United States Patent 0 " "ice 3,740,331

Patented June 19, 1973

1 2
process in which co-precipitated, mixed metal sul?de com
3,740,331 pounds are formed.
METHOD FOR PRECIPITATION 0F HEAVY Yet another object is to provide a precipitation process
METAL SULFIDES for removing heavy metals from aqueous solutions which
John R. Anderson, Cranbury, and Charles 0. Weiss, is more effective than commercially available hydroxide
Princeton, N..l'., assignors to Sybron Corporation, precipitation processes.
Rochester, N.Y. ‘Other objects and advantages of this invention will be
No Drawing. Filed June 23, 1971, Ser. No. 156,085
Int. Cl. C02b 1/20 apparent from the following description.
U.S. Cl. 210-53 8 Claims SUMMARY OF THE INVENTION
10
In the processes of this invention, sul?de ion and a
ABSTRACT OF THE DISCLOSURE heavy metal ion that forms a sul?de having a higher
Heavy metal pollutant ions are removed from an aque equilibrium sul?de ion concentration than the sul?de of the
ous solution in a sul?de precipitation process that avoids heavy metal pollutant to be removed are added to the
generation of noxious amounts of hydrogen sul?de and 15 aqueous solution to be treated. Since the sul?de of the
the formation of soluble complexes of sul?de ions. Sul added heavy metal is more soluble than the sul?de of the
?de ion and a heavy metal ion that forms a sul?de having a pollutant, the heavy metal pollutant ions are precipitated
higher equilibrium sul?de ion concentration than the sul in preference ‘to the added heavy metal ions. However,
?ed of the heavy metal pollutant are added to the solution. the added heavy metal ions act as a scavenger for excess
The added heavy metal acts as a scavenger for excess sul sul?de, thereby preventing the formation of noxious
?de. In some cases the added heavy metal and the heavy amounts of hydrogen sul?de and complex sul?de ions. In
metal pollutant form co-precipitates which result in more addition, in certain cases, the added heavy metal promotes
complete removal of the pollutant ion than could be co-precipitation of insoluble mixed metal sul?de com
achieved by sul?de precipitation of the pollutant alone. pounds that lead to lower pollutant concentration in the
25 effluent.
DETAILED DESCRIPTION
BACKGROUND OF THE INVENTION
In the preferred embodiment of this invention, a soluble
This invention relates to a process for removing heavy salt of the heavy metal to be added is dissolved in the
metal pollutants from aqueous solutions by precipitation. solution before the sul?de ion is introduced. The added
Soluble sul?des such as sodium sul?de have been used heavy metal ion then acts as an excess sul?de scavenger
in the past to precipitate metal values from solutions. With when sul?de is added to. precipitate the less soluble sul?de
proper controls, such separations are generally substantial and prevents the generation of noxious quantities of hy
ly quantitatively complete, however, prior art sul?de pre drogen sul?de and formation of the aforementioned com
cipitation processes have certain disadvantages which have plexes. >
prevented their wide-spread adoption. 35 The following table shows the sul?de ion concentra—
The most serious problem has been the formation of tions for several of the more common heavy metal sul
noxious quantities of hydrogen sul?de. Excess sul?de is ?des as calculated from their solubility products. The
usually added to insure complete precipitation of the heavy
values are arranged in descending order of equilibrium sul
metal pollutant. The excess sul?de forms hydrogen sul ?de ion concentration. Each metal ion can, therefore, be
?de gas, whose vapors are detectible even above highly 40 used as a scavenger for excess sul?de during precipitation
dilute alkaline solutions. of those metal ions lower in the table.
In some cases, the use of excess sul?de, instead of lead
ing to complete precipitation of the heavy metal pollutant, TABLE I
tends to form complex sul?de ions which remained in solu
tion. Among the complex ions which may be formed in 45 Equilibrium sul?de ion concentration
this manner are HgSf, S1183: and AgS=, which are Metal ion: (moles/l.)
