USOO5378447A

United States Patent (19) 11) Patent Number: 5,378.447

Jackson et al. 45) Date of Patent: Jan. 3, 1995
54 METHOD FOR THE PREPARATION OF 4,159,929 7/1979 Grotheer ............................... 204/95
CHLORATES FROM WASTE GAS STREAMS 4,175,038 11/1979 Sakowski .............................. 20/62
OBTANED FROM THE PRODUCTION OF 4,216,195 8/1980 Jaszka et al. . ... 423/478
CHLORINE DOXIDE 4,961,918 10/1990 Norell et al. ........................ 423/478
FOREIGN PATENT DOCUMENTS
75) Inventors: John R. Jackson; Charles L. Pitzer,
both of Wilmington, N.C.; Charles 19189 7/1895 United Kingdom ................ 423/475
O. Buckingham, Storrington 1175352 12/1969 United Kingdom................ 423/475
Township, Canada Primary Examiner-Gary P. Straub
73) Assignee: Huron Tech Corp., Delco, N.C. Assistant Examiner-N. M. Nguyen
21 Appl. No.: 148,356 Attorney, Agent, or Firm-Andrew E. Pierce
57 ABSTRACT
22 Filed: Nov. 8, 1993
A process is disclosed for producing a dilute solution of
Related U.S. Application Data an alkali or alkaline earth metal chlorate from a chlorine
and carbon dioxide waste gaseous stream. The process
63 Continuation of Ser. No. 924,546, Jul. 31, 1992, aban of the invention can be combined in a continuous pro
doned.
cess for the production of an alkali or alkaline earth
51) Int. Cl. .............................................. C01B 11/14 metal chlorate for use in a chlorine dioxide generator
52 U.S. C. .................................... 423/475; 423/478; for the production of chlorine dioxide in which the
423/479; 423/240 R; 204/95 waste gaseous stream from the chlorine dioxide genera
58 Field of Search ........... 423/475, 478,479, 240 R; tor is converted to a dilute solution of an alkali or alka
204/95 line earth metal chlorate and passed to an electrochemi
(56) 4. References Cited
cal cell for the generation of an alkali or alkaline earth
metal sodium chlorate, the product of the electrochemi
U.S. PATENT DOCUMENTS cal cell being in turn passed to the chlorine dioxide
388,217 8/1888 Muspratt ............................. 423/475 generator.
3,690,845 9/1972 Grotheer ............................. 423/475
3,984,523 10/1976 Schajer et al. .................. 423/240 R 14 Claims, 3 Drawing Sheets
U.S. Patent Jan. 3, 1995 Sheet 1 of 3 5,378.447
U.S. Patent Jan. 3, 1995 Sheet 2 of 3 5,378.447

35

25
34
2.

42 18 O 13
N30 22 20 36 37
31. -- - - --V as is - -

43

39 (+) (-)
X
46

28 40 9 Fig-2
44
U.S. Patent Jan. 3, 1995 Sheet 3 of 3 5,378,447

35

CO2 VENT

H2O, NaClO,
NaOH, Na2CO3

CARBONATE- Na2CO-CO2-H2O-D-2NaHCO
2CO3FCO2H2O 3
pH 9-11 Na2CO3*C12--NaCIO+NaCl + CO2

pH 8-9
NaHCO+CI 2 -- NaCl-HC10+CO2
CO2, Cl2
HYPOCHLORITE,
WATER WAPOR

NaHCO3
HCO, NaCO, WATER
Fig-3
 5,378.447
1. 2
or, if desired, sodium hydrogen sulphate in strong sulfu
METHOD FOR THE PREPARATION OF ric acid. The gases carbon dioxide and possibly some
CHLORATES FROM WASTE GAS STREAMS chlorine are produced in the Rapson R-8 process. Pas
OBTANED FROM THE PRODUCTION OF sage of these gases through a sodium hydroxide scrub
CHELORINE DOXDE ber produces an aqueous liquor stream of sodium chlo
ride, sodium hypochlorite and sodium carbonate. It is
This is a continuation of copending application Ser. essential from an economical as well as an environmen
No. 07/924,546 filed on Jul. 31, 1992, now abandoned. tal point of view that this liquor be utilized. However,
BACKGROUND OF THE INVENTION this waste stream cannot be used because of the genera
10 tion of chloroform from the sodium hypochlorite
1. Field of the Invention formed during the scrubbing of chlorine with sodium
This invention relates, generally, to the utilization of hydroxide in the wood pulp bleaching process.
waste gas streams containing chlorine and carbon diox The process of reacting chlorine with caustic to made
ide and, particularly, to waste gas streams produced sodium chlorate has been known for over 100 years.
during the production of chlorine dioxide by the reac 15 Under alkaline conditions chlorine reacts with caustic
tion of an alkali or alkaline earth metal chlorate with a to make sodium hypochlorite:
reducing agent.
2. Description of the Prior Art Cl2+2NaOH-NaClO--NaCl--H2O V.
Chlorine dioxide is an oxidation agent and an impor
tant bleaching agent in the pulp industry where it is the Under approximately neutral conditions, sodium hypo
most common bleaching agent used in the final stages of chlorite reaches an equilibrium with hypochlorous acid
pulp bleaching. Recently, there has been an increased and forms sodium chlorate:
use of chlorine dioxide instead of other bleaching agents
especially sodium hypochlorite and chlorine. It is NaClO-2HCIO-NaClO3-2HCl VI.
known that the use of chlorine in bleaching pulp, lead to 25
the production of dioxins which are released to the Making sodium chlorate this way is generally not prac
environment in the disposed wastes. Sodium hypochlo ticed because it is cheaper to make sodium chlorate by
rite solutions, when used in bleaching pulp, lead to the the direct electrolysis of salt:
formation of chloroform which cannot be tolerated in
the paper industry at any concentration. Accordingly, NaCl-3H2O--6 Faradays-NaClO3-3H2 VII.
there is a decreased use of chlorine and sodium hypo
chlorite as bleaching agents in the wood pulp industry. Presently, caustic is used to remove chlorine from tail
Methods formerly used for the preparation of chlo gas streams from sodium chlorate, chlorine or chlorine
rine dioxide by reduction of sodium chlorate can be dioxide plants according to reaction V. The resulting
summarized in the following gross formulas: 35 sodium hypochlorite solution has typically been a useful
chemical in such applications as pulp bleaching, and the
pulp and paper industry has always provided a useful
2NaClO3 + SO2 -G 2CO2 + Na2SO4 market for this chemical.
(the Mathieson process) Sodium hypochlorite is being phased out of wood
2NaClO3 + CH3OH + H2SO4 - G
II. pulp bleaching because it forms chloroform on the pulp.
2CO2 + HCOOH + H2O -- Na2SO4.
This poses a particularly severe problem in the genera
tion of chlorine dioxide because, whereas tail gases from
(the Solvay process) sodium chlorate and chlorine plants contain only trace
NaClO3 + NaCl + H2SO4 - Ge.
