United States Patent (19) 11) 4,432,880

Talbot 45) Feb. 21, 1984

54 PROCESS FOR THE REMOVAL OF HEAVY 57 ABSTRACT
METALS FROMAQUEOUS SOLUTION A process is described for the removal of one or more
(75) Inventor: Richard S. Talbot, Media, Pa. heavy metals from an aqueous system containing at least
73 Assignee: Richard S. Talbot and Associates, two heavy metals by the addition of a soluble sulfide to
Media, Pa. precipitate at least one of said heavy metals as the sul
fide thereof, which comprises adding an amount of
21 Appl. No.: 329,388 soluble sulfide statistically determined to be sufficient to
22 Filed: Dec. 10, 1981 precipitate as the sulfide substantially all of at least one
heavy metal to the limits of its metal sulfide solubility;
51) int. Cl. ................................................ CO2F1/62 said statistically determined amount of soluble sulfide
52 U.S. C. .................................... 210/725; 210/727; being less than the amount required to precipitate as the
210/739; 210/912 metal sulfide at least one other heavy metal in said sys
58) Field of Search ............... 210/724, 726,912,914, tem having a soluble sulfide equilibrium concentration
210/739, 743, 746, 725,727 sufficiently higher than that of said selected heavy metal
56) References Cited to thus permit selective precipitation of said selected
U.S. PATENT DOCUMENTS metal and of any other heavy metals present having
3,740,331 6/1973 Anderson et al. .................. 210/726
lower sulfide equilibrium solubility concentrations than
4,278,539 7/1981 Santhanam et al. . ... 20/724 that of the selected heavy metal, wtih said precipitation
4,329,224 5/1982 Kin .................................. 210/724 X being to the limits of the metal sulfide solubilities; and
precipitating at least a portion of at least one heavy
OTHER PUBLICATIONS metal remaining in said system after said sulfide precipi
Kim "Treatment of Metal Containing Wastewater by tation by a means other than by sulfide precipitation
Sulfide Precipitation,' presented at AICHE 73rd An whereby an aqueous effluent is obtained which contains
nual Meeting, Chicago, Ill., Nov. 16-20, 1980. no sulfide.
Primary Examiner-Thomas G. Wyse
Attorney, Agent, or Firm-Eugene E. Renz, Jr. 21 Claims, No Drawings
 4,432,880
2
trol the process to avoid addition of soluble sulfides in
PROCESS FOR THE REMOVAL OF HEAVY excess of the stoichiometric amount to precipitate all
METALS FROM AQUEOUS SOLUTION insoluble heavy metal sulfides.
The prior art is replete with patents disclosing the
BACKGROUND OF THE INVENTION 5 precipitation of heavy metals from aqueous solutions by
It has long been recognized that heavy metals are a the use of hydroxides or by the use of excess sulfide. All
very serious environmental pollutant since they are of these prior processes were subject to various disad
poisonous to many forms of life including man and are vantages which have been recognized in the prior art.
frequently introduced to natural waters, including More specifically, Anderson et al. U.S. Pat. No.
10 3,740,331 issued June 19, 1973, notes that hydroxide
streams, ponds, lakes and the oceans. This is very seri
ous, not only due to the direct contamination of such precipitation of heavy metal, is not entirely satisfactory,
waters with consequent detrimental or even lethal ef since it is not as complete as precipitation with excess
fect on the life of aquatic organisims which enter into sulfide in other prior art.
the food chain, but due to the fact that heavy metals 15
Indeed one of the principal objects of the invention of
tend to build up in such organisims with resulting in the Anderson et al. patent was to provide a precipitation
creased concentration over a period of time. Indeed, the process more effective than the commercially available
heavy metal concentrations in many types of fish and hydroxide processes.
other sea food has reached a level in some localities Anderson et al. also recognized the disadvantages of
such that it is not recommended that these foods by 20 precipitating heavy metals with excess sulfide, as in
eaten by man. This problem is itself aggravated by the other prior art processes, since the excess sulfide forms
tendency of the heavy metals to build up in concentra hydrogen sulfide gas, the vapors of which are detect
tion in any organism which ingests them, including able even above highly dilute alkaline solutions.