formed according to the following equations: Mn“!-+ _________________________ __ 3.75>< 10*8
Fe++ ___ 6.1 X 10“10
Zn++ __________________________ __ 3.46 ><10—12
50 Ni++ __________________________ __ 1.18><10—12
Sn++ __________________________ __ 3.1 X 10-13
Co++ __________________________ __ 1.73><10"13
Due to these undesirable secondary effects of sul?de Pb++ __________________________ __ 1.84><10~14
precipitation processes, hydroxide precipitation has been Cd++ __________________________ __ 6.()><10‘15
used more widely than sul?de precipitation for the re 55 Ag+ ___________________________ __ 3.4 ><10-1"
moval of heavy metals. vUnfortunately, hydroxide precipita Bi’r-l'+ _________________________ __ 4.8 ><10—21
tion is generally no longer as complete as sul?de precipita Cu++ __________________________ __ 92x10‘-23
tion because most metal bearing waste streams now con Hg++ __________________________ __ 4.5><10-25
tain complexing agents which have been used in conjunc
tion with the heavy metal pollutants and which in large 60 The choice of the heavy metal salt to be added to the
measure stabilize the pollutant ions against hydroxide ‘but solution to be treated depends upon what ions are to» be
not against sul?de precipitation. removed from the solution, the use to which the water is
OBJECTS OF THE INVENTION to be put after it has been treated and such practical con
siderations as cost and availability of the various heavy
An object of this invention is to provide a process for 65 metal salts. For most waste treatment applications it is
precipitating heavy metal pollutants from an aqueous solu desirable to use a heavy metal salt which is relatively non
tion without generating noxious quantities of hydrogen toxic and generally innocuous since the Water may sub
sul?de. sequently be discharged to reservoirs Where stringent
Another object is to provide a sul?de precipitation proc water quality standards are observed. Salts of metals at
ess which avoids the formation of soluble complex sul?de 70 the top of the foregoing table are preferred since they
10ns. can precipitate a greater variety of pollutant io-ns. Man
Still another object is to provide a sul?de precipitation ganese forms the most soluble of these sul?des, however,
 3,740,331
3 4
iron salts will frequently be preferable because they are Regardless of the mode of addition, the processes of
generally cheaper than manganese salts. this invention will frequently reduce the pollutant con
After the added heavy metal salt is dissolved in the centration below the levels that can be obtained by hy
solution, a soluble sul?de is added to precipitate sul?des droxide precipitation processes, because many metal bear
of the various metals. The process may be manipulated to ing Wastes also contain complexing agents, which in large
selectively precipitate the ions at the bottom of Table I measure stabilize the pollutant ions against hydroxide,
by adding just enough sul?de to precipitate the pollutant but not against sul?de precipitation.
or pollutants which form the least soluble sul?des. Alter With certain combinations of pollutants and added
natively, a heavy metal salt which forms a sul?de of in heavy metal salts, the removal of pollutants may be even
termediate soubility; i.e., a sul?de that is more soluble 10 more complete than would be theoretically expected from
than the sul?des to be precipitated but less soluble than consideration of their solubility products, due to the co
the sul?des of some of the pollutants in the solution; may precipitation of the pollutant ions and the added heavy
be used to achieve the same result. In general, however, metal ions. For example, if mercury, copper and/or
a metal salt is chosen whose sul?de is more soluble than nickel ions are to be removed from solution and the
the sul?des of all of the pollutants and enough sul?de ion 15 added heavy metal is iron; co-precipitated, mixed metallic
is added to precipitate all of these less soluble sul?des. sul?des such as FeS-HgS, FeS-NiS, and/ or FeS'Cus may
Under equilibrium conditions, the resulting sul?de ion be formed. The formation of these mixed sul?des may
concentration is somewhere between lO—8 to 10*"25 moles reduce the mercury, copper and/or nickel level in the
per liter, depending upon the pH of the solution and the solution below the levels that could be achieved by sim
solubility of the added heavy metal sul?de. If the soluble 20 ple sul?de precipitation of the mercury, copper and/or
sul?de is introduced below the surface of the solution and nickel ions alone.
agitation is su?‘icient to prevent a localized concentration In addition to precipitating metal ions that form sul?des
of sul?de ions, the formation of the sul?de of the added directly, the processes of this invention can be used to
heavy metal instantaneously reduces the sul?de ion con eliminate certain pollutant ions, such as chromium (VI),
centration below the level at which it can form noxious 25 which must be reduced before they will form insoluble
amounts of hydrogen sul?de or soluble complex sul?des, precipitates. The thermodynamics of these reactions are
while simultaneously allowing several orders of magni not known precisely. A reasonable assumption, however,
tude more su?de ion than that required to precipitate is embodied in the following equation:
the metallic pollutants in the solution. As a result, no
objectionable odors are created and, since soluble com
plex sul?de ions are not formed, substantially all of the
metallic pollutants in the solution are precipitated.