II, amounts of chlorine, chlorine dioxide generators of the
CO2 -- Cl2 + H2O -- Na2SO4. 45 R2, R3, and SVP type produce 0.6-0.7 lb of chlorine
per 1b of chlorine dioxide and frequently the concentra
(the R-2, R-3, and SVP process) tion of chlorine in the tail gases is over 70%. Further
contributing to the problem is the trend in the pulp and
Thus, the reducing agent in these processes is sulphur paper industry to increase chlorine dioxide production
dioxide, methanol and chloride ion respectively. Other SO because chlorine dioxide has been shown to reduce
reducing agents, such as chromic acid or nitrogen ox formation of dioxin and chlorinated organics when
ides have also been tested, but, principally, due to their substituted for chlorine in the pulp bleaching process.
higher prices they have not been commercially utilized Any NaCl which enters a chlorine dioxide generator
to a considerable degree. results in an equivalent amount of Cl2 by-product. To
A modern method for chlorine dioxide production is 55 address this concern pulp and paper mills are switching
as follows: to a new type of chlorine dioxide generator which uses
methanol as the reducing agent instead of NaCl, thereby
producing CO2 as a by-product rather than Cl2. How
ever some by-product chlorine can still be produced
from generator inefficiency or decomposition, or from
any salt present in the sodium chlorate feed. For exam
(The Rapson R-8 Process) ple, sodium chlorate from solution sodium chlorate
plants would contain 0.1-0.3 moles of NaCl per mole of
All these processes take place with an excess of a NaClO3. Also, although claims are made that the use of
strong acid, usually sulfuric acid. In process for the methanol as a reducing agent in chlorine dioxide gener
production of chlorine dioxide in which sulfuric acid is ators allows the omission of chloride ion in the sodium
used, the spent liquor or saltcake of the reactor will chlorate feed, it is well documented that their operation
consist of sodium sulphate and/or strong sulfuric acid is more stable if some chloride ion is present.
 5,378,447
3 4.
Chlorine resulting from any of these reasons can end railcar or truck and (2) manufacture an aqueous solution
up in the chlorine dioxide generator chlorine tail gas of sodium chlorate on the site of the pulp mill. The
scrubber where it will be removed according to reac advantages of manufacture of an aqueous solution of
tion V. However, by-product CO2 from the methanol sodium chlorate at the pulp mill are well documented in
will also be scrubbed according to reaction VIII below the literature. Most of the advantages to be obtained are
thus creating a scrubber effluent which is no longer a the result of the ability of pulp mill sodium chlorate
simple sodium hypochlorite solution, but rather a mix manufacturing facilities to prepare the aqueous sodium
ture of sodium hypochlorite and sodium carbonate. chlorate solution at the proper concentration and qual
CO2+2NaOH-Na2CO3--H2O V. 10 ity desired so as to properly feed the chlorine dioxide
generators directly. This procedure eliminates crystal
Since these sodium hypochlorite solutions are no lizing the sodium chlorate, shipping, unloading, and
longer desirable pulp bleach chemicals, they have to be handling the sodium chlorate which would be other
dealt with in other ways. An obvious approach is to wise purchased from off-site manufacturers. With pulp
neutralize the solutions with acid so the sodium hypo 15 mill sodium chlorate requirements ever increasing, the
chlorite will convert to sodium chlorate according to advantages of on-site sodium chlorate solution manufac
reaction VI, and then reprocess the resulting sodium ture are greater than ever.
chlorate solution in the chlorine dioxide generators or Alkali metal chlorate, and in particular sodium chlo
in any available sodium chlorate plant. However the rate has been produced by the electrolysis of aqueous
presence of sodium carbonate in the solutions makes 20 solutions of alkali metal chlorides, such as sodium chlo
this approach impractical by any conventional means ride, in electrolytic cells equipped with or without
because the neutralization process will drive off the membranes or diaphragms. Typically, electrolytic cells
sodium carbonate as CO2 which causes several prob make sodium chlorates within the cell by reacting chlo
lems which render prior art processes unusable: rine produced at the anode with sodium hydroxide
(a) The liberated CO2 will contain high levels of 25 produced at the cathode. One such representative elec
chlorine and/or sodium hypochlorite and will trolytic cell of this type is shown in U.S. Pat. No.
therefore have to be scrubbed, but any conven 3,732,153 by C. J. Harke et al. Various other arrange
tional scrubber will also remove the CO2 as sodium ments of both electrochemical and combinations of
carbonate thereby creating a closed system where electrochemical and chemical methods for manufactur
sodium carbonate will build up to the saturation 30 ing sodium chlorates have also been proposed, such as
point and eventually shut down the process. the use of a two compartment permselective membrane
(b) The tiny bubbles of CO2 forming in the solution equipped electrolytic cell operating in conjunction with
cause severe foaming which renders most conven a diaphragmless-type electrolytic sodium chlorate cell.
tional reactors unusable.
(c) The sodium carbonates will consume expensive This method is disclosed in U.S. Pat. No. 3,897,320 to E.
acid and yield only low value sodium chloride salt 35 H. Cook. However, to obtain improved current effi
according to reaction IX. below: ciencies and significant reductions in electrical power
requirements in the production of inorganic sodium
Na2CO3-2HC-CO2--2NaCl--H2O IX. chlorate, U.S. Pat. No. 3,464,901 provides for the elec
trochemical preparation of chlorine and caustic soda in
In a similar fashion, sodium carbonate could also a diaphragm type chloralkali cell. The caustic soda
build up over time from chlorine tail gas scrubbers in containing unreacted alkali metal chloride and alkali
sodium chlorate, chlorine or water treatment plants, or metal chlorate is then removed from the cell and mixed
any other process where chlorine is used, because of and chemically reacted with chlorine from the anolyte
CO2 coming from the atmosphere, floor washings or of the cell. The chemical reaction is carried out at a pH
from a brine purification area. Therefore a system is 45 of 6 to 8 to convert the sodium hypochlorite to sodium
needed which will treat any chlorine tail gas or sodium chlorate. However, in order to maintain the conditions
hypochlorite solution in such a way that unwanted CO2 most favorable for converting sodium hypochlorite to
or sodium carbonate will be separated and purified of sodium chlorate, additional caustic and/or acid over
entrained chlorine or sodium hypochlorite compounds and above that supplied by the cell has to be added to
such that the unwanted CO2 can be safely discharged 50 the reaction mixture. In the case of Japanese Pat.
from the process, and the sodium hypochlorite and/or No.792,025 dilute chlorine is reacted with less than 20
any free alkalinity in the effluent will be converted to a percent caustic soda to produce a concentrated sodium
usable sodium chlorate solution suitable for reprocess hypochlorite solution with sufficient caustic remaining
ing even in a closed loop system. in it to produce a pH of 8 to 10. The solution is subse
Ninety-five percent of the sodium chlorate produced 55
is used in the pulp and paper industry to manufacture quently diluted from about 13 to 15 percent sodium
chlorine dioxide. Chlorine dioxide has been shown not hypochlorite to 6 to 8 percent sodium hypochlorite
to produce dioxins and other chlorinated organics when with a recycled stream of sodium chloride and sodium
substituted for chlorine in the pulp bleaching process. chlorate. The diluted stream is then acidified with hy
Accordingly, the use of chlorine for bleaching with drochloric acid to a pH of about 6.0 and finally fed to an
pulp has been sharply reduced and the demand for chlo electrolysis cell.
rine dioxide in the pulp and paper industry has risen In U.S. Pat. No. 4,175,038 to Sakowski, a process is
rapidly over the past few years. Since chlorine dioxide disclosed for reducing the available chlorine content of
is made by reducing an aqueous solution of sodium aqueous waste streams, especially calcium hypochlorite
chlorate, as indicated above, pulp mills have two op 65 waste streams. In the process of this reference, the avail
tions for supplying chlorine dioxide generators with an able chlorine content is reduced by chlorinating the
aqueous solution of sodium chlorate: (1) purchase so impure stream at a temperature in the range of about 80'
dium chlorate crystal and obtain shipment thereof via to 100 C. at a pH in the range of about 5.5 to about 8.5.