man. Therefore, human health may be and indeed has Anderson et al. proposed to obviate the disadvan
been seriously adversely affected not only by drinking tages of the prior hydroxide and excess sulfide heavy
water containing heavy metals but by ingesting fish or 25 metal precipitation processes, by using sulfide in excess
sea food from such waters or even eating animal or of that required to precipitate the heavy metal pollut
vegetable food raised using such waters. ants and scavenging the excess sulfide by the addition of
This problem has become so serious that the U.S. a heavy metal salt having a higher equilibrium sulfide
Environmental Protection Agency (EPA) has estab ion concentration than the sulfide of the pollutant heavy
lished very stringent standards for heavy metals in in 30 metal. The preferred added heavy metal for this pur
dustrial or other waste waters which are discharged to pose is manganese since its sulfide is the most soluble of
the environment. In particular, EPA regulations have all heavy metal sulfides. However the cost of manga
recently been promulgated for regulating the amount of nese sulfide is so high that ferrous sulfide is used as a
heavy metals discharged by the electroplating industry practical matter. The sulfide precipitant may be sodium
into waters subject to processing by Publicly Owned 35 sulfide, sodium hydrosulfide or hydrogen sulfide and is
Treatment Works (POTW) for subsequent drinking used in amounts two to ten times that required to pre
purposes. Similar EPA regulations are expected to be cipitate the heavy metal pollutants initially present, but
promulgated for as many as 20 other categories of in
dustry. less than the amount needed to precipitate all of the
While a great deal of technology exists concerning added heavy metal. Therefore, a small amount of added
the removal of heavy metals from wastewater or other heavy metal remains in solution, some of which is re
aqueous solutions, the new EPA regulations for the moved by the hydroxides released by the sulfide re
electroplating industry and further regulations to be placement reactions.
expected in the future clearly require improved technol Santhanam et al. U.S. Pat. No. 4,278,539, issued July
ogy to meet the stringent standards for direct discharge 45 14, 1981, summarizes much of the prior art and points
of heavy metals into receiving streams or the indirect out that existing technology is probably inadequate to
discharge into the POTW referred to above. meet the present and proposed future standards for
heavy metal content of wastewaters. More specifically,
THE PRIOR ART Santhanam et al indicate that the heavy metals anti
Existing technology for the removal of heavy metals 50 mony, cadmium, chromium, copper, lead, mercury,
from aqueous solutions from industrial or other sources selenium, silver, tin and zinc, represent an extremely
generally makes use of either hydroxide or sulfide pre serious pollution potential. Of these, Santhanam et al
cipitation of the heavy metals. Conventional hydroxide indicate that new technologies may be required for
precipitation has serious limitations since the solubilities removing at least copper, lead, zinc, cadmium, sele
of the hydroxides of many heavy metals are too high to 55 nium, arsenic and mercury to met the new and proposed
meet the stringent standards now in force and others to toxicity standards.
be expected in the future. Moreover, in hydroxide pre Santhanam et al. also teach that the recovery of
cipitation systems there is no single pH at which all of heavy metals from industrial processes may offer appre
the heavy metals can be brought down as is the case ciable economic advantages; for example, the recovery
with sulfide precipitation systems. While the solubilities 60 of cobalt and nickel from leach liquors, or of copper,
of heavy metal sulfides are much lower than those of lead, and zinc from effluents from smelter operations, or
the corresponding hydroxides, most previously sug of chromium, selenium, cadmium, and tin from process
gested processes have recommended the use of stoichio effluents, or of other sulfides from various hydrometal
metric or even excess sulfide which has resulted in the lurgical processes, and, particularly, the recovery of
discharge to the environment of hydrogen sulfide, a 65 heavy metals from electroplating solutions.