Practically any sul?de which is more soluble than the In cases where a simple process is desired, chromium
metallic ions which are to be precipitated can be used as precipitation according to the processes of this invention
a source of sul?de ion. For reasons of availability and 35 is preferable to conventional hydroxide processes for
economy, sul?des such as sodium sul?de, sodium hydro elimination of chromium (VI) because a one step process
sul?de and hydrogen sul?de are preferred. Hydrogen sul can be employed. In conventional hydroxide processes,
?de and sodium hydrosul?de may be used effectively in the pH of the solution is reduced to around 2 or 3. A 1'e~
the process of this invention if a source of alkali such as dncing agent such as sulfur dioxide, a soluble sul?te or
sodium hydroxide is simultaneously added to maintain the metabisul?te is then used to reduce the chromium (VI)
pH in the preferred range of 7.0-8.0 and thereby prevent to chromium (HI). The pH of the solution is then raised
evolution of hydrogen sul?de gas. to about 8 to precipitate chromium hydroxide. Thus, at
The amounts of heavy metal salt and sul?de to be least two steps are required whereas in the processes of
added to the solution will depend chie?y upon the quan this invention a one step process may be employed be~
tity of pollutants to be precipitated. Preferred sul?de ion 45 cause the preferred pH for carrying out the reduction, i.e.,
addition quantities will generally be between two to ten 7.0-8.0, will suffice to substantially completely precipitate
times the pollutant ion concentration. The excess heavy all Cr(OH)3.
metal sul?de maintains a sul?de ion reservoir su?iciently The following are representative examples of the pre
large to be able to handle increases in pollutant ion load cipitation of heavy metal ions according to the process
ings. Thus, assuming a waste stream of 10 p.p.m. of of this invention.
heavy metal ions, somewhere between 20 and 100 mg. of
sul?de ion will be added per liter of solution to be EXAMPLE IA
treated.
The amount of heavy metal salt added to the solution In this test, the waste sample was a composite of all
is usually adjusted so that most, but not quite all, of the 55 the. discharges from an electronics plant. Due to the com
added heavy metal is precipitated as the sul?de along plex nature of the material, analysis for all metallic im
with the pollutant ions. This provides a slight excess of purities was regarded as impractical. However, following
scavenger to prevent formation of free sul?de ion and its sul?de and hydroxide treatment respectively the waste
potential problems. was analyzed for metals known to be initially present that
The precipitates produced by this process may be re are generally regarded as serious pollutants. These data
moved by ?ltration or by any of a number of conven are shown in Table II.
tional gravity separators, such as sedimentation basins, Prior to sul?de treatment, the waste was hypochlori
up?ow sludge blanket clari?ers or rapid tube settlers. nated at a pH of about 8.5 to destroy NH3. Using a 1700
Coagultants such as ferric sulfate, clay, polyelectrolytes ml. sample of hypochlorinated waste, the excess C10
or the like may be added to facilitate removal of the pre 65 was destroyed by the addition of 0.8 g. of sodium sul?te
cipitates. They may also be removed by ?otation and ?l (Na2SO3) and after ?ve minutes of agitation, the waste
tration and the like. was further treated with 0.58 g. of manganous sulfate
In some cases, it may be desirable to add the heavy monohydrate (MnSO4-H2O) followed by 0.75 g. of so
metal salt and the soluble sul?de simultaneously in order dium sul?de nonahydrate (N?zS'HgO). The treated waste
to simplify the equipment needed or to shorten the time 70 was agitated for ?ve minutes and then allowed to stand
required for addition of the materials. This can be done, for one hour to allow the precipitates to settle. No hydro
provided that a certain amount of care is taken in order gen sul?de odors were detected during either the ?ve
to insure that localized concentrations of sul?de ion do minute agitation period or the one hour settling period.
not develop. For example, increased agitation may be At the end of the one hour settling period, a sample of
needed if simultaneous addition is. employed. ' 75 the supernatant was reserved for analysis. '
 3,740,331
5 6
EXAMPLE IB this invention is far superior to conventional hydroxide
In order to compare the processes of this invention
precipitation and may be accomplished more simply.