 5,378.447 6
5
During this reaction, the available chlorine is reacted to rine dioxide of high purity and converting the chlorine
form the corresponding calcium chlorate. to sodium chlorate and sodium chloride which may
In U.S. Pat. No. 4,159,929 to Grotheer, a process is then be recirculated to a chlorine dioxide generator.
disclosed for producing alkali metal chlorates by the Various processes are disclosed in the prior art for the
reaction of an aqueous solution of an alkali metal chlo destruction of an alkalimetal hypochlorite, for instance,
ride, alkali metal chlorate and an alkali metal hypochlo by reacting an alkali metal hypochlorite with an acid to
rite with an alkali metal hydroxide. Chlorine is added to produce chlorine, U.S. Pat. No. 4,404,179; the reaction
the reaction mixture in an amount sufficient to maintain of chlorine with hydrazine in U.S. Pat. No. 3,823,225; or
the pH of the reaction mixture at about 5-7.5 in order to the reaction of an alkali metal hypochlorite with urea,
promote the conversion of alkali metal hypochlorite to 10 U.S. Pat. No. 4,508,697.
alkali metal chlorate. Subsequently, the reaction prod In U.S. Pat. No. 4,620,969 to Wilkinson, a process is
uct is led to an electrolysis cell for the production of an disclosed for the production of chlorine by the electrol
alkali metal chlorate. Instead of feeding brine to the ysis of an aqueous solution of sodium chloride. In part
electrolytic sodium chlorate cells, the feed solution is of this process, a gaseous stream containing chlorine
made, for instance, by reacting a sodium hydroxide 15 and carbon dioxide are passed into a first reaction vessel
solution with chlorine at neutral pH to make a weak and thence into a second reaction vessel and aqueous
sodium chlorate solution which is then electrolyzed in sodium hydroxide solution is charged to the first reac
electrochemical cells to a strong sodium chlorate solu tion vessel and aqueous sodium hydroxide is separately
tion. Gaseous chlorine is added to the caustic in an charged to the second reaction vessel. An aqueous solu
in-line mixer at 70-80 C. in an amount such that the tion containing sodium hypochlorite is removed from
pH of the mixture is controlled at 5.0–7.5. The resulting the first reaction vessel and an aqueous solution contain
sodium hypochlorite solution is then held in an aging ing sodium carbonate is removed from the second reac
tank to allow the sodium hypochlorite to convert to tion vessel.
sodium chlorate. In U.S. Pat. No. 4,129,484 to Larsson, a process is
In Grotheer, the chlorine and chemical feeds to the 25 disclosed for the utilization of residual solutions ob
process are relatively pure and no provision is made to tained from a chlorine dioxide reactor in which sodium
deal with situations where sodium carbonates may be chlorate is reduced to chlorine dioxide in the presence
present, such as tail gases from a methanol type chlorine of an acid. The residual solutions are converted to so
dioxide generator. The system does not provide any dium chlorate by leading the residual solutions to an
way to purify or handle effluent gases which may ema 30 electrolytic cell having at the anode region of the cellan
nate from the chlorine/caustic reaction, nor does it acid enriched fraction of the residual solution.
show any way to deal with foam which would accom The process of the instant invention is particularly
pany such gases. Also, the in-line mixer and aging tank suited for the removal and reuse of the large volumes of
are not vented and any gases emanating from the reac alkali or alkaline earth metal hypochlorite produced
tion, such as CO2, could create unsafe pressures. Vent 35 subsequent to scrubbing the chlorine and carbon diox
ing these vessels would release chlorine and sodium ide gases produced during the generation of chlorine
hypochlorite to the atmosphere, but employing a scrub dioxide by the reduction of an alkali or alkaline earth
ber would return such gases as CO2 to the system as metal chlorate in the presence of an acid and methanol
sodium carbonate or sodium bicarbonate which would as a reducing agent. The carbon dioxide is vented to the
build up to the saturation point and shut the process atmosphere and the an alkali or alkaline earth metal
down. hypochlorite is converted by the process of the instant
Also, Grotheer does not produce a sodium chlorate invention to a dilute solution of an alkali or alkaline
solution low enough in sodium hypochlorite concentra earth metal chlorate by reaction with chlorine gas or an
tion to be purified by conventional means, such as ion acid. If desired, the alkali or alkaline earth metal chlo
exchange. This means that dilute sodium hypochlorite 45 rate can be recycled in a continuous process to an elec
solutions, such as would be discharged from a chlorine trolytic cell for the production of an alkali or alkaline
tail gas scrubber, would not be suitably treated to be, for earth metal chlorate as a feed for a chlorine dioxide
example, saturated with NaCl and purified for recycle generator.
to electrolytic sodium chlorate cells. SUMMARY OF THE INVENTION
In summary, the described process of Grotheer is not 50
able to handle chlorine tail gases or sodium hypochlo A batch or continuous process is disclosed which is
rite solutions which contain CO2 or sodium carbonate, particularly suited for the removal and reuse of the
nor is the process able to produce a sodium chlorate large volumes of alkali or alkaline earth metal hypo
solution which can be recycled in a closed loop system chlorite which are present in an aqueous waste stream
unless the component chemicals are predictably very, 55 subsequent to scrubbing the waste gases, chlorine and
pure. carbon dioxide, with an alkali or alkaline earth metal
In U.S. 4,216,195 to Jaszka, the production of chlo hydroxide. These waste gases are produced in the gen
rine dioxide having a low chlorine content is disclosed. eration of chlorine dioxide by reducing an alkali or
A separation technique is utilized in which a gaseous alkaline earth metal sodium chlorate in the presence of
product stream from a chlorine dioxide generator is sulfuric acid and methanol as a reducing agent. For
scrubbed with an aqueous salt mixture containing an convenience the alkali or alkaline earth metal salt reac
approximately stoichiometric quantity of sodium hy tants and products produced in the process of the inven
droxide. The scrubbing media is a controlled solution of tion will be exemplified in the description below as
sodium chlorate, sodium chloride and sodium hydrox sodium salts. One skilled in this art will understand that
ide which is free of sodium carbonate. The process is 65 other alkali metal salts as well as alkaline earth metal
not applicable for processing of sodium hypochlorite salts can be used.
effluent streams. The sodium hydroxide reacts preferen In the process of the invention a waste gaseous stream
tially with the chlorine in the gas stream, yielding chlo comprising chlorine and carbon dioxide is converted to
 5,378,447
7 8
an aqueous waste stream mixture, generally, comprising optimum performance of the whole system is used.
an alkali or alkaline earth metal hypochlorite, carbon Sodium chlorate is made at conversion efficiencies
ate, and chloride, preferably, comprising an alkali metal equivalent to those achieved by electrochemical tech
hypochlorite, carbonate, and chloride, and, most prefer niques. The sodium chlorate which is made is essentially
ably, comprising the sodium salts. Sodium hypochlorite free of sodium hypochlorite and can be purified by a
is converted by the process of the invention to sodium conventional ion exchange purification process to make
chlorate as a dilute aqueous solution which can be uti a suitable recycle stream so as to avoid the carry over
lized as a portion of the feed solution of an electrochem and build-up of impurities such as heavy metals.
ical cell for the production of sodium chlorate. The A process for the production of chlorine dioxide in a
aqueous waste stream mixture from the chlorine dioxide 10 chlorine dioxide reaction zone is also disclosed in which
generator after scrubbing with aqueous sodium hydrox the by-products of said reaction are converted to an
ide contains, besides an aqueous sodium hypochlorite, aqueous mixture comprising an alkali or alkaline earth
an aqueous solution of a mixture of sodium carbonate, metal hypochlorite, carbonate, and chloride and re
sodium hydroxide, and sodium chloride. In the process acted in a scrubbing zone while venting gases compris
of the invention, the carbon dioxide produced is vented 15 ing carbon dioxide from said scrubbing zone and succes
to the atmosphere. The remaining components of the sively reacting said aqueous mixture from said scrub
aqueous waste stream mixture are converted to an aque bing zone in at least a first and second reaction zone
ous sodium chlorate, bypassing said waste stream com with an acid or an acid gas reactant to produce an alkali
ponents counter-currently to a gaseous mixture derived or alkaline earth metal chlorate and, subsequently, pass
from subsequent reaction zones. Said gaseous mixture, 20 ing said alkali or alkaline earth metal chlorate to an
preferably, comprising an acid gas, and, most prefera electrolytic cell for the production of an aqueous solu
bly, comprising chlorine, carbon dioxide, and water tion of an alkali or alkaline earth metal chlorate together
vapor is subsequently reacted at elevated temperature with an aqueous solution of an alkali or alkaline earth
with an acid or an acid gas reactant in at least two metal chloride. The alkali or alkaline earth metal chlo
successive co-current reaction zones, preferably, in 25 rate product of said electrolytic cell is then passed to
three successive reaction zones. Effluent gases from said chlorine dioxide reaction zone to complete the
said reaction zones comprise carbon dioxide, chlorine, process which can be continuous.