very poisonous gas with an unpleasant characteristic Santhanam et al. list the various available technolo
rotten-egg odor. This problem is especially prevalent in gies for the recovery of such heavy metals, but indicate
continuous feed systems in which it is difficult to con that none of these processes is adapted to handle large
 4,432,880
3. 4.
volumes of aqueous liquids to effectively, reliably and addition of said insufficient amount of soluble sulfide, a
economically remove trace amounts of the heavy met sulfide analyzer is optionally used to ensure that no
als in a continuous feed process. They teach that this is excess sulfide has been or is being added.
particularly true of the use of hydrogen sulfide, since SUMMARY OF THE INVENTION
the resulting precipitates are very small in particle size,
often colloidal in nature, and are thus difficult to sepa The foregoing and other objects of the invention,
rate especially on a continuous basis. The Santhanam et which will become apparent below, are achieved by an
al. process, which is not particularly pertinent to the improved process for the treatment of aqueous solutions
present invention, involves the controlled sulfide pre containing at least two heavy metals, which provides
cipitation of heavy metals in such a way as to promote 10 for the selective removal by sulfide precipitation of
crystal growth and facilitate separation of the precipi substantially all of at least one selected heavy metal and
tates by settling or filtrations. the removal, to the degree desired, of another heavy
Blythe et al., in an EPA Project Summary entitled metal in the solution having a sulfide solubility equilib
"Characterization of Boliden's Sulfide-Lime Precipita rium concentration higher than the selected heavy
tion System' published in August 1981 (EPA-600/S2 5 metal, by a different precipitation means, in such a way
81-031) describe a combination sulfide-hydroxide pre that hydrogen sulfide is not evolved from the solution in
cipitation process for heavy metals in the wastewater an amount sufficient to significantly pollute the atmo
from a copper/lead smelting operation in Sweden. The sphere.
entire disclosure of the Blythe et al. reference and of More specifically, the new process employs two dis
each of the six references cited therein is hereby incor 20 tinct means of precipitating heavy metals, which may be
porated in this specification by reference. Blythe et al. carried out sequentially with the sulfide precipitation
suggested the use of less than the stoichiometric amount first followed by precipitation by other means, or simul
of soluble sulfide in bench scale tests. However, in full taneously.
scale tests, they resorted to the use of an excess of sul One of the precipitation operations is initiated by the
fide addition above that required to precipitate all of the 25
introduction of a soluble sulfide to the solution to be
heavy metals that could be precipitated as the metal treated to pecipitate sulfides of at least one heavy metal
sulfide. Since the amount of sulfide added in their stud
ies was calculated on the total amount of metal present, or a plurality of selected heavy metals initially present,
without regard for the equilibrium metal solubilities as the amount of soluble sulfide employed being insuffi
the metal sulfide, rather than on the amount that could 30 cient to precipitate all of at least one other heavy metal
be precipitated as the sulfide, they in fact used more in the solution. In this way, the sulfide ion concentration
than the amount of sulfide necessary to precipitate all in the solution never exceeds the stoichiometric amount
the precipitable metals as metal sulfides. Moreover, it is required to precipitate all of the heavy metal content
apparent that Blythe et al. failed to teach the art how to originally present in the solution. This being the case, a
control such a process on a large continuous scale since 35 portion of the excess heavy metal content of the solu
they found it necessary to add excess sulfide while em tion is more than sufficient to scavenge any sulfide ion
ploying pH as the control mechanism. above the amount required to precipitate all of the se
In view of the foregoing, it is apparent that while the lected heavy metal. Therefore, no significant amount of
prior art is replete with technology relating to the re unreacted sulfide ion is ever present in the solution to
moval of heavy metals from aqueous solutions, there is 40 permit the formation of hydrogen sulfide, which is char
a clear and well-recognized need in the art for improved acteristic of the methods of the prior art employing
technology to meet the more stringent standards which excess soluble sulfide, and substantially no hydrogen
have been recently imposed and the still more stringent sulfide is evolved to significantly pollute the atmo
Standards to come. sphere.
