (inches of mercury)
at a rate of 13 pounds/minute; the cake was about 1" on the first belt wherein the cake was soupy and wet;
thick on the belt; the cake was Soupy and wet. about a 13/4" —2" cake was formed on the belt.
10) The cake was introduced to Reactor 2 off the end of 6) The cake was washed with tap water on the belt by
the belt; ammonium carbonate solution had been added overflow weir at about 0.4 gpm rate.
to Reactor 2 to complete the reaction: 100% of the 55 7) Cake was introduced off end of belt to Reactor 1.
Stoichiometrically required ammonium carbonate was 8) Since 50% conversion was desired in Reactor 1, 0.378
added to Reactor 2, or 134 pounds of ammonium molesx0.5-0.189 moles of ammonium carbonate had
carbonate Solution. been added to Reactor 1; this equals 18.1 pounds of
11) Cake was mixed with solution in the Reactor 2 by ammonium carbonate or 55 pounds of the 33% solu
agitator for 10 minutes at ambient conditions; the 60 tion.
temperature in Reactor 2 remained at 73 degrees F. pH 9) 50% of stoichiometric required ammonium sulfate had
remained relatively unchanged at 9.1. also been added to Reactor 1; a 36% ammonium sulfate
12) After 10 minutes, slurry was pumped to the Reactor Solution had been made from bagged feed grade ammo
2 belt filter at a rate of 15 pounds/minute; the cake was nium sulfate crystals dissolved in tap water, 0.189
about 1" thick and was wet coming off belt. 65 moles of ammonium sulfate or 25 pounds of ammo
13) Cake was washed with about 0.4 gpm of tap water on nium sulfate was added, and this amounted to 89.4
belt. pounds of the ammonium sulfate solution.
 US 9,682,868 B2
37 38
10) The acid washed gypsum cake was mixed in Reactor Pilot Plant Test on Oct. 6, 2014
1 by agitator for 15 minutes at ambient conditions; no
external heat was applied; the temperature remained 50%. Conversion in Both Reactors 1 and 2 Using
around 71 to 74° F.; pH decreased from 8.66 to 7.64 Plant Miller Stack Gas with No Acid Wash (Metals
over the course of 15 minutes; there was minimal Analysis)
foaming.
11) The slurry was then pumped to the Reactor 1 filter belt Test objective: In order to show the effectiveness of
at a rate of about 15 pounds/minute; the cake was about treating raw Plant Miller gypsum with an acid wash, the
34" thick on the belt; very dry cake: 18 to 22" Hg same test that was performed on Oct. 3, 2014 with an acid
vacuum on the belt filter. 10 wash, described above, was performed on Oct. 6, 2014
12) The cake was introduced to Reactor 2 off the end of without an acid wash. A further objective was to achieve
the belt; ammonium carbonate solution had been added 50% conversion in Reactor 1 and Reactor 2 using ammo
nium carbonate solution made from Plant Miller's stack
to Reactor 2 to finish off the reaction; 100% stoichio
metric amount required for the initial gypsum was (flue) gas.
added=0.378 moles=110 pounds of 33.0% ammonium 15 1) The ammonium carbonate Solution employed in this
carbonate Solution. test had been made at Plant Miller from Jun. 16-Jun. 27,
13) The pH of Reactor 2 before cake was added was 9.50 2014 by bubbling stack gas through a drum of ammo
(a 70.1°F.; after all the cake was added and as retention nium hydroxide; because of the time lapse between
time started, pH was 9.43 (a 72.1° F.; at end of 15 production of the Solution and the time of conducting
minutes, pH was 9.25 (a) 74.1 F.; there was minimal the present test, the solution measured low in percent
foaming. nitrogen (6.903%) and percent carbon (2.627%); expe
14) Slurry was pumped to the final belt filter at a rate of rience with the process shows that conversion is diffi
about 17 lbs/min. cult to achieve with such a weak solution; the solution
was added back to the ammonium carbonate column
15) Cake was washed with about 0.5 gpm of tap water on 25 and sparged with anhydrous ammonia and CO to raise
belt by overflow from nozzle spray.
16) Final product cake was analyzed for conversion to the analysis back to % N=9.178 and % C=4.285
calcium carbonate. Samples heated in moisture balance (N/C=2.14); pure ammonium carbonate has N/C ratio
showed 44.1 moisture and 82.8% conversion. Because of 2.33; the solution was slightly nitrogen limited with
of the apparent low conversion relative to the slurry excess carbon; % ammonium carbonate solution=31.5.
samples, samples of final product were washed in the 30 2) Since 50% conversion was desired in Reactor 1, 0.378
lab with Grade I water, dried, and reanalyzed. The molesx0.5-0.189 moles of ammonium carbonate was
reanalyzed samples showed 100% conversion to cal added to Reactor 1; this equals 18.1 pounds of ammo
cium carbonate, not including impurities indicating that nium carbonate or 57.7 pounds of the 31.5% solution.
ammonium sulfate Solution was retained by the amor 3) 50% of stoichiometric required ammonium sulfate had
phous agglomerates and required further washing. 35 also been added to Reactor 1; a 36% ammonium sulfate
17) Cake analysis by LECOR instrumentation showed Solution had been made from bagged feed grade ammo
19% conversion in Reactor 1 and 81% conversion in
Reactor 2.
nium sulfate crystals dissolved in tap water, 0.189
18) LECOR analysis for Sulfur, Nitrogen, and Carbon moles of ammonium sulfate or 25 pounds of ammo
confirmed that ammonium sulfate was made and was nium sulfate was added, this amounted to 89.4 pounds
40 of the ammonium sulfate Solution.
coming out of Reactor 1 with S/N ratio=1.14 which is 4) The ammonium carbonate and ammonium sulfate
correct for ammonium sulfate; % solution=20.3%. solutions were allowed to mix by agitation for several
Nitrogen analysis was performed by using a LECO
Model FP-528. Carbon and Sulfur analysis was per minutes in Reactor 1 before addition of the gypsum.
formed by using a LECO Model SC-144DR. The pH in Reactor 1 before gypsum addition was
Samples of the raw Miller gypsum, the acid wash filtrate, 45 9.05 (a 65.8° F.
Reactor 1 filtration cake, Reactor 1 filtrate, final product 5) 75.2 pounds of Plant Miller gypsum was weighed out
filtration cake, Reactor 2 filtrate, and final water wash and placed on the gypsum wash belt filter. Since the
underwent metals quantitative analysis; metals analyzed gypsum contains about 13.5% moisture, this equals
were arsenic, selenium, aluminum, and magnesium; mer about 65 pounds of dry gypsum or 0.378 moles. The
cury analysis was also performed. The analytical results are 50 belt was used to slowly add the gypsum to Reactor 1
shown below in Table 1. over the span of 15 minutes to prevent settling of the
gypsum and ensure good agitation.
TABLE 1. 6) The pH of the slurry in Reactor 1 after all of the
gypsum had been added was 8.69(a) 67.9° F.
Metals Analysis With Process using Acid Wash of raw FGD Gypsum 55 7) A steep drop in pH occurred after about 12/2 minutes
Magne of agitation. The pH continued to drop steadily at 15
Test Step Arsenic Selenium Aluminum sium Mercury minutes elapsed time, so the agitation was allowed to
Raw gypsum O.656 1O.S 369 1220 1.19
continue. At 20 minutes, the pH was 7.96 (a) 68.5° F.
Acid wash filtrate 0.128 4.14 144 665 O.OOS33
The slurry was allowed to mix until the pH stabilized
Reactor 1 cake O488 3.65 137 108 O.800 60 which it did after approximately 28 minutes. The pH at
Reactor 1 filtrate 0.0185 1.08 O.O270 15.1 ND this time was 7.68 (a 68.6 F. No foaming occurred in
Product cake 0.679 2.11 262 173 O668 Reactor 1.
Reactor 2 filtrate 0.0190 2.46 O.962 ND O.OO905
Final water wash 0.00825 1.12 O.338 ND O.OO2S6
8) During the mixing within Reactor 1, 115.3 pounds of
the 31.5% ammonium carbonate solution had been
Solution results are reported in mg L and solid results are reported in mg/kg, 65 added to Reactor 2. This equaled 36.3 pounds of
ND = Not detected at the reporting limit. ammonium carbonate or 0.378 moles. The pH in Reac
tor 2 before addition of cake was 9.37 (a 65.3° F.
 US 9,682,868 B2
39 40
9) The slurry was then pumped to the Reactor 1 filter belt 1) Gypsum acid wash belt:
at a rate of about 15 pounds/minute; the cake was about Filtration area=19'x36"=4.75 ft
!/2-3/4" thick on the belt; very dry cake; 16 to 26" Hg Feed rate ranged from 11 to 21 lbs/min, average of 16
vacuum on the belt filter. lbs/min
10) After all the filter cake was conveyed from the Reactor 5 Filtration rate=3.37 lbs/min/ft
1 filter belt and as retention time started, pH Wash Zone area=19"x48"=6.33 ft
was 9.33 (a) 66.6° F.; at end of 15 minutes, pH was Filtration rate=2.53 lbs/min/ft (washed with ~0.4 gpm
9.26 (a) 66.9° F.; there was minimal foaming. water which is not sufficient, need 1 gpm to match
lab rate)
11) Slurry was pumped to the final belt filter at a rate of 10 2) Reactor 1 belt (2' filter):
about 17 lbs/min. Area=9/2"X42"=2.77 ft
12) Filter cake was washed with about 0.5 gpm of tap Typical flow rate=15 lbs/min of slurry to belt
water on belt by overflow from nozzle spray. Filtration rate=5.42 lbs/min/ft
3) Reactor 2 belt (3" filter):
13) Final product cake was analyzed for conversion to 15 Filtration area=6"x24"=1 ft
calcium carbonate. Samples were heated in moisture Typical flow rate=17 lbs/min of slurry to belt
balance and showed 44.9% moisture and 92.1% con Filtration rate=17 lbs/min/ft
version; because of the low conversion relative to the Wash Zone are=6'x18"=0.75 ft
slurry Samples, samples of final product were washed Filtration rate=22.7 lbs/min/ft (washed with -0.5 gpm
in the lab with Grade I water, dried, and reanalyzed: water which is not sufficient; need 1.9 gpm to match
these showed conversion of 100% not counting impu lab rate)
rities.
14) Cake analysis by quantitative instrumentation (made Example 5
by LECOR) showed 34% conversion in Reactor 1 and 25 Tests for Process Boundary Conditions
66% conversion in Reactor 2
15) LECOR analysis for S, N, and C confirmed ammo The above described pilot plant tests were performed so
nium sulfate was made coming out of Reactor 1 as S/N that approximately 50% of the reaction occurred in each
ratio=1.14 which is correct for ammonium sulfate; % Reactor (Reactor 1 and Reactor 2). However, the present
solution=21.9%. Nitrogen analysis was performed by 30 multistage, partially continuous countercurrent process Suc
using a LECO Model FP-528. Carbon and Sulfur cessfully operates at selected reactor ratios including 50/50
analysis was performed by using a LECO Model reactions to control crystal sizes.
SC-144DR Thus the following are two examples that describe testing
of reactor reaction ratios wherein 10% of the reaction would
Samples of the raw Miller gypsum, Reactor 1 filtration 35 occur in one reactor and 90% would occur in the other.
cake, Reactor 1 filtrate, final product filtration cake, Reactor In the reactors which contained only 10% of the reaction,
2 filtrate, and final water wash underwent metals quantita the reaction was complete since the driving force was
tive analysis; metals analyzed were arsenic, selenium, alu extreme towards finishing the reaction of the Small concen
minum, and magnesium; mercury analysis was also per tration of ammonium carbonate left in the ammonium Sul
formed. The results are shown in below Table 2. Comparing 40 fate solution fed to Reactor No. 1. Here, the full complement
the results shown in Table 1 (with acid wash of raw gypsum) of gypsum was present, or the Small complement of gypsum
with the results shown in Table 2 (no acid wash of raw left in the calcium carbonate slurry of Reactor 2 where there
gypsum) demonstrates that the acid wash was particularly was with a full complement of ammonium carbonate.
effective in reducing the amount of arsenic, selenium, alu When trying to react 90% of the gypsum with 100%
minum and magnesium. 45 complement of ammonium carbonate (or 10% excess of
ammonium carbonate), the reaction in Reactor 2 proceeded
TABLE 2 to about 70% in 10 minutes, but took approximately one (1)
hour to reach 100% conversion. This showed that for quick
Metals Analysis With Process Without Acid Wash of raw FGD Gypsum conversion of most gypsum with ammonium carbonate at
Magne 50 least 20% of the reaction should be done in one of the vessels
Test Step Arsenic Selenium Aluminum sium Mercury and this must require a stoichiometric advantage of one
reaction over the other of about 25 to 30% in each reactor in
Raw gypsum O.656 1O.S 369 1220 1.19
Reactor 1 cake O.914 9.08 52O 1370 O916 the present partially continuous counter-current batch pro
Reactor 1 filtrate 0.01.31 1.71 O.O140 3.32 ND cess. While no boundary conditions were determined perse,
Product cake O.997 4.19 780 1660 O491 55 this process information provides for flexibility and reduced
Reactor 2 filtrate 0.0207 3.89 1.01 ND 0.00557 process control of the operating plant.
Final water wash 0.00790 1.30 OSO1 ND O.OO154 To test the reactivity of the counter-current flow process
Solution results are reported in mg L and solid results are reported in mg/kg, with reactions of less than 50% in each reactor the following
ND = Not detected at the reporting limit. tests were performed.
60
Test 1
Pilot Plant Filtration Rates in Example 3 and Example 4
Filter rates have a significant impact on the steady and 10% of Reaction in Reactor No. 1 and 90% of
consistent flow of the multistage, partially continuous coun Reaction in Reactor No. 2
tercurrent processes of the present invention. Accordingly, 65
the following process parameters regarding rates of filtration Plant Miller FGD gypsum was washed with 93.7% sul
are set forth below: furic acid diluted to 1% by volume with water, followed by
 US 9,682,868 B2
41 42
water washing. The washed gypsum cake containing 65 mixed, the pH decreased from 9.20 to 7.68 with a significant
pounds of gypsum was fed to Reactor No. 1 where it was amount of foam formed. Aqua ammonia was sprayed in the
mixed with a liquid containing 10.5 pounds of 34.6% tank for about 10 seconds until the foam dissipated. After 10
solution ammonium carbonate or 0.0378 moles of ammo minutes of agitation at 77 to 82°F. the slurry was filtered.
nium carbonate, equal to 10% of that needed to react with 5 The gypsum conversion was 34.7%. Thus the filtrate con
0.378 moles of gypsum. In addition to the ammonium tained an ammonium sulfate content of about 44.7% leaving
carbonate solution, a solution containing 45 pounds of about 55.3% of the ammonium carbonate in the filtrate from
ammonium sulfate at 36% ammonium Sulfate was added to Reactor No. 1.
the mixture. The resulting solution mixture represented 90% Continuation of Test 2
of the reaction in Reactor No. 2. After 10 minutes of 10 In a continuation of the above Test 2, the resulting slurry
was filtered and the cake fed to Reactor No. 2. A 100%
agitation in Reactor No. 1, the slurry was filtered and Stoichiometric amount of ammonium carbonate based on the
ammonium carbonate was completely converted to ammo original gypsum feed to Reactor No. 1 was fed to Reactor
nium sulfate. The filtered gypsum cake was then fed to No. 2 simulating a partially continuous counter-current flow
Reactor No. 2 where 100% of the stoichiometric amount of
required ammonium carbonate for the original gypsum feed
15 process, thus resulting in 0.378 moles or 105 pounds of
34.6% ammonium carbonate. No external heat was added
was mixed with it under agitation. No external heat was during the reaction. After agitation of the mixture at 76.4 to
added during the reaction. To measure the completion of the 78.8°F. for five minutes, a slurry sample was pulled and the
reaction in Reactor No. 2, which represented a 10% excess rest of the gypsum was found to be 99% converted to
of ammonium carbonate in moles of reactant over that calcium carbonate. After 10 minutes in Reactor No. 2, the
needed by the original gypsum, slurry samples were taken in gypsum in the discharged slurry was completely converted
timed intervals where the reactant slurry was measured for to calcium carbonate.
gypsum conversion to calcium carbonate after filtration and
washing. The following Table 3 shows the results: Example 6
25
TABLE 3 Retention Time Tests
Product Yield as a Function of Reactor Retention Time
Objective: These tests checked the effect that the time
Retention Time (min) pH Temperature (deg. F.) % Conversion spent in the reactors has on crystal size, crystal morphology
5 46.9
30 and completeness of reaction with 50% of the gypsum
10 692
reacting in each reactor while simulating the process of
15 72.2 embodiment number 1, shown in FIG. 1.
30 8.58 82.3 83.6 Feed Material:
45
60
8.39
8.28
82.5
82.8
846
85.8%
Miller gypsum (8.3% water)
35 Ammonium Carbonate Solution (up to 33% by weight)
This value was determined by measuring carbon, nitrogen, and sulfur using the afore Ammonium Sulfate Solution (up to 36% by weight)
referenced LECO laboratory instruments. However, polarized light microscopy and Sulfuric Acid (1% by volume)
electron scanning microscope studies (see SEM image of FIG. 13) show that there was
100% conversion to calcium carbonate. Conversion at 30 minutes is estimated to be
approaching 100%,
Aqua Ammonia (29%)
Process Constant Parameters
Polarized light microscopy showed the calcium carbonate 40 For the tests, the reactor retention times used were 2, 5,
crystals measured less than one micron which is below the 10, 15, 20, 30, and 60 minutes.
size limits of polarized light microscopy but within the size Process Variable Parameters
limits of Scanning electron microscope detection. Scanning Parameters monitored and/or adjusted during the tests
electron microscope imaging of the product calcium car include pH, temperature, percent reaction of gypsum in each
bonate resulting from above Test 1 is shown in FIG. 13. 45 reactor, and aqua ammonia addition. The pH and tempera
From analysis of FIG. 13, the product is shown to be ture of the reactions were monitored throughout the reac
abundant in fine, well formed crystals that are 200 nanome tions. The pH remained between 6.8 and 8.8 with aqua
ters in size and Smaller. ammonia added as needed to stop any foaming. Tempera
tures were not controlled during the reaction and remained
Test 2 50 between 20.5° C. and 38° C. for all of the runs. The tests
were designed to produce a 50% reaction of gypsum in each
90% of the Ammonium Carbonate/FGD Gypsum in reactOr.