and water vapor. The advantages of the use of a gaseous BRIEF DESCRIPTION OF THE FIGURES
chlorine reactant over the use of an acid is that the
sodium chlorate product obtained is not further diluted 30 The objects and advantages of the present invention
with water from the acid solution and increased yield of will be more clearly understood when considered in
the sodium chlorate product is obtained in accordance conjunction with the accompanying drawings, in
with reactions V. and VI. which:
In the process disclosed, aqueous waste product so FIG. 1 is a schematic flow sheet illustrating one em
dium hypochlorite solutions containing sodium carbon 35 bodiment of the process of the invention for the conver
ates or chlorine tail gases and carbon dioxide are treated sion of the waste gases chlorine and carbon dioxide to a
with a chlorine gas reactant in a high temperature co dilute sodium chlorate solution. FIG. 2 is a schematic
current reactor in such a way that the sodium hypochlo flow sheet illustrating the conversion in a continuous
rite and any free alkalinity associated with it are con process of the waste gases chlorine and carbon dioxide,
verted to sodium chlorate at a high efficiency, while produced in a chlorine dioxide generator, to a dilute
any sodium carbonates are simultaneously separated solution of sodium chlorate; the subsequent leading of
and removed as effluent CO2 gas. The effluent CO2 gas this solution into an electrolytic cell; and, thereafter, the
is scrubbed free of chlorine in a counter-current reactor conversion of this sodium chlorate solution in the pres
by a sodium hypochlorite solution so that the effluent ence of methanol and acid in a chlorine dioxide genera
gases exiting the process are essentially free of chlorine 45 tor to chlorine dioxide with the subsequent production
and sodium hypochlorite and can be discharged to the of more of the waste gases chlorine and carbon dioxide.
atmosphere. The preferred process of the invention Expected chemical compounds, chemical reactions and
comprises the following: the expected reaction sequence taking place in packed
1) The chlorine is scrubbed from the effluent gases bed scrubber column 4 are illustrated in FIG. 3.
with an aqueous sodium hypochlorite scrubber 50
DETAILED DESCRIPTION OF THE
solution.
2) The heat in the effluent gases emanating from the INVENTION
process reactors is used to preheat said scrubber It is a principle object of the present invention to
solution while the sodium hypochlorite scrubber provide a process for the removal and reuse of the large
solution cools and condenses water vapor and so 55 volumes of alkali or alkaline earth metal hypochlorite
dium hypochlorite from the effluent gases. containing aqueous waste solutions generated in the
3) The last traces of chlorine from the effluent gases production of chlorine dioxide, where carbonates may
can be removed with an optional reducing agent. be present. The process is particularly suitable for the
4) Any strong acid can be used as a substitute for said treatment of waste gas streams produced in a chlorine
chlorine gas reactant provided that the sodium dioxide generator in which an alkali or alkaline earth
hypochlorite is converted to sodium chlorate and metal chlorate is reacted with an acid and methanol as
free alkalinity is converted to sodium chloride or a reducing agent. An alkali or alkaline earth metal hy
other salts. pochlorite is produced by scrubbing the waste gas
Unique advantages of the process of the invention stream, containing chlorine and carbon dioxide, with an
include: Foaming from CO2 liberation is virtually elimi 65 aqueous solution of an alkali or alkaline earth metal
nated as a problem and the process works whether hydroxide.
sodium carbonate is present or not. A unique pH con In the process of the invention, sodium hypochlorite,
trol system with a single pH control point which allows produced by scrubbing with sodium hydroxide a gas
 5,378,447
9 10
stream containing chlorine and carbon dioxide, can be about 100° C. The heated liquid is initially reacted in
recycled, after conversion to an aqueous solution of zone 26 with chlorine gas, the amount of which is con
sodium chlorate, to an electrochemical cell for the pro trolled by pH controller 12 by way of control circuit 16
duction of sodium chlorate and utilized in admixture acting upon chlorine gas controller 30. Chlorine gas
with a brine feed for such an electrochemical cell. For 5 enters gas controller 30 through line 31 and exits
instance, sodium hypochlorite is converted to sodium through line 32. Measurement of the reaction solution
chlorate by reacting sodium hypochlorite with chlorine pH in second reaction zone 8 is effected by leading a
gas and/or an acid reactant at elevated temperature portion of the reaction mixture in reaction zone 8
and, most preferably, at acid pH conditions. The waste through lines 17 and 18 and by way of heat exchanger
constituents of the aqueous waste stream, after scrub O 24, the amount of reaction mixture withdrawn being
bing with aqueous sodium hydroxide comprise sodium controlled by pump 22. The reaction mixture is led to
hypochlorite, sodium hydroxide, sodium carbonate, and pH controller 12 by way of line 20. After pH sampling,
sodium chloride. The sodium carbonate is converted to the reaction mixture is led to reaction zone 10 through
carbon dioxide and vented to the atmosphere and the line 23. The converted liquids exit reaction zone 10
remaining components of the waste aqueous stream are 15 through line 27 as dilute, aqueous sodium chlorate solu
converted to an aqueous solution of sodium chlorate tion while gaseous products produced in second reac
and sodium chloride which can be cycled, if desired, to tion zone 8 and third reaction zone 10 are led to the
an electrochemical cell together with brine for the pro bottom of packed bed column 4 by way of lines 21 and
duction of sodium chlorate. Alternatively, the aqueous 15, respectively, which join line 25. The gaseous prod
solution of sodium chlorate and sodium chloride pro ucts produced in second reaction zone 8 and third reac
duced by the process of this invention can be combined tion zone 10, carbon dioxide and chlorine, together with
with additional water to provide the water required to sodium hypochlorite and water vapor rise in packed
dissolve solid sodium chlorate for use as a feed for a bed column 4 and initially react with the descending
chlorine dioxide generator. sodium hypochlorite, sodium carbonate and sodium
Instead of using gaseous chlorine as a reactant in the 25 hydroxide. Carbon dioxide is released throughline 35 to
process of the invention, an acid can be used such as the atmosphere at the top of packed bed column 4 to
hydrochloric acid or sulfuric acid. However, the use of complete the process. The second reaction zones 8 and
chlorine gas as a reactant in the process of the invention the third reaction zone 10 are reaction completion
provides an aqueous sodium chlorate product in higher ZOcS.