It is an object of the present invention, therefore, to 45 The heavy metals having sulfide solubility equilib
provide an improved process for the removal of heavy rium concentrations above that of the heavy metal or
metals from an aqueous system whether a solution, heavy metals selectively removed by sulfide precipita
suspension, or slurry, which will meet the current and tion, can be removed to the degree necessary or desir
proposed standards. able by any other method known to the art for precipi
It is another object of the invention to provide a 50 tating heavy metals. For example, these remaining
process for the removal of heavy metals from aqueous heavy metals may be removed wholly or in part by
solution by sulfide precipitations without the generation simply raising the pH of the solution to a value which
of sufficient hydrogen sulfide gas to cause any environ will cause these heavy metals to precipitate as the hy
mental impact. droxides. Such a value will be in the range from about
It is still another object of the invention to provide a 55 pH 4 to about 12 and preferably about pH 8 to about
process for the substantially complete removal of all, or 10.5. This may be done by any suitable means, whether
Selected, heavy metals from aqueous solution which can by the addition of an alkaline material such as lime, soda
be conducted on a large scale in continuous flow con ash, ammonia, alkali metal or alkaline earth metal hy
ventional equipment at low cost. droxides or otherwise. Indeed, any chemical reaction,
It is still another object of this invention to provide a 60 other than sulfide precipitation, which will remove the
method for controlling the addition of sulfides to selec remaining heavy metals may be employed without limi
tively precipitate metal sulfides. tation. The important consideration is that less than
It is another object of the invention to provide a enough sulfide be employed to precipitate all of the
continuous method for the precipitation of heavy metal heavy metal content originally present; the remainder
sulfides from wastewater in which the wastewater is 65 of the heavy metal can be removed to the degree neces
first analyzed to determine a statistically satisfactory sary or desired by any other means.
level of soluble sulfide insufficient to precipitate all of The two different means of precipitating heavy met
the heavy metal content originally present, then after als may be employed either simultaneously or the sul
 4,432,880
5 6
fide precipitation first followed by precipitation by having lower sulfide solubility equilibrium concentra
other means. tions.
The invention also includes a statistical method for For example, suppose a wastewater system contains
controlling the process on a batch or continuous basis only Mn++, Fe++, Zn- +, Nith +, Pb----, Cdt +, and
for determining the amount of soluble sulfide to be Hgt + ions. If it were desired to remove nickel as the
employed in order to precipitate substantially all of a nickel sulfide, then sufficient sulfides would have to be
selected heavy metal or metals but to avoid employing added to react with all those heavy metals which have
an amount of sulfide sufficient to cause the formation a lower equilibrium sulfide ion concentration than the
and evolution of a significant amount of hydrogen sul metal desired to be removed as the sulfide, plus the
fide to the atmosphere. 10 metal itself. Using the above table of equilibrium sulfide
The control method utilizes statistics to select the ion levels, sufficient sulfide would have to be added to
dosage of soluble sulfide to apply that will be statisti react with all of the Hght, Cdt +, Pb----, and Ni----.
cally insufficient to react with all of heavy metals it is In actual practice, it is likely that some excess of this
desired to precipitate as the metal sulfides. An optional amount would be added to be sure of removing all the
practice of the invention is to use a sulfide analyzer to 15 nickel. Since there are also present Znt +, Fe++, and
sense any excess sulfide in the wastewater or atmo Mn++ ions, the excess sulfides would preferentially
sphere resulting from the low probability of random react with the zinc before the ferrous before the manga
over-dosing above a statistically insufficient amount. nese ions. But, in any event, insufficient soluble sulfide
DETAILED DESCRIPTION OF THE
would be added to precipitate all of the heavy metals
20 originally present in the wastewater.