Reactor No. 1 and the Remainder in Reactor No. 2 Procedure
General Description of the Tests
The following procedure was performed. After washing 55 Each test was performed to simulate the partially con
the Plant Miller FGD gypsum with 93.7 sulfuric acid diluted tinuous countercurrent process illustrated in FIG. 1 (refer to
to 1% by volume with water, filtering and water washing, the FIG. 1) using two runs (a “run” is one completion of the
washed gypsum cake containing 65 pounds of gypsum was process from beginning to end). Run 1 was performed to
fed to Reactor No. 1. The washed gypsum cake was mixed produce the Ammonium Sulfate/Ammonium Carbonate
with a solution containing 94.2 pounds of 34.6% solution 60 Solution (18) for Reactor No. 1 (8) of Run 2 in order to
ammonium carbonate or 0.340 moles of ammonium carbon simulate the Solution produced by the countercurrent pro
ate, equal to 90% of that needed to react with 0.378 moles cess. Both of the runs were designed for 50% of the reaction
of gypsum. In addition to the ammonium carbonate solution, of the starting gypsum occurring in each reactor. Run 1 used
a solution of five (5) pounds of ammonium sulfate (at 36% a separately made (not made within operation of the process)
ammonium sulfate) was added to the mixture. The resulting 65 stoichiometric solution of 50:50 ammonium carbonate to
mixture represented 10% of the reaction to be performed in ammonium sulfate solutions to be used as the Ammonium
Reactor No. 2. Further, while all this material was being Sulfate/Ammonium Carbonate Solution (18) in Reactor No.
 US 9,682,868 B2
43 44
1 (8). This 50:50 solution contained the amount of ammo 5. After the designated retention time (2, 5, 10, 15, 20, 30,
nium carbonate needed to react with 50% of the Gypsum or 60 minutes), the slurry was filtered, and the filtrate
Cake (6) being fed to Reactor No. 1 (8) and the amount of was the Reactor No. 1 (8) Ammonium Sulfate Solution
ammonium sulfate solution that would result from 50% of Product (19). A 50 mL sample of this filtrate was
the gypsum having reacted. The Ammonium Carbonate/ 5 collected. In addition, a 1 g sample of the Calcium
Ammonium Sulfate Solution (18) from Reactor No. 2 (11) Carbonate and Gypsum Cake (10) was dried in a
of Run 1 was saved and used as the Ammonium Carbonate/ moisture balance and saved.
Ammonium Sulfate Solution (18) for Reactor No. 1 (8) of 6. Fresh up to 33% ammonium carbonate solution con
Run 2. The final Calcium Carbonate Product Cakes (14) taining 100% stoichiometric of Ammonium Carbonate
from Run 2 of each test were analyzed by polarized light 10 Solution (12) (calculated as mentioned above) was
microscopy. Percent nitrogen, Sulfur, and carbon were mea added to a beaker serving as Reactor No 2 (11). The
Sured using LECOR quantitative instruments (nitrogen ana residual Calcium Carbonate and Gypsum Cake (10)
lyzer was a LECOR) Model FP-528; carbon/sulfur analyzer from Reactor No. 1 (8) was added to this Ammonium
Carbonate Solution (12).
was a LECOR) Model SC-144DR). 15 7. The resulting slurry was mixed on a stir plate for the
For all runs of all tests, 50 mL samples were collected of designated retention time (2, 5, 10, 15, 20, 30, or 60
the Ammonium Sulfate Solution Product (19) from Reactor minutes). Any foaming was stopped by spraying aqua
No. 1 as well as a 1 g sample of the Calcium Carbonate and ammonia into Reactor No. 2 (11).
Gypsum Cake (10) from Reactor No. 1. In addition, the final 8. The slurry was filtered by Buchner funnel, and the
Calcium Carbonate Product Cakes (14) from each run were resulting Calcium Carbonate Product Cake (14) was
collected. washed and filtered with 268 mL of Grade I water.
Preparing Solutions 9. The Ammonium Sulfate/Ammonium Carbonate Solu
Ammonium Carbonate (up to 33%) prepared fresh daily tion (18) filtrate from Reactor No. 2 (11) before the
Placed 495 g of reagent grade ammonium carbonate with wash was kept to provide the Ammonium Sulfate/
1005 g of DI water in a beaker on a magnetic stir plate set 25 Ammonium Carbonate Solution (11) for Reactor No. 1
at 45° C. This solution was stirred until dissolved. (8) in Run 2 of the test. The Calcium Carbonate Product
Ammonium Sulfate (up to 36%) Cake (14) was dried overnight in an oven at 55° C.
Added 360 g of ammonium sulfate to 640 g of DI water. General Procedures for Retention Time Tests—Run 2:
This solution was stirred with no heat on a magnetic stir 1. 175 g of Miller gypsum was acid washed as described
plate until dissolved. 30 in Steps 1-2 of Run 1 above.
Calculating the Amounts of Ammonium Sulfate and 2. The washed and filtered gypsum was placed in a 1 L
Ammonium Carbonate to Use for the Test beaker with the Ammonium Sulfatef Ammonium Car
1. The percent of ammonium carbonate and ammonium bonate Solution (18) from Reactor No. 2 (11) of Run 1.
sulfate in each solution was found prior to the test work This beaker served as Reactor No. 1 (8) for Run 2.
by measuring the percent nitrogen in the solution using 35 3. Steps 4-8 of Run 1 were followed.
the LECOR). 4. The Calcium Carbonate Product Cake (14) was dried
2. Based on the percent nitrogen measurements, the overnight in an oven at 55° C. and the Ammonium
correct Stoichiometric amounts of ammonium carbon Sulfate/Ammonium Carbonate Solution (18) was dis
ate and ammonium Sulfate Solution to add were calcu carded.
lated using accepted methods. This calculation 40 Results
assumed that all of the nitrogen was in the form of The Calcium Carbonate Product Cakes from Reactor No.
ammonium carbonate or ammonium sulfate, depending 2 of Run 2 for each of the tests were evaluated optically by
on the Solution being measured. The number of moles polarized light microscopy (PLM) to check for any com
per mL were calculated and the amount needed to react pleteness of the reaction converting gypsum to calcium
with the desired percentage of gypsum (after adjusting 45 carbonate as well as crystal size and morphology of the
the weight for moisture content) was found in terms of calcium carbonate product. PLM provides an effective way
grams of solution. to directly detect the presence of even small amounts of
Procedure for Retention Time Tests—Run 1: residual unreacted gypsum in the product. The ability to
1. 175 g of Miller gypsum was washed in a 1% sulfuric distinguish the gypsum from the calcium carbonate is due to
acid solution (by Volume, adjusting for the moisture in 50 the difference in the refractive indices of gypsum and
the gypsum). The 1% sulfuric acid solution was pre calcium carbonate.
pared by adding 3.9 mL of concentrated sulfuric acid to Polarized Light Microscopy (PLM) General Description
371.6 mL of Grade 1 water and mixing well. After of the Calcium Carbonate Product
adding the gypsum, the slurry was mixed for 10 min This process of charging CaSO4.2H2O to concentrated
utes in a beaker using a magnetic stir plate. 55 solutions of (NH4)2CO results in the rapid precipitation of
2. The slurry was filtered, and the filtered Gypsum Cake Vaterite (CaCO) on the surface of the CaSO2HO crystals
was then rinsed with approximately 320 mL of Grade resulting in soft agglomerates of Vaterite spherulites ranging
1 water and filtered again. in size from 2L or less up to spherulites of 8L in diameter.
3. The washed and filtered Gypsum Cake (6) was placed The precipitation is so rapid that the Ca" ions are depleted
in a 1 L beaker with the calculated amount of fresh, up 60 before the spherulites are grown larger. Also, Subsequent
to 33% ammonium carbonate solution and up to 36% nucleation occurs before the original spherulites can develop
ammonium Sulfate solution. This beaker served as into larger units. These spherulites result when a seed crystal
Reactor No. 1 (8) as shown in FIG. 1. grows very rapidly on one face in all directions. The single
4. The slurry was mixed on a stir plate for the designated crystal length is half of the spherulite diameter and probably
retention time (2, 5, 10, 15, 20, 30, or 60 minutes). Any 65 /100 that size in diameter.
foaming was dissipated by spraying aqua ammonia into The spherulites form "husks” or “shells' at the surface of
the reactor. the gypsum crystal as they grow. They break away from the
 US 9,682,868 B2
45 46
Surface due to agitation of the slurry and form fragments that gypsum due to extremely low Surface area to weight
are loose agglomerates of spherulites. ratios is a good retention time in each reactor.
(2) A more preferred retention time in each reactor is 4
TABLE 4 minutes to 60 minutes.
PLM Results of Run 2 Calcium Carbonate Product Cake
(3) The most preferred retention time in each reactor is 8
minutes to 20 minutes.
Spherulite Estimated Using the reaction ratio of 50% reaction of gypsum in
**Diameter Residual Reactor No. 1 and Reactor No. 2 and a temperature of 25°
Reactor Spherulite of Gypsum Optically C., the retention times in the reactors shown above may be
Sample Retention Diameter Bulk Weight Observed Estimated % 10 used to produce a 100% conversion of gypsum to calcium
ID Time Range Fraction Optically Conversion
carbonate and ammonium Sulfate. However, as shown in
SCPO36
SCPO26
60
30
min.
min.
1-5.
2-7L
*NA
2-51.
Ole
Ole
100%
100%
further results, complete conversion was obtained at Reactor
SCPO16 20 min. 2-81. 3-41. Ole 100%
No. 1 to Reactor No. 2 gypsum reaction ratios of 20%:80%,
SCPO21 15 min. 2-51. *NA Ole 100% 30%:70%, 70%:30%, and 80%:20% as well as at reactor
SCPO31 10 min. 2-7L *NA Ole 100% 15 temperatures of 35° C., 45° C., and 55° C.
SCPO41
SCP051
5
2
min.
min.
2-81.
1-8.
5-81.
*NA
Ole
<10%
100%
90-100%
Note: Although not tested for these other reaction ratios
and temperatures, it would follow from understanding of
NRA = Not Available reaction speeds that some gypsums may require more than
**Diameter of Bulk Weight Fraction is the diameter of 95% by weight of the waterite a 10 minutes retention time in each reactor based on the size
spherulites,
and morphology of the gypsum crystals and the temperature
Analysis of Results of the reaction.
Referring to the test results presented in Table 4, polarized Example 7
light microscopy indicates that the calcium carbonate prod
uct from all of the retention time tests was consistently 25 Temperature Control Tests
formed as very small Vaterite spherulites between 1 and 8.
in diameter. By weight, 95% of the spherulites diameters Objective: This set of tests was designed to determine the
were between 2L and 5L for all but the 5 Minute Retention effect that temperature has on the completeness of reactions
Time Test.
and size and morphology of the calcium carbonate crystals
Polarized light microscopy results found residual gypsum 30 formed by the partially continuous countercurrent process
indicating an incomplete reaction in only of the 2 Minute by simulating the process shown in FIG. 1 and using two
Retention Time Calcium Carbonate Product Cake. reactors with 50% of the gypsum reacting in each reactor
Percent carbon for the Calcium Carbonate and Gypsum and using a retention time in each reactor of 20 minutes.
Cake from Reactor No. 1 of Run 2 of the 20 Minute Feed Materials: Same as described in the Retention Time
Retention Time test was measured. This test was chosen 35 tests
because the 20 minute retention time closely simulates the Process Constant Parameters
way the actual process will be run due to considerations of The temperatures 15° C. (599 F), 25° C. (77 F.), 35° C.
continuous filtration from dual 2-stage reactors feeding one (95° F.), 45° C. (113° F.), and 55° C. (131° F.) were tested
filter in sequence and was used as the retention time for in a simulation of the process shown in FIG. 1.
testing other process parameters discussed later. The carbon 40 Process Variable Parameters
measured by LECO was 4.45% which very closely matches Parameters monitored and/or controlled during the test
the expected value of 4.41% calculated for a stoichiometric include pH, retention time in the reactors, percent reaction of
mixture of 50% calcium carbonate and 50% gypsum, dem gypsum in each reactor, and addition of aqua ammonia to
onstrating that the recycled Ammonium Sulfate/Ammonium control foaming. The pH and temperature of the reactions
Carbonate Solution must have contained a 50% stoichio 45 were monitored throughout the reactions. The pH remained
metric amount of ammonium carbonate solution and that between 7.4 and 8.8 with the addition of aqua ammonia to
50% of the reaction is occurring in each reactor during the control foaming. The tests were designed to produce a 50%
partially continuous countercurrent process. This informa reaction of gypsum in each reactor.
tion combined with the 100% yield of calcium carbonate in Procedures
Reactor No. 2 means that there was a 100% yield of 50 The ammonium sulfate and ammonium carbonate solu
ammonium Sulfate. To further Support this, the Ammonium tions were prepared as described in the retention time tests
Sulfate Product Solution from the 20 Minute Retention Time of Example 6. The amount of each to use was determined as
Test, was crystalized and measured for percent Sulfur and described in those tests.
percent nitrogen using a LECOR) Model SC-144DR ana As discussed in the Retention Time Tests of Example 6,
lyzer for sulfur and a LECOR) Model FP-528 analyzer for 55 each test was performed with two runs to simulate the
nitrogen. The resulting measurements were 23.4% sulfur partially continuous countercurrent process shown in FIG. 1.
and 20.2% nitrogen. This gives a S:N ratio of 1.16 which The first run was done to produce the Reactor No. 2 filtrate
very closely matches the expected ratio of 1.14 for to use in Reactor No. 1 of the second run.
(NH4)2SO. Description of Run 1 for Each Test:
Conclusions 60 1. The gypsum was acid washed as described in Steps 1-2
Using the reaction ratio of 50% reaction of gypsum in of the Retention Time tests.
Reactor No. 1 and Reactor No. 2 and a temperature of 25° 2. To create a synthetic Solution representing the Ammo
C., the retention times in the reactors shown below produce nium Sulfate/Ammonium Carbonate Solution for Reac
a 100% conversion of gypsum to calcium carbonate and tor No. 1, a calculated amount of fresh up to 33%
ammonium sulfate: 65 ammonium carbonate Solution and up to 36% ammo
(1) 1 minute for highly reactive gypsum Such as finely nium sulfate solution representing a 50%:50% stoichio
ground gypsum to 24 hours for extremely unreactive metric amount of each was brought to the appropriate
 US 9,682,868 B2
47 48
temperature in a 1 L beaker either by heating or cooling TABLE 5-continued
the solution. This beaker served as Reactor No. 1 in
FIG. 1 and was either placed on a hot plate or in a PLM Results on Run 2 Calcium Carbonate Product Cake
waterfice bath as needed to maintain the desired tem Estimated
perature. During this time, the gypsum was either 5 Reactor Spherulite Residual
heated or cooled to the appropriate temperature. SCP Tem- Spherulite * Diameter of Gypsum Optically
Sample perature Diameter Bulk Weight Observed Estimated %
3. When the temperatures were stabilized, the gypsum ID (° C.) Range Fraction Optically Conversion
was added to the solution.
SCP057 35 1-61 2-51. Ole 100%
4. The desired slurry temperature was appropriately main 10 SCPO62 45 <1-61 <1-41. Ole 100%
tained as the slurry was mixed on a stir plate for 20 SCPO67 55 1-5. 2-31 Ole 100%
minutes, measuring the temperature and pH every 2
seconds. Any foaming was dissipated by spraying aqua
ammonia into the reactor. *Diameter of Bulk Weight Fraction is the diameter of 95%
by weight of the Vaterite spherulites.
5. After 20 minutes of reacting, the slurry was filtered, and 15 Polarized light microscopy analysis also showed that the
the filtrate was the Ammonium Sulfate Product Solu morphology of all of the Calcium Carbonate Product Cakes
tion. A 50 mL sample of the filtrate was collected as was characterized as Vaterite in the shape of spherulites of
well as a 1 g sample of the Calcium Carbonate and needle crystals radiating from a center point.
Gypsum Cake. Analysis of Results
6. Fresh up to 33% ammonium carbonate solution con Referring to the test results presented in Table 5, polarized
taining a 100% stoichiometric amount of ammonium light microscopy showed the conversion to be 100% for all
carbonate was added to a 1 L beaker serving as Reactor but the 15° C. Test which showed 99-100% conversion.
No. 2. The temperature of this solution was adjusted to Conclusions
the desired temperature. Using the reaction ratios of 50% reaction of gypsum in
25 Reactor No. 1 and Reactor No. 2 with a retention time of 20
7. The residual cake from Reactor No. 1 was also brought minutes in each, the following range of process temperature
to the desired temperature and then added to the parameters in each reactor may be used for 100% reaction of
ammonium carbonate Solution in Reactor No. 2.
gypsum to produce ammonium sulfate and calcium carbon
8. The slurry temperature was appropriately maintained, ate: 5° C. (41°F) to 80° C. (1769 F).
and the slurry was mixed on a stir plate for 20 minutes. 30
The temperature and pH were recorded every 2 sec Example 8
onds. Any foaming was dissipated by spraying aqua
ammonia into Reactor No. 2. Ratio Tests
9. The slurry was filtered by Buchner funnel. The result
ing Calcium Carbonate Product Cake was then washed 35 Objective: These tests simulated the process in FIG. 1 to
with 268 mL of Grade I water, filtered, and dried check the limits of the percentage of gypsum that must react
overnight in an oven at 55° C. in Reactor No. 1 to ensure completeness of reaction. For the
10. This filtrate before washing with water from Step 9 tests, a retention time of 20 minutes and ambient tempera
was saved to use as the Ammonium Sulfate/Ammo tures were used since they most closely simulate the time
nium Carbonate Solution in Reactor No. 1 of Run 2. 40 and temperatures for the way the actual process will run due
to considerations of continuous filtration from dual 2-stage
Description of Run 2 for Each Test: reactors feeding one filter in sequence and was used as the
1. The gypsum was acid washed as described previously. retention time for testing other process parameters dis
2. The Reactor No. 2 Ammonium Sulfate/Ammonium cussed.
Carbonate Solution filtrate from Run 1 was brought to 45 Feed Material: Same as described in the Retention Time
the desired temperature in a 1 L beaker serving as tests of Example 6.