yield which is not further diluted by the water in the 30 In another aspect of the invention of the instant appli
hydrochloric acid or sulfuric acid reactant. In addition, cation, one embodiment of which can be readily under
a higher yield of sodium chlorate is obtained in accor stood by referring to FIG. 2, the conversion of the
dance with reactions V. and VI. waste gases chlorine and carbon dioxide to a dilute
sodium chlorate solution as shown in the schematic
DETAILED DESCRIPTION OF THE FIGURES 35
flow sheet of FIG. 1, the description of which is incor
The invention can be readily understood by referring porated herein, can be combined into a continuous pro
to FIG. 1 which is a schematic flow sheet illustrating cess, as shown in FIG. 2, in which a dilute sodium chlo
one embodiment of the process for conversion of a rate solution exiting in line 27 from third reaction zone
mixture of waste gases comprising chlorine and carbon 10 is led through line 27 to salt saturator 29 and com
dioxide to a dilute aqueous solution of sodium chlorate. 40 bined therein with a brine solution entering salt satura
In the following description of FIGS. 1-3, sodium chlo tor 29 in line 13. A saturated salt solution exits salt satu
rate is described as a specific alkali metal chlorate rator 29 through line 37 and enters chemical or ion
which is produced in the process of the invention. One exchange purification zone 36 and thence by line 38
skilled in this art will understand that the process of the enters an electrolytic cell 9 for the production of so
invention is applicable to other alkali metal chlorates as 45 dium chlorate. The aqueous sodium chlorate product
well as alkaline earth metal chlorates. In the embodi solution is led through line 46 from electrolytic cell 9 to
ment of the process of the invention shown in FIG. 1, chlorine dioxide generator 43. Heat exchanger 28 is
the waste gases are first led through line 34 into an used to provide heat for accelerating the reaction in
aqueous sodium hydroxide scrubber 2. An aqueous chlorine dioxide generator 43 using lines 44, 39, and 41
solution of sodium hydroxide is led into scrubber 2 to circulate the contents of chlorine dioxide generator
through line 3. Said waste gases are converted in scrub 43. A reducing agent and an acid, preferably, methanol
ber 2 to a mixture of sodium hypochlorite, sodium car and sulfuric acid, are also added through line 41 to
bonate and sodium chloride as an aqueous, alkaline chlorine dioxide generator 43. Salt cake is withdrawn
solution. This aqueous solution is, thereafter, led from chlorine dioxide generator 43 through line 40 and
through line 5 to the top of a packed bed column 4 in 55 the remaining products of the reaction, chlorine diox
which the aqueous liquid passes downward by gravity ide, carbon dioxide, chlorine and water vapor exit
while contacting sodium hypochlorite and rising vapors through line 33 from chlorine dioxide generator 43 to
of chlorine, carbon dioxide and water which enter at absorber 45 which is fed with chilled water through line
the bottom of packed bed column 4 through lines 21 and 48. Waste gases are led through line 34 to tail gas scrub
25 from reaction zone 10 and through line 15 from 60 ber 2. Chlorine dioxide is withdrawn through line 42
reaction zone 8. The solution exiting the bottom of the from absorber 45. The tail gases pass counter-currently
packed bed column 4 is led through line 7 to heat ex to an aqueous solution of sodium hydroxide which en
changer 6 and thereafter exits through line 14 and is led ters scrubber 2 through line 3. The waste gases are
successively to first reaction zone 26 and then through converted to an aqueous solution of sodium hypochlo
line 11 to second reaction zone 8. The reaction tempera 65 rite, sodium carbonate, and sodium chloride and are
ture in reaction zones 26, 8, and 10 is, generally, about subsequently led through line 5 from scrubber 2 to
60° C. to about 105 C., preferably, about 85° C. to packed bed column 4 for initial reaction with gases
about 100 C. and, most preferably, about 95 C. to comprising chlorine gas which enters at the base of
 5,378,447
11 12
packed bed column 4 through line 25. Said converted NaCIO-2HCIO-NaClO3-2HC XI.
products after reaction are passed through the bottom
of packed bed column 4 through line 7 into heat ex A unique aspect of the process of the invention is that
changer 6 and thence through line 14 to first reaction a single pH control point controls the overall perfor
zone 26 which is fed with chlorine gas through lines 31 5 mance of the system. Good pH control is necessary to
and 32 by way of gas control valve 30, the amount of achieve optimum performance, which, generally, is
gas or acid being controlled by pH controller 12 achieved when the pH of the final weak sodium chlo
through control circuit 16. rate solution exiting from second reaction zone 10 is in
Where bicarbonate is not present, a pH, generally of the most preferred pH range of about 6.4 to about 6.9.
about 4.0 to about 8.5, preferably, about 5 to about 7, 10 The pH is controlled, generally, by adding chlorine gas
and, most preferably, about 6.4 to about 6.9 is main or acid to reaction zone 26 via line 32, and measuring
tained in second reaction zone 8 and third reaction zone the pH in reaction zone 8. The addition of the preferred
10 by sampling the liquid in second reaction zone 8 chlorine gas reactant to reaction zone 8 lowers the pH.
through lines 17 and 18 by way of heat exchanger 24 The desired pH control range in reaction zone 8 to
and pump 22. Where bicarbonate is present, the pH in 15 achieve optimum performance is dependent on the
second reaction zone 8 may be controlled at a lower pH composition of the sodium hypochlorite feed solution,
than the resulting pH of the third reaction zone 10, for the temperature of the sodium hypochlorite feed solu
example, if the bicarbonate concentration in line 11 is 5 tion, and the specific engineering design of the system.
gpl, the pH control range in second reaction zone 8 In systems where some sodium bicarbonate is still pres
would be 4.0 to 6.0 and preferably, 4.8 to 5.2. Said liquid 20 ent in the sodium hypochlorite solution entering reac
is led through line 20 to pH controller 12. After sam tion zone 10 via line 19, the sodium bicarbonate will
pling, said liquid is returned through line 23 to third cause the pH in reaction zone 10 to go up and, accord
reaction zone 10. The contents of first reaction zone 26 ingly, the pH control range in reaction zone 8 has to be
are led through line 11 subsequent to an initial reaction set proportionally lower. For example, if the sodium
to second reaction zone 8 and then through line 19 to a 25 bicarbonate concentration in line 19 is 5 gpl, the pH
third reaction zone 10 in which the reaction is com control range in second reaction zone 8 would be, pref
pleted. Gases produced in reaction zones 8 and 10 are erably, about 4 to about 6 and, most preferably, about
withdrawn through lines 15 and 21, respectively, for 4.8 to about 5.2. If no sodium bicarbonate is present, the
return to packed bed column 4 by way of line 25. In pH control range in second reaction zone would, pref
third reaction zone 10, a dilute sodium chlorate solution 30 erably, be about 5 to about 7 and, most preferably, be
which is produced is withdrawn through line 27. about 6.4 to about 6.9.
It is noted that the gaseous products produced in The method of controlling the pH by adjusting the
second reaction zone 8 and third reaction zone 10, flow of chlorine gas or acid into one vessel and then
namely, carbon dioxide, chlorine, and water vapor, measuring the pH in a different vessel, thereby inten
provide chlorine as a reactant for the initial reaction 35 tionally introducing measurement lag time, is an uncon
with the sodium hypochlorite, sodium carbonate, and ventional method of pH control. Conventionally, the
sodium hydroxide aqueous solution passing down pH of a chemical system is measured as close as possible
wardly through packed bed column 4. The carbon diox to the point of chemical mixing. Otherwise conven
ide entering at the bottom of packed bed column 4 tional systems become insensitive to changes in chemi
ultimately is vented through the top of packed bed cal feed rate and run out of control. Applying conven
column 4 to the atmosphere through line 35. tional methods to the present system would put the pH
The mainly sodium hypochlorite aqueous solution measurement and control point in first reaction zone 26.
entering packed bed column 4 through line 5 in FIGS. However, pH control in reaction zone 26 was found to
1-3 may be any concentration and does not have to be be unachievable because of the violent evolution of gas
pure. The sodium hypochlorite solution may be alkaline 45 and foam, and also because even small changes in the
and may contain sodium chloride, sodium chlorate, chlorine feed rate, or of the pH of the incoming sodium
carbon dioxide, sodium carbonate or sodium bicarbon hypochlorite solution, cause large and rapid pH fluctua
ate in any combination up to the saturation point. tions in reaction zone 26. In reaction zone 8, the foam
Where the compounds are in the sodium form, the maxi and gases are dissipated and short term pH fluctuations
mum sodium ion concentration would be 5.4 gm 50 are damped out by the larger volume of solution. Mea
moles/liter with a preferred range of 1.0–4.0 gm-mole/- surement lag time unexpectedly turns out not to be a
liter. The pH of the sodium hypochlorite solution is problem because of the nature of the system, as de
normally between 11 and 14, although other pH's are scribed below.
possible. There is no temperature limitation on the en If chlorine is added in excess relative to the amount of
tering sodium hypochlorite solution, although a temper 55 incoming sodium bicarbonate in the sodium hypochlo
ature of about 10 to about 30° C. is preferred. The rite solution entering reaction zone 26, the chlorine
source of the sodium hypochlorite may be from chlo enters reaction zone 8 via line 11 with the gas liquid
rine scrubbers in sodium chlorate plants, chlorine mixture leaving reaction zone 26. Hypochlorous acid
plants, or chlorine dioxide generators, as shown in FIG. and hydrochloric acid are made which lowers the pH.