INVENTION This invention uses statistics as an aid in helping to
It is well known to those skilled in the art that the select the amount of soluble sulfide to add to precipitate
solubility of heavy metal sulfides may be determined the desired heavy metals from the water or wastewater
experimentally or by calculation. as the metal sulfide in continuous flow systems and in
The equilibrium sulfide ion concentration of some 25 batch feed systems. The water or wastewater is charac
representative heavy metals is set forth in the table terized as to the concentration of heavy metals present.
below. This is accomplished by analyzing at least one and pref
erably a minimum of three composite samples of the
water or wastewater completely for those heavy metals
EQUILIBRIUM SULFIDE ION CONCENTRATIONS 30 known or expected to be present therein. Three com
FOR REPRESENTATIVE HEAVY METALS posite samples is the minimum acceptable from a statis
Equilibrium Sulfide Ion Concentration tics viewpoint, although as little as one composite could
Metal Ion (moles/1.)
Mnh h 3.75 X 10-8
be analyzed, but with a higher degree of risk in the
statistical analysis of the data. A determination is made
Fe++ 6.1 x 10-10 35 of what heavy metals must be precipitated as the metal
Zn--- 3.46 x 10-12 sulfide in order to satisfy the standards of a regulatory
Ni++ 1.18 x 10-12 agency or interested party. Enough sulfide must be
Sn 3.1 x 10-13 provided to precipitate all of the selected heavy metal
Co+ + 1.73 X 10-13
Pb++ 1.84 X 10-14 which can be precipitated as the sulfide and all those
Cd+ + 6.0 x 10-15 heavy metals with lower equilibrium concentrations of
Ag-- 3.4 x 10-7 soluble sulfide which can be precipitated as the sulfide.
Bi+++ 4.8 x 10-21 To determine this quantity of sulfide, on each of the
composite samples so analyzed, a calculation is made of
Cu+ + 9.2 x 10-23 the stoichiometric amount of sulfide required to react
45 with these heavy metals at the desired pH. A statistical
Hg++ 4.5 x 10-25 analysis of the amount of sulfide required based on an
individual composite or the mean of the composites is
It will be seen that the representative heavy metals in made. An upper confidence level for an individual con
the foregoing table are listed in order of their decending posite or for the mean of the composites is established
degree of solubility as the metal sulfide; i.e. the most 50 for a certain selected level of confidence using methods
soluble heavy metal sulfide is manganese sulfide at the of statistics commonly known to those skilled in the art.
top and the least soluble heavy metal sulfide is mercury The confidence level selected might be in the range of
sulfide at the bottom. 95 to 99.9%, depending on what percent of the time the
It will be apparent to those skilled in the art that, heavy metals might be allowed to exceed the specifica
knowing the concentration of any given heavy metal in 55 tions, but not limited to these percentages. The quantity
a solution and the solubility of its sulfide, the stoichio of sulfide required at this confidence level would be
metric amount of soluble sulfide necessary to precipi added to the water or wastewater to remove the metals
tate all of any given metal in excess of its solubility desired to be removed as completely as possible by
equilibrium concentration can be calculated. sulfide precipitation. In fact for further safety in meet
It has now been discovered that the metals having the ing the heavy metal standards, the quantity of sulfide
lowest sulfide solubility concentration have the greatest actually added could be some factor larger than the
affinity for sulfide ion and will be precipitated substan amount calculated from the upper confidence level
tially completely before any metal present in the solu using statistics.
tion having a significantly higher sulfide solubility equi The maximum amount of soluble sulfide that should
librium concentration will begin to precipitate. 65 be added is also determined using statistics. To deter
Therefore, it is possible to select a given metal in a mine this quantity of sulfide on each of the composite
solution and add sufficient soluble sulfide to precipitate samples previously analyzed, a calculation is made of
not only that metal but all other metals in the solution the stoichiometric amount of sulfide that can be reacted
 4,432,880
7 S
with all of the heavy metals present at the desired pH to and Nil but still insufficient to precipitate all of the
precipitate their metal sulfides. A statistical analysis of Zn++.