Process Constant Parameter
Reactor No. 1. At the same time the gypsum was also
brought to the desired temperature. The reactor percent ratio of gypsum reacting in each
reactor to be tested are 80%:20%, 20%:80%, 70%:30%,
3. Steps 3-9 were completed as described in Run 1 above. 50 30%:70%. These values represent the percentage of gypsum
Results that is reacted in FIG. 1, Reactor No. 1 and Reactor No. 2,
The Calcium Carbonate Product Cake for each test from respectively. For example, the 80%:20% ratio means that
Reactor No. 2 of Run 2 were evaluated optically by Polar 80% of the gypsum is reacted in Reactor No. 1 and 20% is
ized Light Microscopy (PLM) to check for completeness of reacted in Reactor No. 2. So for the 80%:20% test, the
reaction and product size and morphology. 55 Ammonium Sulfate/Ammonium Carbonate Solution fed to
Reactor No. 1 contains the Stoichiometric amount of ammo
TABLE 5 nium carbonate to react with 80% of the gypsum in Reactor
No. 1. It follows then that the Calcium Carbonate and
PLM Results on Run 2 Calcium Carbonate Product Cake Gypsum Cake feeding Reactor No. 2 of FIG. 1 contains 20%
Estimated
60 remaining unreacted gypsum that reacts in Reactor No. 2.
Reactor Spherulite Residual Process Variable Parameters
SCP Tem- Spherulite * Diameter of Gypsum Optically Parameters monitored and/or adjusted during the reaction
Sample perature Diameter Bulk Weight Observed Estimated 9% include pH, temperature, retention time, and aqua ammonia
ID (° C.) Range Fraction Optically Conversion addition. The pH and temperature of the reactions were
SCPO77 15 1-12. 2-4. <1% 99-100% 65 monitored throughout the reactions. The pH remained
SCPO72 25 1-7. 3-41. Ole 100% between 7.3 and 8.8 even with aqua ammonia added as
needed to stop any foaming. Temperatures were not con
 US 9,682,868 B2
49 50
trolled during the reaction and remained between 20.5° C. TABLE 6-continued
and 38° C. for all of the runs. The retention time in each
reactor was 20 minutes. Polarized Light Microscopy of Run 2 Calcium Carbonate Product Cakes
Procedures Test Description Estimated Residual
All solutions were prepared as described in the Retention 5 SCP Sample Based on 96 Reaction Gypsum Observed %
Time tests in Example 6. As discussed in Example 6, each ID of Gypsum in *R1:R2 Optically Conversion
test was performed with two runs using the Reactor No. 2 SCPO92 30:70 Ole 100%
filtrate from the first run as the Ammonium Sulfate/Ammo SCP097 70:30 Ole 100%
nium Carbonate Solution in Reactor No. 1 of the second R1 = Reactor No. 1 and R2 = Reactor No. 2
10
Run. This is done so that Run 2 best simulates the process
shown in FIG. 1. Analysis of Results
Ratio 20:80 Test Run 1: Referring to the test results shown in Table 6, both the
1. 175 g of Miller gypsum was acid washed as described PLM results show that all of the retention times tested
in Steps 1-2 of the Retention Time Test. 15 converted gypsum to calcium carbonate with a percent yield
2. The calculated amount of fresh up to 33% ammonium of 99-100%.
carbonate solution and up to 36% ammonium sulfate Conclusions
Solution was placed in a 1 L beaker (representing Using a reactor retention time of 20 minutes in each
Reactor No. 1) with the washed gypsum. The amount reactor at 25°C., the Stoichiometric percent ratios of gypsum
of ammonium carbonate and ammonium Sulfate solu reacting in Reactor No. 1 to Reactor No. 2 of 20%:80%,
tion to use was found based on the nitrogen analyses of 80%:20%, 30%:70%, and 70%:30% were tested and showed
the solutions and the appropriate weights to provide the a 99-100% conversion of gypsum to calcium carbonate.
Stoichiometric amount of ammonium carbonate for Reducing the retention time to less than 20 minutes in each
20% of the gypsum fed to Reactor No. 1 to react and reactor may produce an incomplete reaction.
the Stoichiometric amount of ammonium Sulfate that 25
would have resulted from 80% of that gypsum having Example 9
reacted. This simulates the Ammonium Sulfate/Ammo
nium Carbonate Solution that would have come from Excess Aqua Ammonia in Reactor No. 1
Reactor No. 2 of the process in FIG. 1 for a reaction 30
ratio of 20%:80%. Objective: This test was designed to check the use of
3. The rest of Run 1 was completed by following Steps excess ammonia in Reactor No. 1 by simulating the process
4-9 of Run 1 of the Procedure for Retention Time Tests. shown in FIG. 1. The excess aqua ammonia was added to
Ratio 20:80 Test Run 2: prevent loss of carbon dioxide due to foaming.
1. 175 g of fresh Miller gypsum was acid washed as Feed Materials: Same as described in the Retention Time
35
before. tests of Example 6.
2. The Ammonium Sulfate/Ammonium Carbonate Solu Process Constant Parameters
tion filtrate from the 20:80 Reactor No. 2 Run 1 Test While simulating the process in FIG. 1 for this test, the pH
was placed with the washed and filtered gypsum in a 1 was monitored and remained between 8.1 and 9.1. A reten
L beaker serving as Reactor No. 1. 40 tion time of 20 minutes was used in each reactor and the
3. Steps 5-8 of Run 1 of the Retention Time tests were reactions were designed for a 50% reaction of gypsum in
completed. each reactor. Aqua ammonia was added initially in Reactor
10. The slurry from Reactor No. 2 was filtered by Buchner No. 1. Additional aqua ammonia to prevent foaming was
funnel, and the resulting Calcium Carbonate Product needed only in Reactor No. 2. The temperature of the slurry
Cake was washed and filtered with 268 mL of Grade I 45 was not monitored during the process and was not controlled
Water. with any addition or removal of heat.
4. The product cake was dried overnight in an oven at 55° Procedures:
C. The test simulated the process shown in FIG. 1 by making
The above described test was repeated, changing the feed two runs through the process. Run 1 was designed to
Solutions to produce an 80% reaction of gypsum in Reactor 50 produce an Ammonium Sulfate/Ammonium Carbonate
No. 1 and 20% reaction in Reactor No. 2. The test was also Solution (18) from Reactor No. 2 (11) to use in Reactor No.
repeated for 30%:70% and 70%:30% reactions. 1 of Run 2. The flow of materials in both Runs are similar
Results to the flows used in the Retention Time tests.
As discussed in Examples 6 and 7, polarized light micros Extra Aqua Ammonia Run 1
copy was used to check for completeness of reaction by 55 1) All solutions were prepared as previously described in
checking for residual gypsum in the calcium carbonate the Retention Time Tests.
product. 2) 175 g of acid washed gypsum as described in the
Retention Time Tests was added to a 1 L beaker with
TABLE 6 serving as Reactor No. 1 in FIG. 1.
Polarized Light Microscopy of Run 2 Calcium Carbonate Product Cakes
60 3) The stoichiometric amounts of up to 33% ammonium
carbonate and up to 36% ammonium sulfate that would
Test Description Estimated Residual be the amounts related to a 50% reaction of gypsum
SCP Sample
ID
Based on 9% Reaction Gypsum Observed
of Gypsum in *R1:R2 Optically
%
Conversion
was added to the beaker. The weights of each were
calculated as described in the Retention Time Test.
SCPO82 20:80 <1% 99-100% 65 Also, 19.7 g of 29% aqua ammonia was added.
SCP087 80:20 Ole 100% 4) The slurry was mixed for 20 minutes, and no foaming
was seen during the process.
 US 9,682,868 B2
51 52
5) The Calcium Carbonate and Gypsum Cake was filtered, Conclusions
and a 1 g sample was collected. A 50 mL sample of the Referring to the test results shown in Table 7, use of
resulting Ammonium Sulfate Solution Product was also excess aqua ammonia in the first reactor stopped foaming in
saved. the reactor. The foaming was also reduced in the second
reactOr.
6) The residual Calcium Carbonate and Gypsum Cake Polarized light microscopy (PLM) identified approxi
was placed in a 1 L beaker with 100% of the stoichio mately 33% calcite and approximately 67% Vaterite in the
metric amount of ammonium carbonate needed to react product.
with the starting gypsum. This served as Reactor No. 2. To neutralize the ammonia added for control of foaming,
7) This slurry was mixed for 20 minutes. The slurry began 10 Sulfuric acid may need to be added to the ammonium sulfate
foaming immediately and 5.0 g of aqua ammonia was product.
added to control foaming.
8) After 20 minutes of mixing, the slurry was filtered and Example 10
the Ammonium Sulfate/Ammonium Carbonate Solu
tion was saved to use in Reactor No. 1 of Run 2. The Calcium Sulfate Hemihydrate Test
15
cake was rinsed with 268 g of Grade 1 water and Objective: Since gypsum may easily be converted to
filtered again. The resulting Calcium Carbonate Prod calcium sulfate hemihydrate with the use of pressure and/or
uct Cake was dried in a 55° C. oven overnight. heat, a test was performed to check the use calcium sulfate
Extra Aqua Ammonia Run 2 hemihydrate as a reactant in the partially continuous coun
1) 175 g of acid washed gypsum as described previously tercurrent process to produce calcium carbonate and ammo
was added to a 1 L beaker with the Ammonium nium sulfate.
Sulfate/Ammonium Carbonate Solution from Reactor Feed Material: The materials used are the same as those
No. 2 of Run 1. This served as Reactor No. 1. used for the Retention Time Tests of Example 6, except that
2) 20.0 g of 29% aqua ammonia was added to Reactor No. Millergypsum was replaced with Plaster of Paris. Note that
1 at the start of the process. The slurry was mixed for 25 Plaster of Paris, is produced by heating gypsum to calcium
20 minutes. No foaming was seen during the process. Sulfate hemihydrate according to the reaction:
3) The resulting Calcium Carbonate and Gypsum Cake CaSO2H2O+heat->CaSO.0.5H2O+1.5H2O (released as
was filtered. A 50 mL sample of the filtrate was saved steam).
as the Ammonium Sulfate Solution Product. A 1 g, Process Variable Parameters
sample of the Calcium Carbonate and Gypsum Cake 30 Parameters monitored and/or adjusted during the tests
was collected. The residual Calcium Carbonate and include pH, temperature, percent reaction of gypsum in each
Gypsum Cake was placed in a 1 L beaker with a 100% reactor, and aqua ammonia addition. The pH of the reactions
Stoichiometric amount of ammonium carbonate needed were monitored throughout the reactions. The pH remained
to react with the starting gypsum. This served as between 7.6 and 8.8 with aqua ammonia added as needed to
Reactor No. 2. 35 stop any foaming. Temperatures were not monitored or
4) This slurry was mixed for 20 minutes. Initially, slight controlled during the reaction, and there was no addition or
foaming that quickly dissipated on its own occurred. removal of heat. The tests were designed to produce a 50%
No acqua ammonia was added. reaction of calcium sulfate hemihydrate in each reactor
5) After 20 minutes of mixing, the slurry was filtered, using Plaster of Paris.
rinsed with 268 g of Grade 1 water and filtered again. 40 Procedure
The resulting Calcium Carbonate Product Cake was Preparing Solutions
dried in a 55° C. oven overnight. All solutions were prepared as described in the Retention
Results Time Tests.
The product Calcium Carbonate Product Cake from Run Hemihydrate Run 1:
2 was analyzed by polarized light microscopy (PLM) to 45 1. 160.0 g of calcium sulfate hemihydrate was mixed with
check the crystal size, morphology, and completeness of 166.4 g of ammonium carbonate solution (7.97% N)
reaction. and 175.7 g of ammonium sulfate solution (7.55% N)
serving as a synthetic Ammonium Sulfate/Ammonium
TABLE 7 Carbonate Solution for Reactor No. 1 as shown in FIG.
50 1. This was mixed in a 1 L beaker for 20 minutes which
PLM Analysis of Calcium Carbonate Product served as Reactor No. 1. Due to extensive foaming,
Estimated 19.6 g of aqua ammonia was added.
Residual 2. The slurry was filtered and the residual Calcium
Gypsum Optically Carbonate and Gypsum Cake was used in Reactor No.
Sample Observed Estimated 96 55 2. The filtrate was the Ammonium Sulfate Solution
ID # Description PLM Summary Optically Conversion Product for Run 1 and a 50 mL sample was saved.
SCP122 Extra Aqua This sample is Ole 100% 3. The Calcium Carbonate and Gypsum Cake was mixed
Ammonia
Run 2
estimated to
be -2.3 waterite as
with 332.9 g of up to 33% ammonium carbonate
agglomerates of solution (7.97% N) in a 1 L beaker. This beaker served
spherulites. These 60 as Reactor No. 2.
spherulites range up 4. The slurry was mixed for 20 minutes. It was then
to 71 in size. About filtered and rinsed with 268 mL of Grade 1 water. The
1/3 of this sample filtrate before rinsing was collected as the Ammonium
is single crystals Sulfate/Ammonium Carbonate Solution for use in
of calcite up to
61 in size. 65 Reactor No. 1 of Run 2. The Calcium Carbonate
Product Cake collected was dried overnight in a 55° C.
OVC.
 US 9,682,868 B2
53 54
Hemihydrate Run 2: normally is Ammonium Sulfate/Ammonium Carbonate
5. 160.0 g of calcium sulfate hemihydrate was mixed for Solution from Reactor No. 2 of the process shown in FIG.
20 minutes with the Ammonium Sulfate/Ammonium 1.
Carbonate Solution from Run 1 in a 1 L beaker that Steps of the Test:
served as Reactor No. 1. 5 1) All solutions were prepared as previously described in
6. Due to extensive foaming, 19.4 g of aqua ammonia was the Retention Time Tests.
added during the process. 2) 175 g of acid washed Miller gypsum (prepared as
7. The slurry was filtered and filtrate was the Ammonium described in the retention time tests) was added to a 1
Sulfate Solution Product for Run 2. The residual Cal
10
L beaker serving as Reactor No. 1 in FIG. 1 with 20 mL
cium Carbonate and Gypsum Cake was used in Reactor of 29% aqua ammonia (15.8 g) and a 50% stoichio
No. 2. metric amount of up to 36% ammonium sulfate. After
8. The Calcium Carbonate and Gypsum Cake was slurried mixing the slurry, a 50% stoichiometric amount of up
with 332.9 g of Ammonium Carbonate Solution in a 1 to 33% ammonium carbonate was added. The weights
L beaker serving as Reactor No. 2. This slurry was 15
of each were calculated as described in the Retention
mixed for 20 minutes with no foaming during the Time Test.
process. 3) The slurry was mixed for 20 minutes. During the course
9. The slurry was then filtered and rinsed with 260 mL of of the reaction, an additional 16.0 g of 29% aqua
Grade 1 water. The resulting Calcium Carbonate Cake ammonia was added to maintain the pH of the reaction
was dried overnight in a 55° C. oven. at 9.0. No foaming was seen during the process.
Results 4) The Calcium Carbonate and Gypsum Cake was filtered
The Run 2 Calcium Carbonate Product Cake was evalu and placed in a 1 L beaker with 100% of the stoichio
ated by polarized light microscopy. The results are presented metric amount of ammonium carbonate needed to react
below. with the starting gypsum. This served as Reactor No. 2.
SCP-127 Run 2 Calcium Carbonate Product Cake 25 5) The slurry was mixed for 20 minutes while adding 54.4
The calcium sulfate hemihydrate has converted to <1-2u. g of 29% aqua ammonia throughout to maintain a pH
crystals of calcium carbonate. No residual calcium Sulfate of 9.0.
hemihydrate was identified. 9) After 20 minutes of mixing, the slurry was filtered,
Analysis of Results rinsed with 268 g of Grade 1 water and filtered again.
The conversion of the calcium sulfate hemihydrate to 30
The resulting filter cake was dried in a 55° C. oven
calcium carbonate was found by PLM; and no residual overnight.
calcium sulfate hemihydrate was identified, indicating a Conclusions
complete reaction of the calcium sulfate hemihydrate to The product was analyzed by polarized light microscopy
calcium carbonate.
Conclusions 35 and no residual gypsum was present, indicating a 100%
The partially continuous countercurrent process using conversion of gypsum to calcium carbonate and ammonium
calcium sulfate hemihydrate demonstrated 100% conversion Sulfate. The Solid product was made up of Submicroscopic
to produce calcium carbonate and ammonium sulfate. The crystalline calcium carbonate.
crystal size of the calcium carbonate product produced was Example 12
up to 2L. The use of calcium sulfate hemihydrate avoids 40
some of the water that dilutes the ammonium sulfate prod
uct. Anhydrous Calcium Sulfate Test
Example 11 Objective: This test checks the viability of using anhy
45 drous calcium Sulfate in the partially continuous counter
pH of 9.0 Maintained with Aqua Ammonia current process by simulating the process shown in FIG. 1
Addition using Anhydrous Calcium Sulfate in place of Gypsum Cake
(6).
Objective: This test was designed check the effects of Feed Material: Same as Retention Time Tests of Example
elevated pH on the calcium carbonate product of the par 50 6, except that Miller gypsum was replaced with reagent
tially continuous countercurrent process by simulating the grade anhydrous calcium sulfate that was ground to -100
process shown in FIG. 1 while adding aqua ammonia mesh and assumed to have no moisture content.
throughout the process to maintain a pH of approximately Process Variable Parameters
9.0 in both reactors.
Feed Materials: Same as described in the Retention Time 55
The pH and temperature were monitored throughout the
tests in Example 6. test and ranged between 6.8 to 8.9 and 26° C. to 45° C.
Procedures respectively. The test was designed to simulate the process
During this test, aqua ammonia was continually added to shown in FIG. 1 and to produce 50% of the reaction of the
each reactor shown in FIG. 1 to maintain a pH of approxi anhydrous calcium Sulfate in each reactor and a 20 minute
retention time which is favored due to the filtration consid
mately 9.0. The retention time tested was 20 minutes in each 60
reactor with a 50% reaction of gypsum in each which is erations mentioned in the Retention Time Tests of Example
favored due to the filtration considerations mentioned in the 6.
Retention Time Tests of Example 1. The temperature Procedure
throughout the process ranged from 20°C. to 45°C. The test Unlike the Retention Time Tests of Example 6, only Run
was run only once with the starting Solution in Reactor No. 65 1 was performed using a simulated 50:50 stoichiometric
1 being a 50%:50% stoichiometric mix of ammonium car mixture of Ammonium Sulfate/Ammonium Carbonate Solu
bonate and ammonium sulfate to simulate the Solution that tion.
 US 9,682,868 B2
55 56
1) All solutions were prepared as described in the Reten Sulfate/Ammonium Carbonate Solution from Reactor No. 2
tion Time Tests. of the process shown in FIG. 1.