2, water treatment plants, etc. Optionally, chlorine gas If chlorine is added in further excess, the excess from
mixed with compounds such as air, hydrogen or carbon reaction zone 8 enters packed bed column 4 through
dioxide may be reacted with any suitable caustic solu lines 15 and 25. This lowers the pH of the sodium hypo
tion fed via line 3 to any suitable scrubber column 2. chlorite solution feeding reaction zone 26 and further
The reactions taking place in reaction zones 26, 8, and lowers the pH in reaction zone 8. If too little chlorine is
10 are as follows: 65 added relative to the amount of incoming sodium bicar
bonate present in the sodium hypochlorite solution,
NaHCO3-Cl2.HClO--NaCl-CO2 X. excess unreacted sodium bicarbonate is carried into
reaction zone 8. This neutralizes the acidity and imme
 5,378.447
13 14
diately raises the pH in reaction zone 8. The overall in the sodium hypochlorite solution in Zone D accord
effect of adding chlorine or acid to reaction zone 26 and ing to the reaction:
measuring the pH in reaction zone 8 is that there is
unexpectedly no apparent measurement lag time, and CO2+2NaOH-Na2CO3 + H2O XII.
pH control over the whole system is easily achieved. 5
If there is a loss of pH control such that there is a The free caustic in the sodium hypochlorite solution is
continued excess of chlorine coming into the system, a removed and the sodium carbonate concentration is
low pH condition will develop at the bottom of packed increased so that the pH of the sodium hypochlorite
bed column 4 and work its way to the top of packed bed solution leaving Zone D and entering Zone C will be
column 4, until chlorine starts to discharge from the 10 approximately 9-11. Wider pH ranges can be used. The
system with the vent gases. If there is a loss of pH con sodium hypochlorite solution cools the effluent gases
trol, and there is a continued deficiency of chlorine and condenses out water vapor and trace amounts of
coming into the system, the pH in reaction zone 8 and sodium hypochlorite in Zone D. The contact time and
reaction zone 10 will increase so that the weak sodium temperature of the sodium hypochlorite solution can be
chlorate solution discharging from reaction zone 10 will 15 optimized for maximum condensation.
be alkaline and will contain substantial amounts of so Effluent gases from Zone D can be treated with an
dium carbonate and unreacted sodium hypochlorite. optional reducing agent to react with the last traces of
Because of the high temperatures and sodium hypo chlorine and sodium hypochlorite in the effluent gases.
chlorite normally present in reaction zone 8, pH mea 20 Any suitable reducing agent such as sodium sulfite,
surement is done in a cooled, continuous external urea, hydroxylamine, or hydrogen peroxide can be
stream. Hot sodium hypochlorite solution is pumped used, but the optional reducing agent should not be
from the reaction zone 8 via line 17 through heat ex reactive with CO2. Sodium sulfite has been found to be
effective. The reaction is as follows:
changer 24 and then through lines 18 and 20 by way of
pump 22 to pH probe and transmitter 12 and then re 25 Cl2-i-Na2SO3-H2O-H2SO4-2NaCl XI.
turned to reaction zone 10 by way of line 23. Heat ex
changer 24 cools the sodium hypochlorite solution to a The optional reducing agent should only be used in
temperature not less than the saturation point of the small quantities approximately equivalent to the trace
solution, usually between about 5 C. to about 40 C. amounts of chlorine and sodium hypochlorite in the
The pH probe and transmitter 12 control the rate of effluent gases, otherwise it could destroy some of the
chlorine or acid addition through control circuit 16 and sodium hypochlorite in the sodium hypochlorite feed
valve 30 so that the desired pH in reaction zone 8 is solution and possibly contaminate the system. The op
achieved. tional reducing agent can also be added in a separate
The weak sodium chlorate solution exiting from reac scrubber, thus isolating the reducing agent from the
tion zone 10 via line 27 can be evaporated to concen 35 process.
trate the salts prior to adding to a sodium chlorate elec Effluent gases move through Zone E containing a
trochemical cell, or added directly to a sodium chlorate mist eliminator and thence to the atmosphere through
cell or to a chlorine dioxide generator. If metal contami line 35. In this zone liquid droplets, which may contain
nants are present, the solution can be purified by any sodium hypochlorite, are removed. The final effluent
suitable chemical means, such as ion exchange. If ion gases are essentially free of chlorine and sodium hypo
exchange resins are used as purification means, any chlorite and can be safely removed from the system,
residual sodium hypochlorite can be removed, if neces although chlorine levels up to 3 ppm weight/volume
sary, with an optional dehypochlorination agent before can be present.
feeding to an ion exchange column. Examples of Sodium hypochlorite solution from Zone D enters
dehypochlorination agents are urea, sodium sulfite, 45 Zone C by gravity. In this zone, any chlorine remaining
hydrogen peroxide, etc. -- in the effluent gases is removed by the carbonate pres
In FIG. 3, one embodiment of packed bed column 4 ent in the sodium hypochlorite solution in accordance
is shown. Zones A-E are shown. A sodium hypochlo with the reaction:
rite feed solution is introduced into Zone D through line
5 and moves by gravity from zone D through A where 50 Na2CO3-Cl2 NaClO--NaCl-CO2 XIV.
it exits the packed bed column 4 via line 7. Gaseous
effluents, such as CO2, are introduced into Zone A via Carbon dioxide in the effluent gases also reacts with
line 25 from reaction zone 10 and reaction zone 8 and sodium carbonate in accordance with the reaction:
move counter-currently to the sodium hypochlorite
solution from Zone A through E so that they are 55 Na2CO3--CO2-i-H2O-2NaHCO3 XV.
cleaned of chlorine.
Zones B, C, and D can be packed with any suitable Most of the sodium carbonate is converted to sodium
packing material. Ceramic saddles are preferred. The bicarbonate in Zone C and the pH of the sodium hypo
packing density is, generally, about 3% to about 50%, chlorite solution leaving Zone C and entering Zone B
preferably, about 5% to about 15%, and, most prefera will be approximately 8-9. Wider pH ranges can be
bly, about 8% to about 11%. The space above Zone D used. The sodium hypochlorite solution also cools the
is not packed. This allows the sodium hypochlorite effluent gases and condenses out water vapor and so
solution and the optional reducing agent to be intro dium hypochlorite in Zone C.
duced into the packed bed column 4 by any suitable Sodium hypochlorite solution from Zone Centers
C3S. -- 65 Zone B by gravity. In this zone, most of the chlorine in
Effluent gases in packed bed column 4 move counter the effluent gases is removed by the sodium bicarbonate
currently to the sodium hypochlorite solution. Carbon present in the sodium hypochlorite solution according
dioxide in the effluent gases will react with free caustic to the reaction:
 5,378.447
15 16
The liquid/foam/gas mixture exited from the top of
NaHCO3- Cl2-HCIO--NaCl-CO2 XVI. reaction zone 26 via line 11 to reaction zone 8. Reaction
zone 8 was a 2" diameter, 40' long piece of titanium
The pH of the sodium hypochlorite solution leaving pipe. Effluent gases were withdrawn from the top of
Zone B and entering Zone A will be approximately reaction zone 8 via line 15 and led by way of line 25 to
about 7 to about 8. Wider pH ranges can be used. The Zone A of packed bed column 4. It was observed that
sodium hypochlorite solution also cools the effluent foam or liquid was carried with the effluent gases into
gases and condenses out water vapor and sodium hypo column 4.