the amount of sulfide required based on an individual The process of the invention was completed by rais
composite or the mean of the composites is made. A ing the pH to about 9.5. This resulted in lowering the
lower confidence level for an individual composite or Pb- + content to less than 0.2 mg/1 and the Cdtt
for the mean of the composites is established for a cer content to less than 0.02 mg/l. This compared favorably
tain selected level of confidence using methods of statis with the results of a conventional hydroxide precipita
tics commonly known to those skilled in the art. The tion process carried out on this wastewater which also
confidence level selected might be in the range of 95 to lowered the Pb- + content to less than 0.2 mg/l but
99.9%. The actual amount of sulfide added should be 10 which left 1.69 mg/l of Cd in solution.
greater than the previously mentioned upper confi EXAMPLE 3
dence limit but less than the lower confidence limit. In
this manner, the sulfide added will be insufficient to An aqueous solution containing 15 mg/1 each of
react with all the metals present most of the time, and Ni++, Pb++, Cdh +, and Cu++, 2.9 mg/1 Hg++ and
sufficient most of the time to completely react with 15 50 mg/l Znt + was treated in separate experiments with
those metals desired to be removed as the sulfide. Nor sodium hydroxide to adjust the pH to 8.0 in one case
mally the value of the upper confidence limit will be less and 9.5 in the other. These two aqueous heavy metal
than the value of the lower confidence limit. However, containing solutions were then treated with 37.1 mg/1
in the low probability event that the value of the sulfide 20
of sulfide in aqueous solution. The calculated amount of
determined by the lower confidence limit is less than the soluble sulfide to precipitate all of metals except the
value determined by the upper confidence limit, the Zn was 22.8 mg/1; the stoichiometric amount of
latter value of sulfide would be recommended for dos sulfide required to precipitate all heavy metals present
ing. was 47.3 mg/1. Therefore, the 37.1 mg/l of soluble sul
In any event, the amount of sulfide added should not 25
fide added was a 62.7% excess over that required to
exceed the amount required to precipitate all the heavy precipitate the nickel, cadmium, lead, copper and mer
metals or other agents reacting with sulfides originally cury, but insufficient to precipitate all the zinc.
present in the water or wastewater for any extended The results of this experiment are set forth in the table
period; otherwise, sufficient excess sulfides would exist, below.
with the potential for noxious odor problems. A sulfide 30
analyzer may be employed to detect incipient excess HEAVY METAL CONCENTRATIONS IN AQUEOUS
sulfide and to reduce the dosage or eliminate it tempo SOLUTION BEFORE AND AFTER TREATMENT
rarily to prevent extended periods of such excess. ACCORDING TO EXPERIMENT 3, INMG/L
The invention will now be illustrated more specifi Heavy Original
No Sulfide
added
Sulfide
added
cally in the following actual examples. 35 Metal Solution pH 8.0 pH 9.5 pH 8.0 pH 9.5
EXAMPLE 1. Znh 50 1.2 0.25 0.57 0.04
Ni++ 15 3.24 <0.05 1.8 <0.05
An aqueous solution containing 15 mg/l Cut and Pb++ 15 <0.05 <0.05 <0.05 (0.05
100 mg/1 Zn was treated with sufficient sodium hy Cd. -- 5 4.8 0.24 <0.05 (0.05
droxide to raise the pH to about 9.3 which caused the Cut --
Hg++
15
2.9
<0.03
2.9
<0.03
2.6
<0.03
<0.00
<0.03
<0.001
formation of a precipitate of cupric hydroxide. Then 25
mg/1 of sulfide was added to the solution which still
contained about 3.0 mg/l of dissolved copper. This The heavy metal is listed in column 1, with the con
amount of sulfide had been calculated to be in excess of centration in the original solution in column 2. The next
the stoichiometric amount to precipitate all of the cop 45 two columns show the effect of pH adjustment alone,
per in solution but insufficient to precipitate all of the i.e. the precipitation of heavy metal hydroxides as in the
zinc in solution. The sulfide precipitation reduced the prior art. The last two columns show the superior re
copper content of the solution to 0 mg/l. In view of the sults of the process of the invention in Experiment 3
fact that no copper remained, it is apparent that no wherein sulfide precipitation (less than stoichiometric)
copper hydroxide existed, otherwise the solubility 50 is used in combination with pH adjustment.