2) 126.6 g of reagent grade anhydrous calcium sulfate (to Steps of the Test:
replace the Gypsum Cake (6) in FIG. 1) was mixed 1) All solutions were prepared as previously described in
5 the Retention Time Tests.
with 162.1 g of ammonium carbonate solution (8.05%
N) and 178.1 g of ammonium sulfate solution (7.33% 2) 175 g of acid washed Miller gypsum (prepared as
N) in a 1 L beaker for 20 minutes. This beaker served described in the Retention Time Tests) was added to a
as Reactor No 1 of FIG. 1. Due to foaming, 11.3 g of 1 L beaker serving as Reactor No. 1 in FIG. 1 with 25.1
29% aqua ammonia was added. 10
g of 29% aqua ammonia and a 50% stoichiometric
3) The slurry was filtered and the residual calcium car amount of up to 36% ammonium Sulfate. After mixing
bonate and anhydrous calcium sulfate cake (which is the slurry, a 50% stoichiometric amount of up to 33%
labeled Calcium Carbonate and Gypsum Cake (10) in ammonium carbonate was added. The weights of each
FIG. 1) was used in Reactor No. 2. The filtrate was the were calculated as described in the Retention Time
Ammonium Sulfate Solution Product. A 50 mL sample 15
Test.
of this filtrate was collected and saved. A 1 g sample of 3) The slurry was mixed for 20 minutes. During the course
the Reactor No. 1 cake was also collected. of the reaction, an additional 45.2 g of 29% aqua
4) The cake from Reactor No. 1 was mixed with 324.3 g ammonia was added to maintain the pH of the reaction
of ammonium carbonate solution (8.05% N), represent at 9.4.
ing a 100% stoichiometric amount of ammonium car 4) The Calcium Carbonate and Gypsum Cake was filtered
bonate, in a 1 L beaker. This beaker served as Reactor and placed in a 1 L beaker with 100% of the stoichio
No. 2. metric amount of ammonium carbonate needed to react
5) The slurry was mixed for 20 minutes. It was then with the starting gypsum and 16.3 g of 29% aqua
filtered and rinsed with 268 mL of Grade 1 water and ammonia. This served as Reactor No. 2.
filtered again. The cake collected was dried overnight 25 5) The slurry was mixed for 20 minutes while adding 77.6
in a 55° C. oven. g of 29% aqua ammonia throughout to maintain a pH
Results of 9.4.
The Calcium Carbonate Product Cake was evaluated by 6) After 20 minutes of mixing, the slurry was filtered,
polarized light microscopy (PLM) to identify the complete rinsed with 268 g of Grade 1 water and filtered again.
ness of reaction by visually estimated any unreacted residual 30
The resulting filter cake was dried in a 55° C. oven
anhydrous calcium sulfate. PLM was also used to measure overnight.
the crystal size. The results are presented below. Conclusions
SCP-138 Anhydrous Calcium Sulfate Test Calcium Car The product was analyzed by polarized light microscopy
bonate Product Cake
The bulk fraction (>95% by weight) of this sample is 35 and no residual gypsum was seen, indicating a 100% con
agglomerates of <1 to 1L spheres of Vaterite. version of gypsum to calcium carbonate and ammonium
Analysis of Results sulfate. As in the pH 9.0 test, approximately 90% of the solid
Since no residual anhydrous calcium sulfate was identi product was made up of Submicroscopic crystalline calcium
fied in the sample, there was a 100% conversion of anhy carbonate.
drous calcium sulfate to calcium carbonate. Also, the crystal 40 Thus, from the results of the Example for Reactor Reten
size of the product was extremely small at <1 to 1L. tion Time Tests in Example 6, and the above results, the
Conclusions process of the present invention, particularly as shown in
Anhydrous calcium sulfate reacted very quickly and dem FIG. 1, operates at a pH range of 6.8 to 9.4 to result in 100%
onstrated 100% conversion in the partially continuous coun or 99-100% yield of product calcium carbonate and ammo
tercurrent process to produce calcium carbonate and ammo 45 nium sulfate.
nium sulfate. Polarized light microscopy showed that the
Solid product was Submicroscopic crystalline calcium car Example 14
bonate.
Tests Employing FGD Gypsum from Different
Example 13 50 Sources

Approximate 9.4 pH Maintained with Aqua The above described Pilot Plant tests and lab tests of
Ammonia Addition Examples 1-5 employed FGD gypsum obtained from South
A test like the 9.0 pH Test in Example 11, was performed 55
ern Company, Miller Electric Power Generating Plant, Ala
with additional aqua ammonia used to maintain a pH of bama. However, gypsum from all sources have distinctive
approximately 9.4 in both reactors. Like the pH 9.0 Test, this crystalline characteristics, including distinguishing charac
test was performed by simulating the process shown in FIG. teristics between FGD gypsum from individual electric
1. power plants. These characteristics have a direct impact on
Procedures 60 the reactivity and purity of the gypsum and thus the product
During this test, aqua ammonia was continually added to yield and purity of products resulting from the processes of
each reactor as shown in FIG. 1 to maintain a pH of the present invention.
approximately 9.4. The temperature throughout the process Accordingly, the two stage, two reactor process embodi
ranged from 22°C. to 40°C. The test was run only once with ment number 1 of the present invention as shown in FIG. 1
the starting solution in Reactor No. 1 being a 50%:50% 65 was tested using FGD gypsum from power plants other than
Stoichiometric mix of ammonium carbonate and ammonium the Miller Plant. Including Plant Miller, FGD gypsum was
Sulfate to simulate the solution that normally is Ammonium tested from the following five power plants:
 US 9,682,868 B2
57 58
1) Southern Company, Miller Electric Power Generating above for laboratory tests in the section, entitled Laboratory
Plant, Quinton, Ala. (Plant Miller) Gypsum Conversion Countercurrent Batch Process Equip
2) Southern Company, Gorgas Electric Generating Plant, ment and Procedure which used gypsum from Plant Miller.
Parrish, Ala. (Plant Gorgas) The FDG gypsum was washed with a 5% solution of
3) Southern Company, Bowen Power Plant in Euharlee, sulfuric acid and then water washed before being fed to
Ga. (Plant Bowen) Reactor 1. A fresh solution of ammonium carbonate was fed
4) Southern Company, Crist Generating Plant, Pensacola, to Reactor 2 as would be needed to supply 100% of the
Fla. (Plant Crist) Stoichiometric requirement for reaction with the incoming
5) Southern Company, Wansley Power Plant in Carroll gypsum. To ensure a 50% reaction of the gypsum in each
ton, Ga. (Plant Wansley) 10 reactor (Reactor 1 and Reactor 2), a fresh ammonium
Tests of employing different FGD gypsum in the two carbonate? ammonium sulfate solution with 50% of the stoi
reactor process of the present invention were the following: chiometric requirement of ammonium carbonate was fed to
a) two pilot plant tests using FGD gypsum from Plant Reactor 1 along with the incoming gypsum. This allowed
Gorgas; and both Reactor 1 and Reactor 2 to operate in simulation of a
b) three laboratory tests using FGD gypsum from Plant 15 partially continuous countercurrent process wherein Reac
Bowen, Plant Crist, and Plant Wansley. tors 1 and 2 were both operating at a 100% stoichiometric
The following tests were performed to assure that the excess, the excess being gypsum in Reactor 1 and the excess
multistage, partially continuous counter current process for being ammonium carbonate in Reactor 2. The reaction time
conversion of gypsum and ammonium carbonate to calcium was 20 minutes in each reactor and 120° F. was the tem
carbonate and ammonium sulfate would perform satisfacto perature in each reactor. The final product contained 97.1%
rily using gypsum of several crystal types. calcium carbonate with 2.9% being impurities consisting
TESTI—Gorgas) FGD Gypsum from the Plant Gorgas has primarily of magnesium, silicon and aluminum compounds.
a thicker crystalline form (see FIG. 3) than the gypsum The process operated successfully to produce 100% conver
produced at Plant Miller (see FIG. 4). With the following sion to calcium carbonate not including impurities and thus
variations, the test was as performed and described in the 25 stoichiometrically, 100% to ammonium sulfate.
above section entitled, Pilot Plant Gypsum Conversion TEST IV Crist) Using gypsum from Plant Crist (see FIG.
Countercurrent Batch Process Equipment and Procedure as 6) a lab test was performed to determine process efficiency.
exemplified in the section entitled, Pilot Plant Tests For Two The test was performed under the same conditions as the
Reactor Process, which used gypsum from Plant Miller: Plant Bowen gypsum described above (TEST III). The final
1) The gypsum was acid washed with 1% sulfuric acid, 30 product was 96.6% calcium carbonate with 3.4% impurities
then washed with water. consisting mainly of magnesium, silicon, and aluminum
2) The filtrate from Reactor 2 which was reclaimed by the compounds. The process operated successfully to produce
last belt filter was fed to Reactor 1. Because analysis 100% conversion to calcium carbonate not including impu
showed that the filtrate was weak in ammonia, anhy rities and thus stoichiometrically, 100% to ammonium sul
drous ammonia was fed to Reactor 1 for three minutes 35 fate.
at a flow rate of 2.21 scfm (standard cubic feet per TEST V Wansley) Using gypsum from Plant Wansley (see
minute). The resulting reactor temperature varied from FIG. 7) a lab test was performed to determine process
100 to 110° F. efficiency. The test was performed under the same condi
3) A reaction time of 20 minutes was used in each reactor. tions as the previous examples using Bowen and Crist
4) In Reactor 2, anhydrous ammonia was added at a rate 40 gypsums (TESTs III and IV). The final product was 96.9%
of 2.17 scfm for three minutes to build the ammonium calcium carbonate with 3.1% impurities consisting mainly
strength up to a normal level. The resulting temperature of magnesium, silicon, and aluminum compounds. The
in Reactor 2 was 100 to 105° F. process operated successfully to produce 100% conversion
The resulting product was 98.7% calcium carbonate with to calcium carbonate not including impurities and thus
1.2% impurities Such as magnesium oxide, silicon oxide, 45 stoichiometrically, 100% to ammonium sulfate.
aluminum oxide and others. The process operated Success In Summary, the results of operating the present two
fully to produce 100% conversion to calcium carbonate not reactor process with different types of gypsum crystals are
including impurities and thus stoichiometric ally, 100% to the following.
ammonium sulfate. Summary of Process Yields and Purities for Converting
TEST II Gorgas) In a second test using FGD gypsum from 50 Gypsum from Various Sources
Plant Gorgas, the operation was in the pilot plant and the Plant Gorgas: 100% conversion to calcium carbonate and
same as above except no anhydrous ammonia was added. thus also to ammonium Sulfate, not including impurities.
However, some extra ammonium carbonate was added to The resulting product was 98.7% calcium carbonate with
Reactor 2 because the ammonia level in the ammonium 1.2% impurities such as magnesium oxide, silicon oxide,
carbonate fed to Reactor 2 was low. Reactor 1 was operated 55 aluminum oxide and others.
at a temperature of 113°F. and Reactor 2 temperature varied Plant Gorgas: 100% conversion to calcium carbonate and
from 100 to 105 F. Again each reactor was operated for 20 thus also to ammonium Sulfate, not including impurities.
minutes. The resulting product was 98.3% calcium carbon The resulting product was 98.3% calcium carbonate with
ate with 1.7% impurities primarily consisting of magnesium, 1.7% impurities primarily consisting of magnesium, silicon
silicon and aluminum compounds as in the previous 60 and aluminum compounds and others.
example (TEST I). The process operated successfully to Plant Bowen: 100% conversion to calcium carbonate and
produce 100% conversion to calcium carbonate not includ thus also to ammonium Sulfate, not including impurities.
ing impurities and thus stoichiometrically, 100% to ammo The final product contained 97.1% calcium carbonate with
nium sulfate. 2.9% being impurities consisting primarily of magnesium,
TEST III Bowen) Using FGD gypsum from Plant Bowen 65 silicon and aluminum compounds.
(see FIG. 5), a lab test was performed to determine process Plant Crist: 100% conversion to calcium carbonate and
efficiency. The gypsum was tested as previously described thus also to ammonium Sulfate, not including impurities.
 US 9,682,868 B2
59 60
The final product was 96.6% calcium carbonate with 3.4% of the solution is increasingly more difficult to achieve
impurities consisting mainly of magnesium, silicon, and unless, as by turbulent flow or using a mixer, the reacted part
aluminum compounds. of the granule is shaken off the remaining particle.
Plant Wansley: 100% conversion to calcium carbonate The thicker and more spherical form of the Plant Gorgas
and thus also to ammonium sulfate, not including impurities. FGD gypsum led to the conclusion that the Gorgas gypsum
The final product was 96.9% calcium carbonate with 3.1% crystals had less Surface area and would be less chemically
impurities consisting mainly of magnesium, silicon, and reactive. Conversely, the thin plate form of the Plant Miller
aluminum compounds. FGD gypsum led to the conclusion that Plant Millergypsum
Plant Miller: 100% conversion to calcium carbonate and
thus also to ammonium sulfate, not including impurities. 10
crystals had more Surface area and would be more chemi
The calcium carbonate content was determined to be 98.8% cally reactive.
and impurities (acid insoluble) were determined to be Additionally, because the Plant Miller gypsum crystals
1.24%. are flatter, they also settle slower, thus providing more time
for chemical reactions to occur.
Characterization of Gypsum Crystals
Samples of FGD gypsum were obtained and microscopi 15 Thus, in demonstrating the wide effectiveness of the
cally observed from five power plants: Plant Miller, Plant present process in converting various gypsums to ammo
Gorgas, Plant Bowen, Plant Crist and Plant Wansley. Dif nium sulfate and calcium carbonate, five different Source
ferences in structure were observed between the FGD gyp FGD gypsums have been described. Scanning electron
sum crystals from all five plants. The Plant Miller gypsum microscope images of the gypsums crystals are shown in
crystals were observed to be very flat and disc like. The Plant FIG. 3, FIG. 4, FIG. 5, FIG. 6, and FIG. 7. The gypsums
Gorgas gypsum crystals were thicker and more spherical. have different crystalline shapes from large cubical crystals
The Plant Bowen gypsum crystals were longer. The Plant (Plant Gorgas, FIG. 3) to plate crystals (Plant Miller, FIG. 4)
Crist gypsum crystals were thicker and large. The Plant and some gypsums contain rod crystals (Plant Bowen, FIG.
Wansley gypsum crystals were thicker, but also smaller and 5, and Plant Crist, FIG. 6). Although there is some variation
more uniform in size. Scanning electron microscope obser 25 in the reactivity of the various FGD gypsums, all reacted
Vation of samples from each power plant confirmed this quickly under the specific Stoichiometric conditions of the
difference in form. See FIG. 3 showing Plant Gorgas FGD present partially continuous, counter-current process. This
gypsum crystals, FIG. 4 showing Plant Miller FGD gypsum appears to be the result of the formation of pseudomorphs of
crystals, FIG. 5 showing Plant Bowen FGD gypsum crys calcium carbonate created under severely aggressive ammo
tals, FIG. 6 showing Plant Crist FGD gypsum crystals and 30
nium carbonate reaction with the gypsum, especially in the
see FIG. 7 showing Plant Wansley FGD gypsum crystals. second stage reactor(s) of the multistage (two or more) stage
The Plant Miller gypsum crystals were determined to be process. In this case the ammonium carbonate is more than
plate crystals 2x30x30 microns up to 10x100x100 microns. 100% excess over that needed to react with the gypsum for
Undissolved dolomite (Ca,Mg,Fe) CO constituted 1-5% of most of the time and increases in concentration over that
the sample up to 60x60x60 microns in size. 35
The Plant Gorgas gypsum crystals were determined to be needed, to more than 1000% of full reaction. Evaluation by
prism crystals 30x30x40 microns up to 40x40x80 microns. polarized light microscopy revealed that there are no crusts
About 1-5% of the sample was unreacted dolomite (Ca,Mg, of produced calcium carbonate attached on the Surface of
Fe) CO with size of 2-80 micron particles. gypsum crystals. Thus, the ammonium can quickly attack
The Plant Crist gypsum crystals were determined to be 40 the whole crystal. The gypsum does not have to go into
single crystals uniform in size from about 5x40x50 microns Solution but is reacted with the ammonium carbonate in a
up to 10x80x100 microns. A trace quantity of two unknown manner which forms porous pseudomorphs of calcium car
compounds was present. bonate in place of the original gypsum crystal. A pseudo
The Plant Bowen gypsum crystals were determined to be morph is a mineral or mineral compound that appears in an
single crystals with some twinned, uniform in size with the 45 atypical form (crystal system), resulting from a Substitution
average size being about 10x50x50 microns, and having size process in which the appearance and dimensions remain
up to about 50x50x30 microns. A trace quantity of two constant, but the original mineral is replaced by another.
unknown compounds was present. Because of this action and the results of the tests using these
The Plant Wansley gypsum crystals were determined to be different crystals of gypsum varying in size and shape, the
single crystals from 10x50x50 microns to 70x70x300 50 same high reactivity can be expected with non FGD gypsum
microns. Most of the crystals were below 10x70x70 crystals varying in makeup from natural gypsums to phoso
microns. The larger crystals were fewer in number, but still phogypsum and others.
represented ~20% of the sample. A trace quantity of two
unknown compounds was present but much less abundant Example 15
than in the Plant Bowen gypsum sample. 55
The Plant Miller gypsum plate crystals ranged from 2 to Tests of Partially Continuous Countercurrent
10 microns thick, whereas the Plant Gorgas gypsum crystals Process to Convert Phosphogypsum to Calcium
were much thicker at 30 to 40 microns thick. The reaction in Carbonate and Ammonium Sulfate
the present partially continuous countercurrent process
occurs on the Surface of the gypsum and penetrates the 60 The two stage, two reactor process of Embodiment 1, as
crystals Surface. Veneers of calcium carbonate were shown in FIG. 1, was tested using gypsum from acid
observed that would form on the surface of the Plant Gorgas treatment of phosphate rock. Such treatment of phosphate
gypsum crystals and then break off. Here, the rate limiting rock is typical in producing phosphogypsum.
step is due to the crystal thickness. Thus, the thicker Plant Process Test Using Phosphogypsum Sample No. 1
Gorgas gypsum crystals require deeper penetration of the 65 Objective: This test was to determine the level of con
ammonium carbonate Solution employed in the present version of phosphogypsum to calcium carbonate and stoi
process. Penetration is not linear because deeper penetration chiometrically, to ammonium sulfate, by simulating the
 US 9,682,868 B2
61 62
partially continuous countercurrent process as shown in 10. The cake was then rinsed with 500 mL of Grade 1
FIG. 1. The phosphogypsum Sample 1 was obtained from (ASTM (American Society for Testing and Materials)
Idaho, United States. laboratory grade water) water and this final wash was
Procedure collected for testing. The residual Calcium Carbonate
The test was performed as one run through the process to 5 Product Cake was dried overnight in an oven 100° C.
simulate the process shown in FIG. 1, starting with fresh Results
acid washed phosphogypsum in Reactor No. 1. The Solution The Calcium Carbonate Product Cake from Reactor No.
used in Reactor No. 1 was a mixture of 36% ammonium 2 was analyzed by polarized light microscopy and showed
Sulfate solution with ammonium carbonate solution made in
the pilot plant described in Examples 3 and 4. Because of 10
that 95% of the calcium carbonate in the sample was present
possible unknown contaminants, excess ammonium carbon as 3-5 micron crystals and that no residual gypsum was
ate solution was used in each reactor.
present.