chlorite in Zone B. The sodium hypochlorite solution was withdrawn
Sodium hypochlorite solution from Zone B enters 10 from reaction zone 8 via line 19 and led to reaction zone
Zone A by gravity. Zone A provides a discharge point 10 by gravity. Reaction zone 10 consisted of a train of
for the sodium hypochlorite solution and an entry point four 2 pinch diameterx36 inch long titanium pipes
for the effluent gases. It remains partially filled with connected so that the, sodium hypochlorite solution
sodium hypochlorite solution at a level sufficient to flowed from the first pipe to the last pipe in the train,
maintain a hydraulic head sufficient to maintain flow 15 and then out as a weak sodium chlorate solution into a
through the downstream heat exchanger and reaction catch tank via line 27 by gravity. The train was heated
zones. The effluent gases from reaction zones 8 and 10 to 97 C.-98 C. by a water bath. Total retention time in
are introduced via line 25 above the liquid level in the the train was 51 minutes.
gas space. The feed rate of chlorine gas to the system was con
The following Examples illustrate the various aspects 20 trolled by manually regulating a needle valve made of a
of the invention but are not intended to limit its scope. plastic sold under the trade name TEFLON so that the
Where not otherwise specified throughout this specifi pH in reaction zone 8 was maintained at an average of
cation and claims, temperatures are given in degrees 6.4. The pH control range was 5.0 to 7.2. The pH was
centigrade and parts, percentages and proportions are measured with a glass combination electrode at pH
by weight/volume. 25 probe and transmitter 12 in external pH sampling loop
EXAMPLE 1. encompassing lines 17, 18, 20, and 23, heat exchanger
24, pump 22, and pH probe and transmitter 12.
This example is described with reference to FIGS. 2 The test was run continuously for 8.6 hrs. over which
and 3. The packed bed column 4 was made of clear time 50 liters of the synthetic sodium hypochlorite feed
plastic pipe sold under the trade name LEXAN. Two 30
solution was processed to a weak sodium chlorate solu
different kinds of packing were used in each of the tion. The conversion efficiency to sodium chlorate was
packed sections B, C and D. The packing density was 98% based on the available sodium hypochlorite and
25-40%. Demister section E was packed with glass alkalinity of the original feed solution. The final weak
wool. sodium chlorate solution withdrawn from reactor 10 via
A synthetic sodium hypochlorite solution containing 35
line 27 had an average pH of 6.1, and, by analysis, con
1.7 gpl sodium hydroxide, 10.6 g.pl sodium chlorate, sisted of 0.82 gp1 NaClO, 0 gp1 Na2CO3, 40.6 g.pl Na
34.3 gpl sodium chloride, 40.6 gpl sodium carbonate, ClO3, and 89.4 gp1 NaCl. The total chlorine and sodium
and 39.1 gpl sodium hypochlorite was fed through line hypochlorite level in the effluent gases discharging
5 to the top of scrubber column 4 at a flow rate of 96.4 from packed bed column 4 averaged 0.91 ppm
ml/min. The synthetic sodium hypochlorite solution (mg/liter), expressed as Cl2. The range was 0.83-1.08
used was made from an aqueous sodium hypochlorite ppm. These levels were not detectable by smell, indicat
sold under the trade name CHLOROX, reagent grade ing that most of the chlorine was probably present as
Na2CO3, NaOH, and tap water. The solution moved sodium hypochlorite mist getting through demister
through the column from Zone D through Zone A by Zone E. Lower chlorine levels would be achieved with
gravity. The sodium hypochlorite solution was flowed 45
better mist eliminating equipment. Summarizing Exam
by gravity through the rest of the system and flow was ple 1:
maintained on a continuous basis. The pH of the sodium
hypochlorite solution was 12.5 entering scrubber col
umn 4 via line 5, and ranged from 7.4 to 7.7 exiting EXAMPLE 1.
scrubber column 4 via line 7. 50 Zone A
The sodium hypochlorite solution was flowed via of
line 7 through heat exchanger 6, and then into reaction Hypochlorite Scrubber Weak
Feed Column Reaction Chlorate
zone 26 via line 14, by gravity. The sodium hypochlo Solution 4. 2one 8 Recycle
rite solution was heated in heat exchanger 6 so that the
temperature in reaction zone 26 was 94° C. Reaction 55 NaCIO
NaClO3
(gpi)
(gpl)
39.
10.4
24-29 0.8
40.7
Zone 26 was made of clear plastic pipe sold under the NaCl (gpl) 34.2 89.4
trade name LEXAN. Chlorine was injected at the bot Na2CO3 (gpl) 40.6 0.0
tom of the reaction zone 26 via line 32. NaOH (gpl) 17 0.0
An immediate reaction between the chlorine and pH 12.5 7.4-7.7 5.0.7.2 6.
Temp. (C) Ambient 94 97-98
sodium hypochlorite solution took place which caused Chlorate % 98.0
the evolution of gas and foam. This was easily observed Conver
in the clear plastic pipe reaction zone 26. The sodium Sion Eff.
hypochlorite solution/foam/gas mixture travelled co Cl2 in (ppm) 0.91
Dis
currently through reaction zone 26 and the mixture charging
appeared visually to be homogeneous. By measurement, Gases
the liquid component of the mixture occupied of the Duration (Hrs)
of test
8.6
volume of reaction zone 26, and the gas component of
the volume.
 5,378.447
17 18
EXAMPLE 2
The process of Example 1 was repeated but with a EXAMPLE 4
variation of the constituents in the scrubber solution as Zon A.
follows: 5 Hypochlorite Scrubber Weak
Feed Column Reaction Chlorate
Solution 4. Zone 8 Recycle
EXAMPLE 2 NaClO (gpl) 36.4 .23
Zone A NaClO3 (gp1) 2.7 13.6
of 10 NaCl (gpl) 38.1 82.
Hypochlorite Scrubber Weak Na2CO3 (gpl) 41.0 0.0
Feed Column Reaction Chlorate NaOH (gpi) 9.8 0.0
Solution 4. Zone 8 Recycle pH 13.0 1.5-5.5 S.O
NaClO (gp1) 39.3 3.5 i.2 Temp. (C) Ambient 82 85-90
NaClO3 (gp1) 1.3 37. Chlorate 2% 96.8
NaCl (gp) 37.4 109.4 15 EE
Na2CO3 (gpl) 50.9 0.0 ---
NaOH (gpl) 9.8 0.0 Skin (ppm) 0.98
pH 12.9 4.9-6.5 5.4 Arai
Temp. (C) Ambient 60 90 97-98 ing
Chlorate % 92.0 Duration (Hrs) S.8
Conver.
sion Eff.
20 of test
Cl2 in (ppm) 1.60
i. Note that the final product is more dilute because of the
g"g water fed in with the HCl.