would have been 3 mg/l copper in the form of cupric The process of the present invention may be carried
hydroxide, as before. For this reason, all the sulfides out in conventional equipment on a large scale with ease
added preferentially reacted with the copper, and any and economy,. For example, the addition of the statisti
excess then reacted with a portion of the zinc. cally calculated amount of soluble sulfide may be made
EXAMPLE 2 55 in a suitable reactor in batch or continuous flow opera
tion. It is preferred that the reaction vessel be supplied
Wastewater from a zinc plating operation in an elec with means to introduce the soluble sulfide below the
troplating plant was obtained and analyzed to determine surface of the water to be treated with sufficient mixing
its content of heavy metals. A statistical analysis of the to prevent localized concentrations of soluble sulfide
heavy metals content of this wastewater showed that 60 which could exceed the stoichiometric amount and
about 6.93 mg/l of soluble sulfide would be required to cause formation of hydrogen sulfide.
precipitate all of the Cu++, Cdt +, Pbt + and Nitt in The pH of the solution is adjusted, if necessary, pref
the wastewater. The amount of soluble sulfide neces erably prior to or simultaneously with the addition of
sary to precipitate all of the Zn++ was calculated to be the soluble sulfide to a level high enough to prevent
27.17 mg/1. 65 evolution of a significant amount of hydrogen sulfide,
Soluble sulfide, 13.86 mg/l was added to the waste generally in the range from about 4 to 12. The pH may
water. This constituted a 100% excess over the amount require further adjustment after the addition of the solu
required to precipitate all of the Cu++, Cdt, Pbt + ble sulfide, to the level necessary to further precipitate
 4,432,880
9 O
those heavy metals having a sulfide solubility equilib 3. The process of claim 2 wherein the soluble sulfide
rium concentration above that of the metal(s) selec in sodium sulfide.
tively removed by sulfide precipitation. 4. The process of claim 1 wherein the means for pre
After pH adjustment, one or more coagulants and/or cipitating heavy metal other than by sulfide precipita
polymers may be added to assist the coagulation and tion is by raising the pH of the solution.
flocculation of the precipitated metals. The liquid then 5. The process of claim 4 wherein the pH is raised to
is passed into a solids separator for solids separation. a value in the range from about 4 to about 12.
The solids separator may be a clarifier, with or without 6. The process of claim 5 wherein the pH is raised to
plate or tube inserts, a reactor clarifier with internal a value in the range from about 8 to about 10.5.
mixing elements, or a centrifuge type device. A portion 10 7. The process of claim 1, 2, 3, 4, 5 or 6 wherein the
(some or all) of the settled sludge may be returned to the pH is raised by the addition of a material selected from
reactor to act as seed for enhanced solids separation, or the group consisting of lime, soda ash, sodium hydrox
to provide metal sulfide precipitation products that may ide or calcium hydroxide.
further release sulfide ions to metals entering the reac 8. The process of claim 1, 2, 3, 4, 5 or 6 wherein a
tor having a lower sulfide equilibrium concentration flocculant metal hydroxide is formed which aids in
than some of the metal sulfide forms present in this
15 separation of the sulfide precipitate.
returned settled sludge. Similarly, in the reactor clari 9. The process of claim 1, 2, 3, 4, 5 or 6 wherein said
fier, the settled sludge may be allowed to form a sludge precipitation of heavy metal sulfide is carried out prior
blanket through which the treated liquid must flow. to precipitation of heavy metal by other than sulfide
precipitation.