Details of the test procedure are listed below: In addition, samples from the process were tested for
1. Up to 36% ammonium sulfate solutions were made as uranium. The results for uranium are presented in Table 6.
described in the Retention Time Tests of Example 6. 15
TABLE 8
2. 175 g of phosphogypsum (19% moisture) was place in
a 2 L beaker and washed with a 1% sulfuric acid Uranium Test Results of Sample No. 1
Solution (including the moisture in the gypsum) that
was prepared by adding 3.92 mL of concentrated Sample Identification Uranium
sulfuric acid to 354.8 mL of Grade 1 water. This slurry Phosphogypsum Raw Cake 17 mg/kg
was mixed for 20 minutes then filtered. This phospho Phosphogypsum Acid Wash Filtrate 2200 g/L
gypsum acid wash filtrate was collected for testing. Phosphogypsum Acid Wash Water 200 g/L
3. The residual cake was then rinsed with 500 mL of Ammonium Sulfate Product 250 g/L
Calcium Carbonate and Gypsum Cake 6.3 mg/kg
Grade 1 water for about 5 minutes and filtered again. Ammonium Sulfate. Ammonium 400 g/L
This phosphogypsum acid wash water was collected for 25 Carbonate Solution
testing. Calcium Carbonate Product Cake Wash 220 g/L
4. An approximately 1 g sample of the acid washed Water
Calcium Carbonate Product Cake 5.5 mg/kg
phosphogypsum cake was collected. The residual cake
served as the Gypsum Cake shown in FIG. 1.
5. 186.7 g of the 36% ammonium sulfate solution and 30 Conclusion
135.6 g of the up to 33% ammonium carbonate solu Polarized light microscope analysis showed that the phos
tion/ammonium bicarbonate was used to simulate the phogypsum reacted to give a 100% conversion of phospho
Ammonium Sulfate/Ammonium Carbonate Solution as gypsum to calcium carbonate.
shown for Reactor No. 1 of FIG. 1. LECO analysis of With reference to Table 8, the radiological test results
the ammonium carbonate solution was 5.26% C and 35 show that the acid wash step of the process washed out a
10.75% N and therefore based on nitrogen being the significant amount of the uranium from the phosphogypsum.
limiting reactant this and accepted methods, this 135.6 This indicates that the uranium levels can be successfully
g was Sufficient to equal a 63% stoichiometric amount controlled by the process in making both process conversion
of ammonium carbonate/ammonium bicarbonate to products of ammonium sulfate and calcium carbonate. The
react with the starting gypsum. 40 acid wash step of the process removed 40 to 75% of the
6. This solution was placed with the Gypsum Cake in a 2 uranium in the gypsum raw cake.
L beaker serving as Reactor No. 1 and mixed for 20 Process Tests. Using Phosphogypsum Samples 2 and 3
minutes. Objective: Tests were performed to determine the com
7. The slurry was filtered and the phosphogypsum Reactor pleteness of reaction simulating the partially continuous
No. 1 liquid filtrate was collected as the Ammonium 45 countercurrent process illustrated in FIG. 1. Tests of the
Sulfate Solution Product. An approximately 1 g sample process used two different samples of gypsum produced in
of the Calcium Carbonate and Gypsum Cake was China as a byproduct of the production of phosphorite for
collected for testing. the production of fertilizer. This gypsum resulted from acid
8. The residual Calcium Carbonate and Gypsum Cake was treatment of phosphorite which is a phosphate rock.
placed in a 2 L beaker serving as Reactor No. 2. A 50 Gypsum Sample No. 2 was produced in LinShu, ShanDong
slurry was made using 271.3 g of Ammonium Carbon Province, China and came from a process that decomposes
ate Solution as described above. This represented an phosphorite by treating with nitric acid to produce nitrate
approximately 125% stoichiometric amount of ammo based fertilizer.
nium carbonate/ammonium bicarbonate solution as Gypsum Sample No. 3 was produced in Guizhou Province,
compared to the starting gypsum. 55 China by a process that decomposes phosphorite by treating
9. The slurry was mixed for 20 minutes and then filtered. with sulfuric acid to produce phosphate fertilizer. Chemical
This Ammonium Sulfate/Ammonium Carbonate Solu analyses of Sample 2 and Sample 3 are presented in
tion was collected for testing. Table 9.
TABLE 9
Chemical Analysis of Phosphogypsum Samples 1 and 2
% Total % Soluble % % %
Gypsum P-Os POs % CaO % SO % MgO Al-O, SiO, FeO,
Sample 1.12 O.OS 28.48 SO.92 O.O2 O.O4 O.29 O.OS
No. 2
 US 9,682,868 B2
63 64
TABLE 9-continued
Chemical Analysis of Phosphogypsum Samples 1 and 2
% Total % Soluble % % %
Gypsum POs POs % CaO % SO2 % MgO Al-O, SiO, Fe2O.
Sample O.11 O.81 27.06 48.60 O.30 O3O 4.OO O.10
No. 3

10
To simulate the partially continuous countercurrent pro 5) The slurry was stirred for 20 minutes without any
cess illustrated in FIG. 1, two runs were performed on each addition of heat. It was then vacuum filtered, and the
gypsum. The first run used the correct amount of synthetic Calcium Carbonate and Gypsum Cake was placed in a
Ammonium Carbonate/Ammonium Sulfate Solution to 2 L beaker (Reactor No. 2) with the 100% stoichio
simulate a 50% stoichiometric amount of each based on the 15
metric amount of ammonium carbonate Solution
weight of the starting gypsum and the '% N measured in the needed to react with the starting gypsum.
Solutions. Run 1 was needed to produce the Ammonium 6) This slurry was mixed without any addition of heat for
20 minutes.
Sulfate/Ammonium Carbonate Solution to use in Reactor 7) The slurry was vacuum filtered and the filter cake was
No. 1 for Run 2. The procedures for each run are described then rinsed with 500 mL of Grade 1 water, and filtered
below. again. The resulting Calcium Carbonate Product Cake
Samples No. 2 and No. 3 Gypsum Test Run 1 Procedure: was dried in an oven overnight at 130° F.
1) Up to 33% ammonium carbonate solution and up to 8) The Ammonium Sulfate/Ammonium Carbonate Solu
36% ammonium sulfate solution were prepared using tion collected from Step 7 before rinsing was saved for
reagent grade compounds and DI water. Samples of Run 2 of the test.
these solutions were tested by LECO for % N and this
25 Gypsum Sample 2 and Sample 3 Test Run 2 Procedure:
value was used to find the weight of the solution for 1) The gypsum was acid washed as described in Steps 1-3
above.
each run in the process as discussed in the Retention 2) The gypsum filter cake was placed in a 2 L beaker
Time Tests of Example 6. (Reactor 1) with the Ammonium Sulfate/Ammonium
2) A 5% solution of sulfuric acid was prepared using 19.5 30 Carbonate Solution from Reactor 2 of Run 1.
mL HSO and 370.5 mL of water. This solution was 3) Steps 5-7 above were followed, and the Calcium
place in a 2 L beaker with 175.7 g of gypsum and Carbonate Product Cake from Step 7 was the final
allowed to stir with no added heat for 20 minutes. product cake.
3) The slurry was vacuum filtered, washed with 500 mL Polarized Light Microscopy Results:
of Grade 1 water, and filtered again. 35 The starting gypsum material and the resulting product
4) The gypsum filter cake was placed in a 2 L beaker cakes from Reactor No. 2 were optically evaluated by
(Reactor No. 1) with the amount of ammonium car polarized light microscopy which provides an effective way
bonate Solution and ammonium sulfate solution calcu to directly detect the presence of even small amounts of
lated as discussed before to simulate the stoichiometric residual unreacted gypsum in the product. The ability to
50%:50% Ammonium Sulfate/Ammonium Carbonate 40 distinguish the gypsum from the calcium carbonate is due to
Solution that would result from Reactor No. 2 in shown the difference in the refractive indices of gypsum and
in FIG. 1 for 50% reaction of gypsum in each reactor. calcium carbonate. The results are presented Table 10.
TABLE 10

Polarized Light Microscopy (PLM) Evaluation of Samples No. 2 and No. 3

Visual
Estimate of
Sample Residual %
Name PLM Description Gypsum Conversion

Sample No. 2 The material is homogenous as coarse *NA *NA

Gypsum blade, twinned crystals of CaSO4·2H2O
up to 25 x 250 x 1500 microns. This
material grew slowly to give these
coarse, twinned crystals.
Run 2 >95% of the calcium carbonate in the <10% 90-100%
Calcium sample is waterite (CaCO) spherulites
Carbonate that are 2-5 in diameter and
Product from agglomerated into units that are up to
Sample No. 2 251. Some of the coarser
Gypsum pseudomorphs still have CaSO4·2H2O
cores. The residual gypsum is very
minor.
 US 9,682,868 B2
65
TABLE 10-continued
Polarized Light Microscopy (PLM) Evaluation of Samples No. 2 and No. 3
Visual
Estimate of
Sample Residual %
Name PLM Description Gypsum Conversion

Sample No. 3 The bulk fraction (>95% by weight) of *NA *NA

Gypsum the gypsum crystals are large plate
crystals of CaSO2H2O usually
present as twinned, Swallow-tail units
up to 20 x 200 x 600. These are well
developed, slowly grown crystals. A
significant quantity (black fraction) of
material is present as amorphous
agglomerates up to 500 and is
tentatively identified as carbonaceous
material. A trace of quartz is present.
Run 2 The -95% of this the calcium <2% 98-100%
Calcium carbonate in this sample are crystalline
Carbonate spherulites of waterite (CaCO) up to 7.
Product from The carbonaceous material has
Sample No. 3 disintegrated into 11 particles and
Gypsum cannot be quantified optically. A trace
amount of residual gypsum remains.
NA-not applicable since the sample is the starting gypsum
25
Test Conclusions: TABLE 12
With reference to the results in Table 10, the completeness Polarized Light Microscopy Evaluation
of reaction was demonstrated by both Sample No. 2 and of Gypsum Samples No. 4 and No. 5
Sample No. 3 gypsums using the partially continuous coun 30
tercurrent process. Polarized light microscopy showed only PLM Description
a minor fraction of unreacted gypsum at the core of the
pseudomorphs formed by the reaction. This small fraction Gypsum This sample is >95% as twinned rod and plate crystals of
requires only an increased retention time or polishing reac Sample CaSO4·2H2O from 5 x 10 x 120 to 110 x 100 x 700 rods.
tion to complete the reaction to 100% conversion. 35 No. 4 Up to 4% of the sample is amorphous particles from 5 to
1001 that are in the refractive index range for silica gel.
Process Tests. Using Phosphogypsum Samples 4 and 5 Gypsum The bulk of this sample (>95%) is CaSO4·2H2O as elongated
Objective: Tests were performed to determine the com Sample plate crystals from 2 x 10 x 40 to 10 x 30 x 7001. A very
pleteness of reaction simulating the partially continuous No. 5 minor (<5%) phase is 2-401 particles that may be silica gel.
countercurrent process illustrated in FIG. 1. Tests of the 40
process used two different samples of gypsum produced in
the Krasnodar Region of Russia: Sample No. 4 and Sample Procedure: Each of the gypsum Samples No. 4 and No. 5,
No. 5. Both Sample No. 4 and Sample No. 5 gypsums were characterized in Tables 11 and 12, were run through the
a product of decomposing phosphate rock using Sulfuric partially continuous countercurrent process as illustrated in
acid. Results from chemical analyses and polarized light 45
FIG. 1. The same procedures for both Run 1 and Run 2
microscopy (PLM) evaluation of the starting (raw) Sample outlined in the 20 Minute Retention Time Test of Example
No. 4 and Sample No. 5 gypsums are presented respectively 6 were followed with the gypsum Samples No. 4 and No. 5
in Table 11 and Table 12. replacing the Miller gypsum in the procedure.
The resulting calcium carbonate product cakes from Run
TABLE 11 50 2 were then analyzed by polarized light microscopy to
identify the completeness of the reaction. The results are
Chemical Analysis of Gypsum Samples No. 4 and No. 5 presented in Table 13.
Gypsum Gypsum TABLE 13
Chemical Property Sample No. 4 Sample No. 5 55
Polarized Light Microscopy Evaluation of
the Run 2 Calcium Carbonate Product
Mass fraction of CaSO2H2O 97% 97% Cake for Gypsum Samples No. 4 and No. 5
expressed as dry dihydrate, %
Optically
Mass fraction of total phosphates 1.0% 1.0% Estimated 96
60
expressed as P.O.5.9% PLM Description Conversion
Mass fraction of water-soluble O.2% O.1%
Calcium This sample comprises soft pseudomorphs of 100%
phosphate expressed as P2O5, 96 Carbonate waterite after gypsum ranging up to 5 x 30 x
Mass fraction of water-soluble fluoride <0.1 <0.1 Product from 600. The entrained <1 to 6 spherulites of
compounds expressed as fluorine, 96 Gypsum waterite are mostly in the <1 to 2 size.
65 Sample
No. 4
 US 9,682,868 B2
67 68
TABLE 13-continued Run 2 of the test started with fresh acid washed Miller
Gypsum Cake (6) in Reactor No. 1 (8) mixed with the
Polarized Light Microscopy Evaluation of Ammonium Sulfate/Ammonium Carbonate Solution (18)
the Run 2 Calcium Carbonate Product
Cake for Gypsum Samples No. 4 and No. 5 reserved as the filtrate from Reactor No. 2 (11) of Run 1.
5 Additional ammonium carbonate solution was added to this
Optically solution for Run 2 to raise it to a 40% stoichiometric amount.
Estimated 96 A 50 mL sample of the filtrate from Reactor No. 1 (8) of Run
PLM Description Conversion 2 was collected as the Ammonium Sulfate Solution Product
Calcium This sample is homogenous as waterite as 100% (19) for Run 2. The Calcium Carbonate and Gypsum Cake
Carbonate <1-6 spherulites. About 7-8% are present in 10 (10) from Reactor No. 1 (8) was then placed in Reactor No.
Product from the 5-6 range. 2 (11) with the Ammonium Sulfate/Ammonium Carbonate
Gypsum
Sample Solution (27) from Reactor No. 3 (22) of Run 1. The filtrate
No. 5 from Reactor No. 2 (11) was saved to use as the Ammonium
Sulfate/Ammonium Carbonate Solution (18) in Reactor No.
Conclusions
15 1 (8) for Run 3. The Calcium Carbonate and Gypsum Cake
With reference to the results presented in Table 13, the (24) from Reactor No. 2 (11) was placed in Reactor No. 3
partially continuous countercurrent process worked effec (22) with a 100% stoichiometric amount of Ammonium
tively and quickly to produce a 100% conversion of the Carbonate Solution (12). The filtrate from Reactor No. 3
(22) was saved to use as the Ammonium Sulfate/Ammonium
gypsum Samples No. 4 and No. 5 to calcium carbonate and Carbonate Solution (27) for Reactor No. 2 (11) for Run 3.
ammonium sulfate. The Calcium Carbonate Product Cake (14) from Reactor
No. 3 was washed with water, dried, and saved as the
Example 16 calcium carbonate product from Run 2.
Run 3 of the test again started with fresh acid washed
Test of Embodiment 3 25 Miller Gypsum Cake (6) in Reactor No. 1 (8) mixed with the
Ammonium Sulfate/Ammonium Carbonate Solution (18)
Three Reactors reserved as the filtrate from Reactor No. 2 (11) of Run 2. A
50 mL sample of the filtrate from Reactor No. 1 (8) of Run
Objective: This test simulates the three reactor process of 3 was collected as the final Ammonium Sulfate Solution
embodiment 3, shown in FIG. 16. 30 Product (19). The Calcium Carbonate and Gypsum Cake
Feed Materials: Same as described in the Retention Time (10) from Reactor No. 1 (8) was then placed in Reactor No.
tests 2 (11) with the Ammonium Sulfate/Ammonium Carbonate
Process Variable Parameters Solution (27) from Reactor No. 3 (22) of Run 2. The filtrate
For the test, a 20 minute retention time was used in each from Reactor No. 2 (11) was discarded. The Calcium Car
reactor. The temperature in the reactors was not controlled 35 bonate and Gypsum Cake (24) from Reactor No. 2 (11) was
and ranged between 20.5° C. and 45° C., and the pH placed in Reactor No. 3 (22) with a 100% stoichiometric
remained between 7.1 and 8.8. As discussed in prior amount of Ammonium Carbonate Solution (12). The filtrate
Examples (e.g. Examples 1-4), aqua ammonia was added as from Reactor No. 3 (22) was discarded. The Calcium
needed to prevent foaming. The reaction was performed in Carbonate Product Cake (14) from Reactor No. 3 (22) was
three runs to simulate the countercurrent process shown in 40 washed with water, dried, and saved as the final calcium
FIG. 16. The first two runs produced the Ammonium Sul carbonate product.
fate/Ammonium Carbonate Solutions for Reactor No. 1 and Procedures
Reactor No. 2 of Run 3. This Example 16 test was designed Calculating the Amounts of Ammonium Sulfate and
to simulate a 40%, 40%, and 20% reaction of gypsum in Ammonium Carbonate to Use for the Test
Reactor No. 1, Reactor No. 2, and Reactor No. 3, respec 45 The weight of ammonium carbonate and/or ammonium
tively. sulfate to use for each step of the reaction was found based
Referring to FIG. 16, Run 1 of the test started with acid on the measured nitrogen for the respective solutions and the
washed Miller Gypsum Cake (6) mixed in Reactor No. 1 (8) desired stoichiometric amount for that reactor as described
with a 40% stoichiometric amount of ammonium carbonate previously in the Retention Time Tests of Example 6.
and a 60% stoichiometric amount of ammonium sulfate. A 50 Three Reactor Test Run 1:
50 mL sample of the filtrate from Reactor No. 1 was 1. 175 g of Miller gypsum was acid washed as described
collected as the Ammonium Sulfate Solution Product (19) in the Retention Time Tests of Example 6.
from Run 1. The Calcium Carbonate and Gypsum Cake (10) 2. The acid washed gypsum was placed in a 1 L beaker
from Reactor No. 1 (8) was then mixed in Reactor No. 2 (11) with the calculated amount of fresh up to 33% ammo
with a 40% stoichiometric amount of gypsum and a 20% 55 nium carbonate Solution for the Stoichiometric amount
stoichiometric amount of ammonium sulfate. The filtrate needed to react with 40% of the gypsum and the
from Reactor No. 2 (11) was saved to use as the Ammonium stoichiometric amount of up to 36% ammonium sulfate
Sulfate/Ammonium Carbonate Solution (18) in Reactor No. solution that would result from 60% of the gypsum
1 (8) of Run 2. The Calcium Carbonate and Gypsum Cake having already reacted. This beaker served as Reactor
(24) from Reactor No. 2 was placed in Reactor No. 3 (22) 60 No. 1 (8) shown in FIG. 16.
with a 100% stoichiometric amount of Ammonium Carbon 3. The slurry was mixed on a stir plate for 20 minutes
ate Solution (12). The filtrate from Reactor No. 3 (22) was while measuring the temperature and pH every 2 sec
saved to use as the Ammonium Sulfate/Ammonium Car onds. Any foaming was dissipated by spraying aqua
bonate Solution (27) for Reactor No. 2 (11) of Run 2. The ammonia into Reactor No. 1 (8).