Duration
of test (Hrs) 8.7 25 EXAMPLE 5
The process of Example 1 was again repeated but
with the exception that 1.5M sulfuric acid was used to
EXAMPLE 3 acidify the system rather than chlorine gas as follows:
The process of Example 1 was repeated but with a 30
variation of the constituents in the scrubber solution and EXAMPLE 5
process conditions as follows: Zone A
of
Hypochlorite Scrubber Weak
EXAMPLE 3 35 Feed Column Reaction Chlorate
Zone A Solution 4 Zone 8 Recycle
of NaClO (gpi) 35.1 0.9
Hypochlorite Scrubber Weak NaClO3 (gpi) 3.5 13.0
Feed Column Reaction Chlorate NaC (gpi) 39.7 40.3
Solution 4 Zone 8 Recycle Na2CO3 (gpl) 42.1 0.3
NaClO (gpl) 39.7 09 NaOH
40 pH (gpl) 0.0 0.0
3.2 4.4-6.5 6.0
NaClO3 (gpl) 1.3 36.0 Temp. (°C) Ambient 92 90-95
NaCl (gp) 36.2 105. Chlorate % 91.8
Na2CO3 (gpi) 41.9 0.0 Conver
NaOH: (gpl) 9.8 O.O sion Eff.
pH 12.7 7.0-8.0 4.6-8.0 6.2 Cl2 in (ppm) 1.17
Temp. (C) Ambient 88 96-97 45 Dis
Chlorate % 95.7 charging
Conver Gases
sion Eff. Duration (Hrs) 6.3
Cl2 in (ppm) 49 of test
Dis
charging SO
Gases x Note that the final product is more dilute because of the
Duration (Hrs) 8.7 water fed in with the sulfuric acid.
of test
EXAMPLE 6
In this example at start up, all vessels were filled with 55 In a separate experiment, the effluent gases discharg
the sodium hypochlorite feed solution of Example 3 and ing from packed bed column 4 via line 35 were bubbled
the system was run under non-equilibrium "upset condi from an open ended " I.D. tube through a 3' deep
tions until equilibrium was established in the CO2/- volume of 50 gpl sodium sulfite solution (Na2SO4) to
sodium carbonate; loop in the scrubber column. Under remove the last trace amounts of chlorine and sodium
"upset conditions pH fluctuations are fairly broad. 60 hypochlorite. The chlorine concentration in the effluent
After equilibrium conditions are established, the pH is gases was analyzed at 1.0 ppm Cl2 before bubbling
controlled in the range of 6 to 7 yielding optimum per through the sodium sulfite solution, and 0.0 ppm after
formance for the system. . wards.
EXAMPLE 4 65 EXAMPLE 7
The process of Example 1 was again repeated but In a separate experiment, the effluent gases discharg
with the exception that 3M hydrochloric acid was used ing from packed bed column 4 via line 35 were bubbled
to acidify the system rather than chlorine gas: from an open ended " I.D. tube through a 3' deep
 5,378,447
19 20
volume of 50 gplurea CO(NH2)2 solution to remove the line earth metal hypochlorite, carbonate, and chlo
last trace amounts of chlorine and sodium hypochlorite. ride, thereafter
The chlorine concentration in the effluent gases was C converting in a second scrubbing zone said first
analyzed at 1.3 ppm Cl2 before bubbling through so aqueous mixture with effluent gases generated in
dium sulfite solution, and 0.6 ppm afterwards. step D to obtain a second aqueous mixture compris
While this invention has been described with refer ing an alkali metal or alkaline earth metal hypo
ence to certain specific embodiments, it will be recog chlorite and bicarbonate and venting effluent gases
nized by those skilled in the art that many variations are comprising an acid gas and carbon dioxide from
possible without departing from the scope and spirit of said second scrubbing zone, thereafter
the invention and it will be understood that it is in 10 Dreacting at elevated temperature said second aque
tended to cover all changes and modifications of the ous mixture with an acid or an acid gas selected
invention disclosed herein for the purposes of illustra from the group consisting of hydrochloric acid,
tion which do not constitute departures from the spirit sulfuric acid, and chlorine in a reaction zone and
and scope of the invention. successively completing the reaction in at least one
The invention in which an exclusive property or 15 reaction completion zone to produce a chlorate
privilege is claimed is defined as follows: and effluent gases while supplying said effluent
1. A process for producing a dilute, aqueous solution gases to step C and recovering said chlorate as a
of an alkali metal or alkaline earth metal chlorate from dilute, aqueous mixture comprising an alkali metal
a gaseous waste stream comprising chlorine and carbon or alkaline earth metal chlorate. thereafter
dioxide, said process comprising: E passing said alkali metal or alkaline earth metal
A) contacting in a first scrubbing zone, said gaseous 20 chlorate together with an aqueous alkali metal or
waste stream with an alkali metal or alkaline earth alkaline earth metal chloride to an electrochemical
metal hydroxide to produce a first aqueous mixture cell for the production of an aqueous alkali metal or
comprising an alkali metal or alkaline earth metal alkaline earth metal chlorate, and thereafter
hypochlorite, carbonate, and chloride, thereafter F passing a product of said cell comprising an aque
B) converting in a second scrubbing zone said first 25 ous alkali metal or alkaline earth metal chlorate to
aqueous mixture by passing said first aqueous mix step A.
ture counter-currently to effluent gases comprising 8. The process of claim 7 wherein said acid gas is
an acid gas generated in step C to obtain a second chlorine and said at least one reaction zone is main
aqueous mixture comprising an alkalimetal or alka tained at a pH of about 5 to about 7.
line earth metal hypochlorite and bicarbonate, 30 9. The process of claim 8 wherein said second aque
thereafter ous mixture is converted to an alkali or alkaline earth
C) reacting said second aqueous mixture comprising metal chlorate and carbon dioxide.
an alkali metal or alkaline earth metal hypochlorite 10. The process of claim 9 wherein said pH is main
and bicarbonate at about 60 C. to about 105 C. tained at about 5 to about 7 by controlling the amount of
together with an acid or an acid gas selected from said chlorine admitted to said reaction zone of Step (D).
the group consisting of hydrochloric acid, sulfuric 35 11. The process of claim 10 wherein said alkali metal
acid, and chlorine in a reaction zone and succes chlorate is sodium chlorate.
sively completing said reacting at said temperature 12. The process of claim 11 wherein said process is
to produce a chlorate and effluent gases while sup continuous.
plying said effluent gases to step B and, thereafter 13. A process for producing a dilute, aqueous solution
D) recovering from step C a dilute, aqueous solution of sodium chlorate from a waste gaseous stream com
comprising an alkali metal or alkaline earth metal prising chlorine and carbon dioxide, said process com
chlorate. prising:
2. The process of claim 1 wherein said second aque (A) passing said waste gaseous stream counter-cur
ous mixture is reacted together with chlorine to pro rently to an aqueous mixture of sodium hydroxide
duce a chlorate and effluent gases. 45 in a first scrubbing zone to produce a first aqueous
3. The process of claim 2 wherein said effluent gases mixture comprising sodium hypochlorite, sodium
from step C of claim 1 comprise carbon dioxide, chlo carbonate, and sodium chloride, thereafter
rine and water vapor. (B) passing said first aqueous mixture counter-cur
4. The process of claim 3 comprising successively rently to effluent gases generated in step C to ob
completing the reaction in at least one reaction comple 50 tain a second aqueous mixture comprising sodium
tion zone at a temperature of about 85°C. to about 100' hypochlorite and sodium bicarbonate and, thereaf
C. ter
5. The process of claim 4 wherein the pH in said at (C) reacting said second aqueous mixture with chlo
least one reaction completion zone is maintained at rine at about 85 C. to about 100° C. in a reaction
about 5 to about 7 by controlling the amount of chlorine 55 zone and successively completing the reaction in at
admitted to said reaction zone. least one reaction completion zone to produce
6. The process of claim 5 wherein sodium chlorate is sodium chlorate and effluent gases wherein said at .
recovered. least one reaction completion zone is maintained at
7. In a process for the production of chlorine dioxide, a pH of about 6.4 to about 6.9 by controlling the
comprising amount of chlorine admitted to said reaction zone
A reducing an aqueous alkali metal or alkaline earth and recycling said effluent gases comprising chlo
metal chlorate with an aqueous inorganic acid and rine, carbon dioxide, and water vapor from said at
methanol in a chlorine dioxide production zone, least one reaction completion zone to said second
the improvement comprising: scrubbing zone and recovering from said at least
B converting by-products of said process comprising one reaction completion zone a dilute, aqueous
chlorine and carbon dioxide in a first scrubbing 65 solution comprising sodium chlorate.
zone by reaction with an aqueous alkali metal or 14. The process of claim 13 wherein said process is
alkaline earth metal hydroxide to produce a first continuous.
aqueous mixture comprising an alkali metal or alka k ck ck k 2k