This sludge blanket also releases sulfide ions to metals 20 10. The process of claim 1, 2, 3, 4, 5 or 6 wherein said
entering the reactor having a lower sulfide equilibrium sulfide precipitation and precipitation by other than
concentration than some of the metal sulfide forms sulfide precipitation are carried out simultaneously.
present in the sludge blanket. 11. The process of claim 1, 2, 3, 4, 5 or 6 wherein the
The process of the present invention is easily con precipitated heavy metals are separated from the system
trolled since the statistically predetermined amount of 25 with the aid of a coagulant polymer or polyelectrolyte.
soluble sulfide is added to the water to be treated either 12. The process of claim 1, 2, 3, 4, 5 or 6 wherein the
batchwise or in proportion to its volume of flow. In a precipitated heavy metals are separated by clarification.
continuous flow wastewater treatment system, the sta 13. The process of claim 1, 2, 3, 4, 5 or 6 wherein the
tistically predetermined amount of soluble sulfide, precipitated heavy metals are separated by filtration.
which is stoichoimetrically insufficient to precipitate all 14. The process of claim 1, 2, 3, 4, 5 or 6 wherein, due
of the heavy metal is added in proportion to the flow of 30 to the introduction of less soluble sulfide than the
wastewater. Excess sulfide addition is optionally pre amount needed to react with all of the heavy metal
vented by the use of a sulfide analyzer to sense any precipitatable as the sulfide, there is no excess soluble
excess sulfide present, and send a signal to the dosage sulfide present, thus precluding the formation of hydro
control to reduce the amount of sulfide being added. gen sulfide in amounts sufficient to significantly pollute
This may be done either by sensing excess sulfide in the 35 the atmosphere.
wastewater or minimal amounts of hydrogen sulfide 15. The process of claim 1, 2, 3, 4, 5 or 6 wherein said
which may be detected above the wastewater. sulfide precipitation is carried out after said precipita
What is claimed is: tion by other than sulfide precipitation.
1. In a process for the removal of one or more heavy 16. The process of claim 1 wherein the probable
metals from an aqueous system containing at least two amount of soluble sulfide to precipitate the selected
heavy metals by the addition of a soluble sulfide to heavy metal and any other heavy metals having lower
precipitate at least one of said heavy metals as the sul sulfide solubility equilibrium concentrations as com
fide thereof, the improvement which comprises: pletely as the metal sulfide solubility relationships allow
adding an amount of soluble sulfide statistically deter is determined statistically on a significant number of
mined to be sufficient to precipitate as the sulfide 45
aqueous samples to be treated, and wherein the amount
substantially all of at least one heavy metal to the of soluble sulfide added to the system being treated is
limits of its metal sulfide solubility; greater than or equal to said amount, but below the
said statistically determined amount of soluble sulfide amount required to precipitate as the sulfide all the
being less than the amount required to pecipitate as heavy metals in said system.
the metal sulfide at least one other heavy metal in 17. A process of claim 16 carried on in a continuous
said system having a soluble sulfide equilibrium 50 flow system controlled by metering the addition of
concentration sufficiently higher than that of said soluble sulfide in proportion to the flow of the heavy
selected heavy metal to thus permit selective pre metal-containing aqueous system to provide said
amount of soluble sulfide.
cipitation of said selected metal and of any other 18. The process of claim 17 wherein a sulfide sensing
heavy metals present having lower sulfide equilib 55 device and associated control system are employed as a
rium solubility concentrations than that of the se fail-safe back-up system for intermittently shutting-off
lected heavy metal, with said precipitation being to the flow of soluble sulfide when said sensor detects
the limits of the metal sulfide solubilities; trace amounts of sulfide.
and 19. The process of claim 18 wherein said control
precipitating at least a portion of at least one heavy system for intermittantly shutting-off the flow of sulfide
metal remaining in said system after said sulfide 60
comprises electronic devices receiving signals from the
precipitation by a means other than by sulfide pre sulfide sensing device and regulating the operation of
cipitation; the sulfide metering system.
whereby an aqueous effluent is obtained which con 20. The process of claim 18 wherein said back-up
tains no sulfide. sensor detects sulfide in the aqueous solution.
2. The process of claim 1 wherein the soluble sulfide 65 21. The process of claim 18 wherein the back-up
is selected from the group consisting of the alkali metal sulfide sensor detects hydrogen sulfide in the atmo
sulfides, the alkaline earth metal sulfides, the alkali sphere above the aqueous system.
metal bisulfides, hydrogen sulfide, or mixtures thereof. it is : it k