Calcium Carbonate Product Cake (14) from Reactor No. 3 65 4. After 20 minutes of reacting, the slurry was filtered and
(22) was washed with water, dried, and saved as the calcium a 50 mL sample of the Ammonium Sulfate Solution
carbonate product from Run 1. Product (19) was collected.
 US 9,682,868 B2
69 70
5. For Reactor 2 (11), fresh up to 33% ammonium nium Carbonate Solution (27) for Run 3. The resulting
carbonate solution containing 40% stoichiometric of Run 2 Calcium Carbonate Product Cake (14) was
ammonium carbonate (calculated as before) and 20% rinsed with 268 mL of Grade 1 water, filtered and dried
Stoichiometric of ammonium Sulfate was added to a overnight at 55° C.
beaker. The residual Calcium Carbonate and Gypsum Three Reactor Test Run 3:
Cake (10) from Reactor No. 1 (8) was added to this 1. 175 g of Miller gypsum was acid washed as described
mixture. previously.
6. The resulting slurry was mixed on a stir plate for 20 2. The washed and filtered gypsum was placed in a 1 L
minutes and foaming began immediately, requiring the beaker with the Run 2 Ammonium Sulfate/Ammonium
addition of aqua ammonia. 10 Carbonate Solution (18). This beaker served as Reactor
7. The slurry was filtered by Buchner funnel, and the No. 1 (8).
filtrate from Reactor No. 2 (11) was saved as the 3. The slurry was mixed on a stir plate for 20 minutes
Ammonium Sulfate/Ammonium Carbonate Solution while measuring the temperature and pH every 2 sec
(18) for Reactor No. 1 (8) of Run 2. onds. Any foaming was dissipated by spraying aqua
8. For Reactor No. 3 (22), fresh up to 33% ammonium 15 ammonia into the reactor.
carbonate solution containing 100% stoichiometric of 4. After 20 minutes of reacting, the slurry was filtered, and
ammonium carbonate was added to a beaker with the the filtrate was the final Ammonium Sulfate Product
Calcium Carbonate and Gypsum Cake (24) from Reac Solution (19). A 50 mL sample was collected.
tor No. 2 (11). 5. For Reactor No. 2 (11), the Run 2 Ammonium Sulfate/
9. The resulting slurry was mixed on a stir plate for 20 Ammonium Carbonate Solution (27) was added to a
minutes. No foaming was observed. beaker with the residual Calcium Carbonate and Gyp
10. The slurry was filtered by Buchner funnel, and the sum Cake (10) from Reactor No 1 (8).
resulting Run 1 Calcium Carbonate Product Cake (14) 6. The resulting slurry was mixed on a stir plate for 20
was rinsed with 268 mL of Grade 1 water, filtered and minutes. Any foaming was stopped by spraying aqua
dried over night at 55° C. The filtrate (before rinsing) 25 ammonia into Reactor No. 2 (11).
from Reactor No. 3 (22) was saved as the Ammonium 7. The slurry was filtered by Buchner funnel, and the
Sulfate/Ammonium Carbonate Solution (27) for Reac residual Calcium Carbonate and Gypsum Cake (24)
tor No. 2 (11) of Run 2. was used in Reactor No. 3 (22).
Three Reactor Test Run 2: 8. For Reactor No. 3 (22), fresh up to 33% ammonium
1. 175 g of Miller gypsum was acid washed as described 30 carbonate solution containing 100% stoichiometric of
previously. ammonium carbonate was added to a beaker with the
2. The washed and filtered gypsum was placed in a 1 L residual cake from Reactor No. 2 (11).
beaker with the Run 1 Ammonium Sulfate/Ammonium 9. The resulting slurry was mixed on a stir plate for 20
Carbonate (18) and an additional 126.4 g of ammonium minutes. No foaming was observed.
carbonate solution was added to ensure a 40% stoi 35 10. The slurry was filtered by Buchner funnel, and the
chiometric amount of ammonium carbonate. This bea resulting final Calcium Carbonate Product Cake (14)
ker served as Reactor No. 1 (8). was rinsed with 268 mL of Grade 1 water, filtered and
3. The slurry was mixed on a stir plate for 20 minutes dried overnight at 55° C.
while measuring the temperature and pH every 2 sec Results
onds. Any foaming was dissipated by spraying aqua 40 By polarized light microscopy analysis, the final (Run 3)
ammonia into the reactor. Calcium Carbonate Product Cake was determined to be
4. After 20 minutes of reacting, the slurry was filtered, and homogenous as spherulites of Vaterite from <1 to 5L in
the filtrate was the Ammonium Sulfate Solution Prod diameter. No residual gypsum was identified. Therefore, the
uct (19) for Run 2. A 50 mL sample was collected. The process produced a 100% conversion of gypsum to calcium
residual Calcium Carbonate and Gypsum Cake (10) 45 carbonate.
was used in the Reactor No. 2 (11). Conclusions
5. For Reactor No. 2 (11), the Ammonium Sulfate/Am The test demonstrated that the partially continuous coun
monium Carbonate Solution (27) from Run 1 was tercurrent process with three reactors as shown in FIG. 16
added to a beaker with the residual cake from Reactor may be used to produce a 100% conversion of gypsum to
No. 1 (10). 50 ammonium Sulfate and calcium carbonate.
6. The resulting slurry was mixed on a stir plate for 20
minutes. Any foaming was stopped by spraying aqua Example 17
ammonia into Reactor No. 2 (11).
7. The slurry was filtered by Buchner funnel. The Calcium Tests of Embodiment 5
Carbonate and Gypsum Cake from Reactor No. 2 (24) 55
was used in Reactor No. 3 (22). The filtrate from Producing Ammonium Carbonate Directly in
Reactor No 2 (11) was saved as Ammonium Sulfate/ Reactors
Ammonium Carbonate Solution (18) for Run 3.
8. For Reactor No. 3 (22), fresh up to 33% ammonium Objective: These tests was performed to demonstrate the
carbonate solution containing 100% stoichiometric of 60 effectiveness of embodiment 5 to produce ammonium car
ammonium carbonate needed to react with the starting bonate directly in the reactors of the partially continuous
gypsum was added to a beaker with the residual cake countercurrent process and efficiently convert gypsum to
from Reactor No. 2 (11). calcium carbonate and ammonium Sulfate with very high
9. The resulting slurry was mixed on a stir plate for 20 yield. This was accomplished by simulating the process
minutes. No foaming was observed. 65 shown in FIG. 15. FIG. 15 replicates the two stage, two
10. The slurry was filtered by Buchner funnel, and the reactor process shown in FIG. 1 with the changes necessary
filtrate was saved as the Ammonium Sulfate/Ammo to implement embodiment 5.
 US 9,682,868 B2
71 72
Feed Material: 6. This slurry was mixed for 20 minutes and showed no
Miller gypsum (8.3% water) foaming. The slurry was filtered and the filtrate was the
Sulfuric Acid (mixed to 1% by volume) Ammonium Sulfate Product Solution.
Aqua Ammonia (29%) 7. The Reactor No. 1 Calcium Carbonate and Gypsum
Anhydrous Ammonia 5 Cake was dried in an oven overnight at 50° C.
Carbon Dioxide Graduated Cylinder Test
Water For this test, a graduated cylinder was used to simulate
Procedures Reactor No. 2 in the process shown in FIG. 15. By using a
Beaker Test graduated cylinder, the height of the slurry was increased
For this test, a beaker was used as in the Retention Time 10 which allowed better solubility of the gaseous carbon diox
Tests. The test began with a simulation of the reaction in ide and ammonia to improve the reaction to produce ammo
Reactor No. 2 (11) of the process shown in FIG. 15 by nium carbonate. Only the reaction in Reactor No. 2 was
feeding a simulated Calcium Carbonate and Gypsum Cake tested. It follows from producing a complete reaction in
(10) for Reactor No. 2 (11) that was created with acid Reactor No. 2 by making the ammonium carbonate directly
washed Millergypsum and reagent grade calcium carbonate. 15 in the reactor that excess ammonium carbonate can be
The mixture was chosen to represent a 50%:50% stoichio produced in that reactor. If needed ammonium carbonate
metric mixture of each. This cake is the Calcium Carbonate may also be produced directly in Reactor No. 1.
and Gypsum Cake (10) that would result from a 50% To shorten the time needed to simulate the process, part of
reaction of gypsum in Reactor No. 1 (8) of FIG. 15. Water the ammonia was added at the start as aqua ammonia. The
was added to the solids to create a slurry that was mixed starting Calcium Carbonate and Gypsum Cake for Reactor
while Ammonia (21) and Carbon Dioxide (12) were sparged No. 2 was simulated with a 50%:50% stoichiometric mix of
in to replace the Ammonium Carbonate Solution added in reagent grade calcium carbonate and acid washed Miller
Reactor No. 2 of the previous Two Reactor process. gypsum. This cake is the Calcium Carbonate and Gypsum
The slurry from Reactor No. 2 (11) was filtered. The Cake that would result from a 50% reaction of gypsum in
Ammonium Sulfate/Ammonium Carbonate Solution (18) 25 Reactor No. 1.
filtrate was reserved to be used in Reactor No. 1 (8). The Graduated Cylinder Test
Calcium Carbonate Product Cake (14) was rinsed with water 1. 43.8 g of gypsum was acid washed with 1% sulfuric
and saved to check by polarized light microscopy. acid as described in previous tests. After filtering,
The process in Reactor No. 1 (8) was then simulated by washing, and filtering again; the gypsum was placed in
using the Ammonium Sulfate/Ammonium Carbonate Solu 30 a 250 mL graduated cylinder with 103 g of water, 20 g
tion (18) saved above and adding to it Gypsum Cake (6) that of 29% aqua ammonia, and 25.4 g of calcium carbon
was acid washed Miller gypsum. After the allotted reaction ate.
time, the slurry was filtered and a sample of the Ammonium 2. The mixture was stirred on a magnetic stir plate while
Sulfate Solution Product (19) was collected. The Calcium ammonia and carbon dioxide gas were sparged into the
Carbonate and Gypsum Cake (10) was dried and saved. 35 mixture at rates of 0.0186 g/min and 0.030 g/min
Anhydrous ammonia and carbon dioxide were sparged only respectively.
into the Reactor No. 2 to replace the Ammonium Carbonate 3. At approximately one hour into the process, the Volume
Solution used in previous tests. of the slurry had increased from 170 mL to more than
Steps of the procedure: 250 mL (with pH probe, temperature probe, and mag
1. 87.5 g of Miller gypsum was acid washed with 1% 40 netic bar) and the contents were transferred to a 500 mL
sulfuric acid as described in previous tests. After fil graduated cylinder. At this time, the flow rates were
tering, Washing, and filtering again; the gypsum was increased to 0.0216 g/min for ammonia and 0.049
placed in a beaker with 50.9 g of reagent grade calcium g/min of carbon dioxide.
carbonate and 236.9 g of Grade 1 water. This beaker 4. At 2.5 hours into the process, 45 g of aqua ammonia
served as the Reactor No. 2 shown in FIG. 15. 45 was added to the beaker due to foaming.
2. While stirring, ammonia and carbon dioxide were 5. At 6.5 hours, the ammonia was stopped and the carbon
sparged into the slurry. The carbon dioxide was sparged dioxide was allowed to continue for another 45 min
at a rate of 0.098 g/min. The ammonia flow was set to utes.
a visual flow. The gases were allowed to sparge for 6. The process was then stopped and the slurry was
approximately 3.5 hours. The pH of the solution ranged 50 filtered. The cake was rinsed with 500 mL of Grade 1
in value between 10 and 11. According to the flow water. The flowmeters showed that a total of 8.3146 g
meter, 12.77 g of carbon dioxide was added. of ammonia and 25.9721 g of carbon dioxide were
3. The slurry was filtered through a polyester filter cloth added.
and the Ammonium Sulfate/Ammonium Carbonate 7. The cake was dried in a 55° C. oven overnight.
Solution filtrate was stored overnight in an airtight 55 Results
bottle. A 50 mL sample of this solution was collected. Polarized light microscopy was used to check the Calcium
4. The residual cake was rinsed with 500 mL of water and Carbonate Product Cakes from the tests as well as the
gave off a strong ammonia Smell. The resulting Cal Calcium Carbonate and Gypsum Cake from Reactor No. 1
cium Carbonate Product Cake was allowed to air dry in of the Beaker Test. Polarized light was used because of the
the hood overnight and then dried the next day in an 60 ability to visually identify even very small amounts of
oven at 55° C. gypsum in the samples. The results are presented below.
5. The next day, 175 g of Miller gypsum was acid washed SCP-105 NH/CO, Beaker Test Reactor No. 1 Calcium
as described in previous tests. The filtered and rinsed Carbonate and Gypsum Cake
gypsum was then combined with the Ammonium Sul This sample is more than 50% CaSO4.2H2O crystals up to
fate/Ammonium Carbonate Solution saved from Reac 65 40x40x200LL that show no reaction. Less than 50% is soft
tor No. 2 above and placed in a 1 L beaker that served husks comprising <1 to 3L spherulites of Vaterite. The husks
as Reactor No. 1. do not contain cores of CaSO4.2H2O.
 US 9,682,868 B2
73 74
SCP-104 Beaker Test Reactor No. 2 Calcium Carbonate Equipment:
Product Cake 1. Metal trough
Most of this sample is spherulites of Vaterite from <1 to 2. 50 mL graduated cylinder
6L in diameter. Single crystals of calcite range up to 30LL 3. 250 mL graduated cylinder
aCOSS. 4. Small storage bottle equipped with a removable septum
5. Sample agitator
SCP-106 NH/CO, Cylinder Test Reactor No. 2 Calcium 6. Tygon tubing
Carbonate Product Cake 7. Stopwatch
Most of this sample is calcite crystals up to 25u. No 8. Glass 90° tube
residual CaSO4.2H2O is present. 10
9. Ring stand and clamps
Note: These tests started with a stoichiometric mix of 50% Set up:
reagent grade calcium carbonate and 50% gypsum in Reac 1. Fill the metal trough 3/4 full of water.
tor No. 2. 2. Fill the calibrated cylinder completely full of water and
Analysis of Results invert with the top of the cylinder beneath the water.
The Calcium Carbonate and Gypsum Cake from Reactor 15
Special attention should be given to fully remove any
No. 1 of the Beaker Test showed calcium carbonate was air or gases that may be trapped in the inverted cylinder.
present. The presence of calcium carbonate is evidence that 3. Secure the inverted cylinder to a ring stand using a
clamp.
excess ammonium carbonate was made directly in Reactor 4. Secure tubing so that the glass joint is feeding directly
No. 2 and fed to Reactor No. 1 as Ammonium Sulfatef under the cylinder. Secure this glass joint in the proper
Ammonium Carbonate Solution. location beneath the calibrated cylinder using a clamp
Since no residual gypsum was found in the Calcium 5. Plug in agitator and place it within range of the
Carbonate Product Cake of the Graduated Cylinder Test, septum end of the tubing.
there was 100% conversion of gypsum to calcium carbonate. Procedure:
Conclusions 1. Place 1.47 grams of EDTA into the storage bottle.
The above tests demonstrate the ability to use ammonia 25 2. Add 20 mL of H.O.
and carbon dioxide directly in the reactors of the partially 3. Cap with a rubber septum and agitate for a few seconds.
Remove the cap when complete.
continuous countercurrent process shown in FIG. 15. Based 4. Weigh 1 gram sample of CaCO into a glass weigh
on feed rates and times for the Beaker Test, a complete funnel.
reaction was not expected. The use of only anhydrous 30
5. Very quickly transfer the CaCO into the storage bottle
ammonia and carbon dioxide did however demonstrate that and cap with the septum connected to the tygon tubing
calcium carbonate and ammonium sulfate were produced and glass joint.
from gypsum by reaction with the reaction product of 6. Start the agitator and hold the bottle on the agitator to
ammonium carbonate from reacting ammonia with carbon promote agitation of the mixture.
dioxide. 35
7. As soon as the first bubble emanates from the glass
Using the graduated cylinder for the second test demon tube, start the stop watch.
strated that completeness of reaction (100% conversion of 8. Note and record the time at 10, 30, and 70 mL volumes
read directly from the calibrated cylinder. If the test is
gypsum to calcium carbonate) is possible if the reaction performed correctly, the liquid should be displaced by
vessel is of Sufficient height to enable high aqueous disso the carbon dioxide being released during the reaction.
lution of ammonia and carbon dioxide. Adding anhydrous 40 9. Once this data is collected, a graph and chart can be
ammonia and carbon dioxide directly in the reactor instead generated comparing the reaction rates of various cal
of using the ammonium carbonate/bicarbonate Solution cium carbonate samples.
helps to avoid some of the water diluting the ammonium Results:
Sulfate product. The results of the above performed reactivity tests are
It is understood by those familiar with Small-scale gas 45 shown in FIG. 14. FIG. 14 shows that the reagent grade
absorption tests that on a commercial basis, the diameter of calcium carbonate takes longer to produce the same amount
the reactor would be much larger and the height of the of carbon dioxide as the calcium carbonate products made
reactor Substantially taller leading to a much better gas by the two stage, two reactor process of embodiment 1 (FIG.
absorption on a single pass and therefore shorter retention 1) of the present invention, with and without wash of FGD
and reaction times. 50 gypsum. In FIG. 14, the “Wash” and “H2O Wash” products
were found by polar light microscopy to be high in Vaterite.
Example 18 The “Oct. 3, 2014' product was similar in size to the “Wash”
and "H2O Wash” products but by polarized light microscopy
Reactivity Analysis of the Process Calcium determined to be calcite. Hence, this test demonstrates that
Carbonate Product 55 the calcite and Vaterite products both react similarly but
faster than the reagent grade calcium carbonate due to their
Purpose: Smaller size.
To determine how the rate of reaction of calcium carbon
ate (CaCO) containing Vaterite compares to that of reagent Example 19
grade calcium carbonate (CaCO). Reactivity Analysis was 60
performed by the carbon dioxide (CO) gas method Storage Effects on Crystallography of Calcium
described below. Principle Concept: Carbonate
The calcium carbonate was reacted with a weak acid in a
sealed container. The reaction produced CO, which was Objective: The purpose of this test was to identify the effects
collected and measured. By measuring the amount of time 65 that storage conditions have on the calcium carbonate prod
required to produce fixed volumes of CO, the rate of uct from simulating the partially continuous countercurrent
reaction could be determined. process shown in FIG. 1.
 US 9,682,868 B2
75 76
Storage Parameters: 2. Anhydrous ammonia was sparged in for 11-30 seconds
For this set of tests, calcium carbonate product was to dissipate the foam.
produced in the laboratory and either washed or not washed 3. The slurry was mixed for 20 minutes.
and dried or not dried before storing according to the list 4. The resulting slurry was vacuum filtered.
bey. t h and stored wet 5 Step 3 Reactor 2
N. WN WE d d 1. The filter cake from Reactor 1 was placed in a 2 L
Water washed and stored wetry beaker (representing Reactor 2) with 535.71 g of
Water washed and stored dry ammonium carbonate Solution. While stirring, foaming
Ammonium Sulfate wash and stored wet 10 occurred and anhydrous ammonia was added for 11-30
Ammonium Sulfate wash and stored dry Seconds using a sparger.
Procedure: 2. The slurry was mixed for 20 minutes, removed, and
All of products using a single run with a simulated Starting vacuum filtered.
Ammonium Sulfate/Ammonium Carbonate Solution in This procedure was repeated and the final product was
Reactor No. 1 of FIG. 1 as described in the procedures is either:
below. a. not washed and stored wet,
Step 1—Acid Wash b. not washed, dried at 130° F. overnight and stored dry,
1. 3.92 mL of sulfuric acid was mixed with 354 mL of c. mixed with 500 mL of water for 20 minutes, filtered,
Grade 1 water in a 2 L beaker. and stored wet,
2. 175 g of Millergypsum was added to the sulfuric acid d. mixed with 500 mL of water for 20 minutes, filtered,
solution. The resulting slurry was mixed for 20 min- and dried at 130° F. overnight and stored dry,
utes. e. mixed with 500 mL of ammonium sulfate (36% solu
3. The slurry was vacuum filtered using the filter cloth tion) for 20 minutes, filtered, and stored wet, or
from the pilot plant operation. f. mixed with 500 mL of ammonium sulfate (36% solu
4. The filter cake was washed with 500 mL Grade 1 water is tion) for 20 minutes, filtered, and dried at 130° F.
and filtered. overnight and stored dry.
Step 2 Reactor 1 Polarized Light Microscopy Results
1. The filter cake was placed in a 2 L beaker (representing All of the stored samples were analyzed by polarized light
Reactor No. 1 in FIG. 1). 186.7 g of up to 36% microscopy after being stored for 9-10 days and again after
ammonium sulfate solution and 267.86 g of up to 33% so being stored one month. The samples that showed no
ammonium carbonate solution were added while stir- significant change after one month were evaluated again
ring on a hotplate. after almost 8 months.
TABLE 1.4
Polarized Light Microscopy Results (PLM) of Stored Samples
of Calcium Carbonate

Sample
Storage Date Date of
Parameters Produced PLM Polarized Light Microscopy Results (PLM)
No Water Jan. 27, 2015 Feb. 6, 2015 Major fraction is single crystals of calcite up to 5 Lim
Wash, in diameter.
Stored Wet Spherulites up to 7 m in diameter of waterite
are a minor component.
Feb. 27, 2015 The sample comprises single prismatic crystals
of calcite from 2-7 Im.
Water Jan. 28, 2015 Feb. 6, 2015 Essentially homogenous as calcite crystals up to
Wash, 6 Im in diameter.
Stored Wet Feb. 27, 2015 The major fraction of this sample is calcite as 1-7.
single crystals. A few agglomerations of
regrown waterite constitute about 5-10% as
intergrown and twinned plate crystals. These
waterite agglomerates range up to 301 and
contain numerous calcite crystals.
Ammonium Jan. 28, 2015 Feb. 6, 2015 The bulk is agglomerates of 3-5 spherulites of
Sulfate 1-21 crystals of waterite.
Wash, A minor fraction has converted to calcite as 1-21
Stored Wet crystals.
Feb. 27, 2015 The major fraction is present as 2-71 single
crystals of calcite. A minor fraction is present as
separate agglomerates up to 251 and contain
both calcite and 1-21 plate and twinned crystals
of waterite as high as 5% of the sample.
No Water Jan. 28, 2015 Feb. 6, 2015 The major to bulk component of the sample is 3-61
Wash, spherulites of 1-2 micron needle crystals of
Stored Dry waterite. Calcite as 2-4L crystals is a very minor
component.
Sep. 11, 2015 This sample comprises waterite as spherulites of
radiating, needle crystals up to 51 in diameter.
The bulk weight fraction (95% by weight) is 3-4
spherulites.
 US 9,682,868 B2
77 78
TABLE 14-continued
Polarized Light Microscopy Results (PLM) of Stored Samples
of Calcium Carbonate

Sample
Storage Date Date of
Parameters Produced PLM Polarized Light Microscopy Results (PLM)
Water Jan. 28, 2015 Feb. 6, 2015 This sample is almost homogenous as 6-10
Wash, spherulites of needle crystals of waterite
Stored Dry agglomerated into 10-201 units.
A few single crystals of calcite up to 41 are
present.
Sep. 11, 2015 Vaterite spherulites range up to 8 in diameter
but the effective upper size limit is 5 with the
bulk (95% by weight) of the spheres being 3-41.
Ammonium Jan. 29, 2015 Feb. 6, 2015 This sample is homogenous as 2-5 spherulites
Sulfate of waterite made up of needle crystals
Wash, Sep. 11, 2015 These waterite spherulites range up to 8 with
Stored Dry an effective upper limit of 5-6 and a bulk
weight fraction (95% by weight) of 3-4
diameter.

Conclusions Results:
The following conclusions are based on PLM analyses The results of the tests are shown in below Table 15. The
presented in Table 14: calcium carbonate product used in Trials 2, 3, 5, and 6 were
b. Samples stored wet convert to calcite in less than a 25 determined by polarized light microscopy to be 80-90%
week unless the sample is rinsed with ammonium Vaterite and produced a much faster rate of change in pH
sulfate. value indicating fast dissolution rates. The calcium carbon
ate product used in Trial 7 was determined by polarized light
a. Ammonium sulfate rinse before wet storage slows the microscopy to be calcite and showed a much slower rate of
conversion of Vaterite to calcite with complete conver 30 change in pH value. The reagent grade calcium carbonate
sion occurring between one week and one month. showed a rate of pH change even slower than that of the
c. Samples stored dry remained mostly waterite even after small calcite product. These differences in dissolution rate
almost eight months of storage. indicate that the material in Trials 2, 3, 5, and 6 was waterite
because of its higher solubility than calcite.
Example 20 35
TABLE 1.5
Surface Area/Solubility Analysis
Calcium Carbonate Particle Surface Area/Solubility Tests
Phenolphthalein Method Sample Time
40 Trial Mass (min:sec) Types of Calcium Carbonate Particles
Purpose: 1 0.1 g 1:38 Reagent grade CaCO - Mix Speed unknown
To demonstrate the differences in particle surface/solubil 2 0.1 g 0:14 Jan. 14, 2015 Lab CaCO (no wash);
ity of various crystalline forms of calcium carbonate majority waterite
(CaCO) containing Vaterite compared to that of reagent 3 0.1 g 0:10 Jan. 14, 2015 Lab CaCO (HO wash);
majority waterite
grade CaCO. 45 4 0.1 g 0:46 Reagent grade CaCO3
Principle Concept: 5 0.1 g 0:14 Jan. 14, 2015 Lab CaCO (HO wash)
A calcium carbonate sample was added to water contain 6 0.1 g 0:12 Jan. 14, 2015 Lab CaCO (HO wash)
ing a phenolphthalein pH indicator. The reaction produces 7 0.1 g 0:30 10/3/14 12:55 PM Lab CaCOs: small calcite
CO, which increases the pH of the solution. By measuring
the amount of time required to change the color of the 50
Solution to a dark pink, the rate of dissolution for each Example 21
sample was determined. Seven trials were performed Calcium Carbonate Acid Insolubles Tests
according to the below procedure with the types of calcium
carbonate particles stated in Table 15. 55 Depending upon the source of the gypsum, the gypsum
Procedure:
may have differing chemical impurities. These impurities
1. Place 50 mL of HO into a 100 mL beaker. generally pass through the process of the present invention
2. Place 5 drops of 1% phenolphthalein into the water. and are present as impurities in the final product ammonium
3. Add a stir bar into the beaker and begin stirring the Sulfate and calcium carbonate. The impurities are usually
Solution. 60 more detrimental when present in the product calcium
4. Weigh 0.1 g of the sample. carbonate because commercial use of the calcium carbonate
5 . Add the sample to the water/indicator solution and often requires purer calcium carbonate.
monitor the time. A lab procedure was employed to measure the chemical
6. Record the time when the solution reaches the correct impurities in product calcium carbonate that are insoluble in
hue. A beaker containing a fully solubilized calcium 65 dilute hydrochloric acid. Such chemical impurities were
carbonate sample, water, and indicator Solution was determined in the calcium carbonate products made in the
used as a visual comparison to identify the endpoint. above described lab and Pilot Plant tests, for instance in
 US 9,682,868 B2
79 80
Examples 1-4. The results from determining chemical impu discharging the first and second precipitate calcium car
rities that are acid insoluble are shown in Table 16. bonate and a solution of ammonium Sulfate and ammo
nium carbonate;
TABLE 16 resuming the flow of reactants into the second reactor,
5 separating the first and second precipitate calcium car
Calcium Carbonate Impurities that are Acid Insoluble bonate from the solution of ammonium Sulfate and
Acid Insolubles ammonium carbonate to result in a product calcium
Test Sample Date Process (% weight of sample) carbonate cake and a residue solution of ammonium
4/24f14 pm Pilot Plant 1.24
Sulfate and ammonium carbonate;
6,314 Lab 1.OS
10 retaining the product calcium carbonate cake; and
8/22/14 12:30 pm Pilot Plant O.882 adding the residue solution of ammonium Sulfate and
8/22/143:05 pm Pilot Plant O.845 ammonium carbonate to the first reactor.
2. The process of claim 1, wherein the step of separating
The average percent weight of acid insolubles, as impu the aqueous slurry of gypsum to result in first and second
rities, of these samples is 1.00%. These calcium carbonate 15 gypsum liquid residues and a gypsum cake is accomplished
samples were all produced by the two stage, two reactor by steps comprising:
process of the present invention, embodiment 1 (FIG. 1) filtering an aqueous slurry of gypsum on a filter having
using Plant Millergypsum. It is assumed that the insolubles two Zones, Zone A and Zone B, wherein Zone A the
would change and increase or decrease in FGD gypsums gypsum slurry is filtered resulting in a first gypsum
from other power plants because of the different coal being liquid residue and a residual gypsum cake; and
burned. transporting the residual gypsum cake on the filter to Zone
The impurities were analyzed using X-ray diffraction and B in which the residual gypsum cake is washed with
were found to be a mixture of chlorite, kaolinite, k-feldspar, water to result in a second gypsum liquid residue.
mica, plagioclase, pyrite, quartz, and amorphous material 3. The process of claim 1, wherein the step of separating
most of which was barium sulfate. 25 the first and second precipitate calcium carbonate from the
Solution of ammonium sulfate and ammonium carbonate is
While only a few exemplary embodiments of this inven accomplished by steps comprising:
tion have been described in detail, those skilled in the art will filtering the first and second precipitate calcium carbonate
recognize that there are many possible variations and modi from the Solution of ammonium sulfate and ammonium
fications which may be made in the exemplary embodiments 30 carbonate on a filter having two Zones, Zone A and Zone
while yet retaining many of the novel and advantageous
features of this invention. Accordingly, it is intended that the B, wherein Zone A the solution of ammonium sulfate
following claims cover all Such modifications and varia and ammonium carbonate is filtered resulting in a
tions. calcium carbonate cake and a residue solution of
ammonium Sulfate and ammonium carbonate;
The invention claimed is: 35 adding the residue solution of ammonium Sulfate and
1. A partially continuous countercurrent flow process for ammonium carbonate to one or both of the first and
converting gypsum to ammonium Sulfate and calcium car second reactors;
bonate comprising the following steps: transporting the calcium carbonate cake on the filter to
separating an aqueous slurry of gypsum to result in a Zone B in which the calcium carbonate cake is washed
gypsum liquid residue and a gypsum cake; 40 with water to result in a product calcium carbonate cake
feeding a flow of reactants being the gypsum cake and a and a wash water Solution of ammonium Sulfate and
Solution of ammonium sulfate and ammonium carbon ammonium carbonate;
ate into a first reactor for chemical reaction; retaining the product calcium carbonate cake; and
stopping the flow of reactants into the first reactor for a feeding the wash water Solution of ammonium sulfate and
retention time selected to achieve a preselected degree 45 ammonium carbonate to an ammonium carbonate
of chemical reaction to form an ammonium Sulfate absorber to retain ammonium carbonate.
Solution containing a first precipitate calcium carbonate 4. The process of claim 1 further comprising the following
and a gypsum remnant; steps:
discharging the ammonium Sulfate Solution containing a washing the product calcium carbonate cake with water to
first precipitate calcium carbonate and a gypsum rem 50 result in a wash residue solution of ammonium sulfate
nant, and ammonium carbonate; and
resuming the flow of reactants into the first reactor; adding the wash residue solution of ammonium sulfate
separating the first precipitate calcium carbonate and and ammonium carbonate to the first reactor.
gypsum remnant from the ammonium Sulfate Solution 5. The process of claim 1 further comprising the following
to result in a product ammonium sulfate solution and a 55 steps:
remnant cake of first precipitate calcium carbonate and washing the product calcium carbonate cake with water to
gypsum, result in a wash residue solution of ammonium sulfate
retaining the product ammonium Sulfate solution; and ammonium carbonate; and
feeding a flow of reactants being the remnant cake of first feeding the wash residue solution of ammonium sulfate
precipitate calcium carbonate and gypsum and ammo 60 and ammonium carbonate to an ammonium carbonate
nium carbonate solution into a second reactor for absorption column.
chemical reaction; 6. The process of claim 1 further comprising the following
stopping the flow of reactants into the second reactor for step:
a retention time selected to achieve a predetermined adding ammonia or ammonium hydroxide to the first
degree of chemical reaction to form a second precipi 65 reactor and second reactor to reduce foaming.
tate calcium carbonate and a solution of ammonium 7. The process of claim 1, wherein the product ammonium
Sulfate and ammonium carbonate; Sulfate Solution contains ammonium Sulfate and the product
 US 9,682,868 B2
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calcium carbonate cake contains calcium carbonate, with nium carbonate solution, selectively into one or both of
ammonium sulfate in a yield of 97 to 100% and calcium a third reactor and a fourth reactor, for chemical reac
carbonate in a yield of 97 to 100%. tion;
8. The process of claim 1, wherein the product ammonium stopping the flow of reactants into one or both of the third
Sulfate Solution contains ammonium sulfate and the product reactor and fourth reactor for a third reactor retention
calcium carbonate cake contains calcium carbonate, with time and a fourth reactor retention time both selected to
both ammonium sulfate in a yield of 100% and calcium achieve a predetermined degree of chemical reaction in
carbonate in a yield of 100%. one or both third reactor and fourth reactor to form a
9. The process of claim 1, wherein the process has a total second precipitate calcium carbonate and a solution of
retention time of 4 to 60 minutes for 100% yield of product 10
ammonium Sulfate and ammonium carbonate;
calcium carbonate and product ammonium sulfate. discharging the first and second precipitate calcium car
10. The process of claim 1, wherein the process is bonate and a solution of ammonium Sulfate and ammo
conducted at temperatures of 41 to 176° F. nium carbonate from one or both third reactor and
11. The process of claim 1, further including mixing
within the first reactor and the second reactor by a mixer 15 fourth reactor;
selected from the group consisting of impeller mixer, paddle resuming the flow of reactants into one or both third
mixer, ultrasonic mixer and homogenizer. reactor and fourth reactor;
12. The process of claim 1, wherein the separating steps separating the first and second precipitate calcium car
are accomplished by a device selected from the group bonate from the solution of ammonium Sulfate and
consisting of belt filter, pan filter, drum filter and centrifuge. ammonium carbonate to result in a product calcium
13. The process of claim 1, wherein contaminants are carbonate cake and a residue solution of ammonium
removed from the gypsum by an acid rinse process com Sulfate and ammonium carbonate;
prising the steps of retaining the product calcium carbonate cake; and
separating the aqueous slurry of gypsum to result in a adding the residue solution of ammonium Sulfate and
gypsum liquid residue and a gypsum cake; 25 ammonium carbonate to one or both first reactor and
rinsing the gypsum cake with an aqueous solution con second reactor.
taining sulfuric acid from 0.01 to 10% concentration to 17. The process of claim 16, wherein the step of separat
result in a purified gypsum cake; and ing the aqueous slurry of gypsum to result in first and second
rinsing the purified gypsum cake with water to remove gypsum liquid residues and a gypsum cake is accomplished
residual Sulfuric acid solution to result in a final puri 30 by steps comprising:
fied gypsum cake. filtering an aqueous slurry of gypsum on a filter having
14. The process of claim 13, wherein the gypsum is a two Zones, Zone A and Zone B, wherein Zone A the
phosphogypsum and a contaminant is uranium wherein gypsum slurry is filtered resulting in a first gypsum
uranium is removed from the gypsum cake to result in a 40 liquid residue and a residual gypsum cake; and
to 75% reduction of uranium in the gypsum cake. 35 transporting the residual gypsum cake on the filter to Zone
15. The process of claim 1, wherein the aqueous slurry of B in which the residual gypsum cake is washed with
gypsum is directly from a SO, scrubber. water to result in a second gypsum liquid residue.
16. A partially continuous countercurrent flow process for 18. The process of claim 16, wherein the step of separat
converting gypsum to ammonium Sulfate and calcium car ing the first and second precipitate calcium carbonate from
bonate comprising the following steps: 40 the solution of ammonium sulfate and ammonium carbonate
separating an aqueous slurry of gypsum to result in a is accomplished by steps comprising:
gypsum liquid residue and a gypsum cake; filtering the first and second precipitate calcium carbonate
feeding a flow of reactants being the gypsum cake and a from the Solution of ammonium sulfate and ammonium
Solution of ammonium sulfate and ammonium carbon carbonate on a filter having two Zones, Zone A and Zone
ate, selectively into one or both of a first reactor and a 45 B, wherein Zone A the solution of ammonium sulfate
second reactor, for chemical reaction; and ammonium carbonate is filtered resulting in a
stopping the flow of reactants into one or both of the first calcium carbonate cake and a residue solution of
reactor and second reactor for a first reactor retention ammonium Sulfate and ammonium carbonate;
time and a second reactor retention time both selected adding the residue solution of ammonium Sulfate and
to achieve a predetermined degree of chemical reaction 50 ammonium carbonate to one or both of the first and
in one or both first reactor and second reactor to form second reactors;
an ammonium sulfate solution containing a first pre transporting the calcium carbonate cake on the filter to
cipitate calcium carbonate and a gypsum remnant in Zone B in which the calcium carbonate cake is washed
one or both first reactor and second reactor; with water to result in a product calcium carbonate cake
discharging the ammonium Sulfate Solution containing a 55 and a wash water Solution of ammonium Sulfate and
first precipitate calcium carbonate and a gypsum rem ammonium carbonate;
nant from one or both first reactor and second reactor; retaining the product calcium carbonate cake; and
resuming the flow of reactants into one or both first feeding the wash water Solution of ammonium sulfate and
reactor and second reactor; ammonium carbonate to an ammonium carbonate
separating the first precipitate calcium carbonate and 60 absorber to retain ammonium carbonate.
gypsum remnant from the ammonium Sulfate Solution 19. A partially continuous countercurrent flow process for
to result in a product ammonium sulfate solution and a converting gypsum to ammonium Sulfate and calcium car
remnant cake of precipitated calcium carbonate and bonate comprising the following steps:
gypsum, separating an aqueous slurry of gypsum to result in a
retaining the product ammonium Sulfate solution; 65 gypsum liquid residue and a residual gypsum cake;
feeding a flow of reactants being the remnant cake of first feeding a flow of reactants being the residual gypsum
precipitate calcium carbonate and gypsum and ammo cake and a second solution of ammonium sulfate and
 US 9,682,868 B2
83 84
ammonium carbonate, selectively into one or both of a separating the second precipitate calcium carbonate and
first reactor and a second reactor, for chemical reaction; gypsum remnant from the second solution of ammo
stopping the flow of reactants into one or both of the first nium Sulfate and ammonium carbonate to result in the
reactor and second reactor for a first reactor retention second residue solution of ammonium Sulfate and
time and a second reactor retention time both selected ammonium carbonate and the second precipitate cal
to achieve a predetermined degree of chemical reaction cium carbonate and gypsum remnant cake;
in one or both first reactor and second reactor to form feeding the second residue solution of ammonium sulfate
an ammonium sulfate solution containing a first pre and ammonium carbonate to the first reactor and Sec
cipitate calcium carbonate and a gypsum remnant in 10
ond reactor, and
one or both first reactor and second reactor; feeding the second precipitate calcium carbonate and
discharging the ammonium Sulfate Solution containing a gypsum remnant cake to the third reactor and fourth
first precipitate calcium carbonate and a gypsum rem reactOr.
nant from one or both first reactor and second reactor; 20. The process of claim 19, wherein the step of separat
resuming the flow of reactants into one or both first 15 ing the aqueous slurry of gypsum to result in first and second
reactor and second reactor; gypsum liquid residues and a gypsum cake is accomplished
separating the first precipitate calcium carbonate and by steps comprising:
gypsum remnant from the ammonium Sulfate Solution filtering an aqueous slurry of gypsum on a filter having
to result in a product ammonium sulfate solution and a two Zones, Zone A and Zone B, wherein Zone A the
first precipitate calcium carbonate and gypsum remnant gypsum slurry is filtered resulting in a first gypsum
cake; liquid residue and a residual gypsum cake; and
retaining the product ammonium Sulfate solution; transporting the residual gypsum cake on the filter to Zone
feeding a flow of reactants being the second precipitate B in which the residual gypsum cake is washed with
calcium carbonate and gypsum remnant cake and an water to result in a second gypsum liquid residue.
ammonium carbonate Solution, selectively into one or 25 21. The process of claim 19, wherein the step of separat
both of a third reactor and a fourth reactor for chemical ing the first, second, third, fourth, fifth and sixth precipitate
reaction; calcium carbonate from the first solution of ammonium
stopping the flow of reactants into one or both of the third Sulfate and ammonium carbonate is accomplished by steps
reactor and fourth reactor for a third reactor retention comprising:
time and a fourth reactor retention time both selected to 30 filtering the first, second, third, fourth, fifth and sixth
achieve a predetermined degree of chemical reaction in precipitate calcium carbonate from the Solution of
one or both third reactor and fourth reactor to form a ammonium sulfate and ammonium carbonate on a filter
third precipitate calcium carbonate and a first Solution having two Zones, Zone A and Zone B, wherein Zone A
of ammonium sulfate and ammonium carbonate in one the solution of ammonium sulfate and ammonium
or both third reactor and fourth reactor; 35 carbonate is filtered resulting in a calcium carbonate
discharging the third precipitate calcium carbonate and a cake and a residue solution of ammonium Sulfate and
first Solution of ammonium sulfate and ammonium ammonium carbonate;
carbonate from one or both third reactor and fourth adding the residue solution of ammonium Sulfate and
reactor, ammonium carbonate to any one or all of the first,
resuming the flow of reactants into one or both third 40 second, third, fourth, fifth and sixth reactors;
reactor and fourth reactor, separating the first, second, transporting the calcium carbonate cake on the filter to
and third precipitate calcium carbonate from the first Zone B in which the calcium carbonate cake is washed
Solution of ammonium sulfate and ammonium carbon with water to result in a product calcium carbonate cake
ate to result in a product calcium carbonate cake and a and a wash water Solution of ammonium Sulfate and
first residue solution of ammonium sulfate and ammo 45 ammonium carbonate;
nium carbonate; retaining the product calcium carbonate cake; and
retaining the product calcium carbonate cake; feeding the wash water Solution of ammonium sulfate and
feeding a flow of reactants being the first residue solution ammonium carbonate to an ammonium carbonate
of ammonium sulfate and ammonium carbonate and absorber to retain ammonium carbonate.
first precipitate calcium carbonate and gypsum remnant 50 22. A partially continuous countercurrent flow process for
cake, selectively into one or both of a fifth reactor and converting gypsum to ammonium Sulfate and calcium car
a sixth reactor, for chemical reaction; bonate comprising the following steps:
stopping the flow of reactants into one or both of the fifth separating an aqueous slurry of gypsum to result in a
reactor and sixth reactor for a fifth reactor retention gypsum liquid residue and a residual gypsum cake;
time and a sixth reactor retention time both selected to 55 feeding a flow of reactants being the residual gypsum
achieve a predetermined degree of chemical reaction in cake and a second solution of ammonium sulfate and
one or both fifth reactor and sixth reactor to form a ammonium carbonate, into a first reactor, for chemical
second solution of ammonium Sulfate and ammonium reaction;
carbonate and second precipitate calcium carbonate stopping the flow of reactants into the first reactor for a
and gypsum remnant in one of both fifth reactor and 60 first reactor retention time selected to achieve a prede
sixth reactor, termined degree of chemical reaction in the first reactor
discharging the first and second Solution of ammonium to form an ammonium Sulfate solution containing a first
Sulfate and ammonium carbonate and second precipi precipitate calcium carbonate and a gypsum remnant in
tate calcium carbonate and gypsum remnant from one the first reactor;
or both fifth reactor and sixth reactor; 65 discharging the ammonium sulfate Solution containing a
resuming the flow of reactants into one or both fifth first precipitate calcium carbonate and a gypsum rem
reactor and sixth reactor; nant from the first reactor;
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85 86
resuming the flow of reactants into the first reactor; 24. The process of claim 22, wherein the step of separat
separating the first precipitate calcium carbonate and ing the second precipitate calcium carbonate and gypsum
gypsum remnant from the ammonium Sulfate Solution remnant from the second solution of ammonium Sulfate and
to result in a product ammonium sulfate solution and a ammonium carbonate is accomplished by steps comprising:
first precipitate calcium carbonate and gypsum remnant 5 filtering the first and second precipitate calcium carbonate
cake; from the Solution of ammonium sulfate and ammonium
retaining the product ammonium Sulfate solution; carbonate on a filter having two Zones, Zone A and Zone
feeding a flow of reactants being the second precipitate B, wherein Zone A the solution of ammonium sulfate
calcium carbonate and gypsum remnant cake and an and ammonium carbonate is filtered resulting in a
10 calcium carbonate cake and a residue solution of
ammonium carbonate Solution, selectively into a third ammonium Sulfate and ammonium carbonate;
reactor for chemical reaction; adding the residue solution of ammonium Sulfate and
stopping the flow of reactants into the third reactor for a ammonium carbonate to any one or all of the first,
third reactor retention time selected to achieve a pre second, and third reactors;
determined degree of chemical reaction in the third 15 transporting the calcium carbonate cake on the filter to
reactor to form a third precipitate calcium carbonate Zone B in which the calcium carbonate cake is washed
and a first solution of ammonium sulfate and ammo with water to result in a product calcium carbonate cake
nium carbonate in the third reactor; and a wash water Solution of ammonium Sulfate and
discharging the third precipitate calcium carbonate and a ammonium carbonate;
first Solution of ammonium sulfate and ammonium retaining the product calcium carbonate cake; and
carbonate from the third reactor; feeding the wash water Solution of ammonium sulfate and
resuming the flow of reactants into the third reactor; ammonium carbonate to an ammonium carbonate
separating the first, second, and third precipitate calcium absorber to retain ammonium carbonate.
carbonate from the first solution of ammonium sulfate 25. A partially continuous countercurrent flow process for
and ammonium carbonate to result in a product calcium 25 converting gypsum to ammonium Sulfate and calcium car
carbonate cake and a first residue solution of ammo bonate comprising the following steps:
nium sulfate and ammonium carbonate; separating an aqueous slurry of gypsum to result in a
retaining the product calcium carbonate cake; gypsum liquid residue and a gypsum cake;
feeding a flow of reactants being the first residue solution feeding a flow of reactants being ammonia, carbon diox
of ammonium sulfate and ammonium carbonate and 30 ide, the gypsum cake, and a solution of ammonium
Sulfate and ammonium carbonate into a first reactor for
first precipitate calcium carbonate and gypsum remnant chemical reaction;
cake, into a second reactor, for chemical reaction; stopping the flow of reactants into the first reactor for a
stopping the flow of reactants into the second reactor for retention time selected to achieve a predetermined
a second reactor retention time selected to achieve a
predetermined degree of chemical reaction in the sec
35 degree of chemical reaction to form an ammonium
ond reactor to form a second solution of ammonium
Sulfate solution containing a first precipitate calcium
carbonate and a gypsum remnant;
Sulfate and ammonium carbonate and second precipi discharging the ammonium sulfate Solution containing a
tate calcium carbonate and gypsum remnant in the first precipitate calcium carbonate and a gypsum rem
second reactor, 40 nant,
discharging the first and second Solution of ammonium resuming the flow of reactants into the first reactor;
Sulfate and ammonium carbonate and second precipi separating the first precipitate calcium carbonate and
tate calcium carbonate and gypsum remnant from the gypsum remnant from the ammonium Sulfate Solution
second reactor, to result in a product ammonium sulfate solution and a
resuming the flow of reactants into the second reactor, 45 remnant cake of first precipitate calcium carbonate and
separating the second precipitate calcium carbonate and gypsum,
gypsum remnant from the second solution of ammo retaining the product ammonium Sulfate Solution;
nium sulfate and ammonium carbonate to result in the feeding a flow of reactants being ammonia, carbon diox
second residue solution of ammonium Sulfate and ide, the remnant cake of first precipitate calcium car
ammonium carbonate and the second precipitate cal 50 bonate and gypsum and ammonium carbonate Solution
cium carbonate and gypsum remnant cake; into a second reactor for chemical reaction;
feeding the second residue solution of ammonium Sulfate stopping the flow of reactants into the second reactor for
and ammonium carbonate to the first reactor, and a retention time selected to achieve a predetermined
feeding the second precipitate calcium carbonate and degree of chemical reaction to form a second precipi
55 tate calcium carbonate and a solution of ammonium
gypsum remnant cake to the third reactor. Sulfate and ammonium carbonate;
23. The process of claim 22, wherein the step of separat discharging the first and second precipitate calcium car
ing the aqueous slurry of gypsum to result in first and second bonate and a solution of ammonium Sulfate and ammo
gypsum liquid residues and a gypsum cake is accomplished nium carbonate;
by steps comprising: 60 resuming the flow of reactants into the second reactor,
filtering an aqueous slurry of gypsum on a filter having venting excess carbon dioxide and ammonia from the first
two Zones, Zone A and Zone B, wherein Zone A the reactor and the second reactor,
gypsum slurry is filtered resulting in a first gypsum separating the first and second precipitate calcium car
liquid residue and a residual gypsum cake; and bonate from the solution of ammonium Sulfate and
transporting the residual gypsum cake on the filter to Zone 65 ammonium carbonate to result in a product calcium
B in which the residual gypsum cake is washed with carbonate cake and a residue solution of ammonium
water to result in a second gypsum liquid residue. Sulfate and ammonium carbonate;
 US 9,682,868 B2
87 88
retaining the product calcium carbonate cake; and reactors, wherein the retention time for a particular one
adding the residue solution of ammonium sulfate and reactor is selected to achieve a predetermined degree of
ammonium carbonate to the first reactor. chemical reaction in the particular one reactor to form
26. The process of claim 25, wherein the step of separat an ammonium sulfate solution containing a first pre
ing the aqueous slurry of gypsum to result in first and second 5 cipitate calcium carbonate and a gypsum remnant in
gypsum liquid residues and a gypsum cake is accomplished one or all reactors of the plurality of reactors;
by steps comprising: discharging the ammonium sulfate Solution containing a
filtering an aqueous slurry of gypsum on a filter having first precipitate calcium carbonate and a gypsum rem
two Zones, Zone A and Zone B, wherein Zone A the nant from one or all reactors of the plurality of reactors;
gypsum slurry is filtered resulting in a first gypsum 10 resuming the flow of reactants into one or all reactors of
liquid residue and a residual gypsum cake; and the plurality of reactors;
transporting the residual gypsum cake on the filter to Zone separating the first precipitate calcium carbonate and
B in which the residual gypsum cake is washed with gypsum remnant from the ammonium Sulfate Solution
water to result in a second gypsum liquid residue.
27. The process of claim 25, wherein the step of separat- 15 to result in a product ammonium sulfate solution and a
ing the first and second precipitate calcium carbonate from remnant cake of precipitated calcium carbonate and
the solution of ammonium Sulfate and ammonium carbonate gypsum,
is accomplished by steps comprising: retaining the product ammonium Sulfate Solution;
filtering the first and second precipitate calcium carbonate feeding a flow of reactants being the remnant cake of first
from the solution of ammonium sulfate and ammonium 20 precipitate calcium carbonate and gypsum and ammo
carbonate on a filter having two Zones, Zone A and Zone nium carbonate solution, selectively into one or all
B, wherein Zone A the solution of ammonium sulfate reactors of the plurality of reactors, for chemical reac
and ammonium carbonate is filtered resulting in a tion;
calcium carbonate cake and a residue solution of
stopping the flow of reactants into one or all reactors of
ammonium Sulfate and ammonium carbonate; 25 the plurality of reactors for a reactor retention time
adding the residue solution of ammonium sulfate and selected for any one or all reactors of the plurality of
ammonium carbonate to one or both of the first and
reactors, wherein the retention time for a particular one
second reactors; reactor is selected to achieve a predetermined degree of
transporting the calcium carbonate cake on the filter to chemical reaction in the particular one reactor to form
Zone B in which the calcium carbonate cake is washed 30
a second precipitate calcium carbonate and a solution
with water to result in a product calcium carbonate cake of ammonium sulfate and ammonium carbonate;
and a wash water solution of ammonium sulfate and
ammonium carbonate; discharging the first and second precipitate calcium car
bonate and a solution of ammonium Sulfate and ammo
retaining the product calcium carbonate cake; and
feeding the wash water Solution of ammonium sulfate and 35 nium carbonate from one or all reactors of the plurality
ammonium carbonate to an ammonium carbonate of reactors;
absorber to retain ammonium carbonate. resuming the flow of reactants into one or all reactors of
28. A partially continuous countercurrent flow process for the plurality of reactors;
converting gypsum to ammonium Sulfate and calcium car separating the first and second precipitate calcium car
bonate comprising the following steps: 40 bonate from the solution of ammonium Sulfate and
separating an aqueous slurry of gypsum to result in a ammonium carbonate to result in a product calcium
gypsum liquid residue and a gypsum cake; carbonate cake and a residue solution of ammonium
feeding a flow of reactants being the gypsum cake and a Sulfate and ammonium carbonate;
Solution of ammonium sulfate and ammonium carbon retaining the product calcium carbonate cake; and
ate, selectively into one or all reactors of a plurality of 45
reactors, for chemical reaction; adding the residue solution of ammonium Sulfate and
ammonium carbonate to one or all reactors of the
stopping the flow of reactants into one or all reactors of plurality of reactors.
the plurality of reactors for a reactor retention time
selected for any one or all reactors of the plurality of k k k k k