The results obtained in the foregoing sul?de and hy
with hydroxide precipitation, a sample whose composition droxide precipitation processes are compared in the fol
was similar to the composition of the sample used in
Example IA was treated as follows. A soluble hypochlorite
lowing table.
was added to the water, which had a pH of 11.0, in order TABLE II
to convert cyanide ions known to be present to cyanate at Pollutant residues from—
which point metal hydroxides were precipitated. Sulfuric Waste Sul?de Hydroxide
acid was then added to reduce the pH to 8.5 and convert oompo- precipi- precipi
the cyanate to nitrogen and bicarbonate. The material was 10 Example No.
sition
in p.p.m.
tation
in p.p.m.
tation
m p.p.m
allowed to stand for one hour after which the liquid was
analyzed. The results, which are listed in Table II, show O. 8
2. 0
that precipitation by this method is not as complete as 95. 8
precipitation by the processes of this invention. , .
NHa, 475.
5. 9
_____________ __
15 IIIA-IIIB .... __ NH3, 475. 1.0
EXAMPLE IIA _____ _ _ 2. 0

In this test, waste from a printed circuit manufacturing IVA-IVB _____ . . {Cr(VI) 0. 05
Zn, 3. 2. 0
operation containing 100 p.p.m. Cu, 7.7 p.p.m. Ni and
475 p.p.m. NH3 was treated via the sul?de process. The These examples demonstrate a few of the many appli
pH of a 100 ml. sample was reduced to 7.7 with dilute 20 cations in which the processes of this invention may be
H2804. A 0.123 g. dosage of ferrous ammonium sulfate used advantageously. It should be understood that these
was added immediately prior to 0.75 g. of Na2S~9H2O. examples and the rest of the- foregoing description are
The sample was agitated for ?ve minutes and allowed to merely illustrative and are not intended to limit the scope
stand for one hour. No hydrogen sul?de odors were of this invention, which is delineated by the appended
detected during either the ?ve minute agitation period or 25 claims.
the one hour settling period. At the end of the one hour We claim:
settling period, the effluent was analyzed for copper and 1. A method of precipitating heavy metal pollutant ions
found to contain 1.8 p.p.m. from an aqueous solution comprising:
EXAMPLE IIB (a) adding a soluble salt of a heavy metal that forms
30 a sul?de having a higher equilibrium sul?de ion con
The same waste used in Example IIA was adjusted to centration than the sul?de of the heavy metal pol
pH 7.7, the sample agitated and settled as described in lutant to the solution; and
IIA. It was found to contain 95.8 p.p.m. Cu and 5.9 p.p.m. (b) adding enough soluble sul?de to the solution to
Ni. This demonstrates the complexing power of NH3 and precipitate the heavy metal pollutant ions but less
the problems it presents in hydroxide precipitation than the amount required to precipitate both the
processes. heavy metal pollutant ions and the added heavy metal
EXAMPLE IIIA-IIIB ions, whereby the heavy metal pollutant ions are pre
cipitated in preference to the heavy metal ion added
The tests performed in Examplesv IIA and IIB were to the solution.
repeated except that 40 p.p.m. Fe2(SO4)3 and 8 p.p.m. 2. A method according to claim 1 wherein the soluble
of an anionic polyacrylamide were added to coagulate sul?de is added after the soluble salt of the added heavy
the precipitates and the sample used in the hydroxide test metal.
was chlorinated to destroy the NI-I3. As can be seen from 3. A method according to claim 1 wherein the soluble
Table II, the results for sul?de precipitation, even in sul?de and the salt of the added heavy metal are added
the presence of NH3, were as good as the results produced 45 to the solution simultaneously.
by hydroxide precipitation after chlorination. _ 4. A method according to claim 1 wherein the amount
EXAMPLE IVA of soluble sul?de added is slightly less than the amount
required to precipitate the added heavy metal ions.
The waste used in this experiment contained 4.8 p.p.m. 50 5. A method according to claim 1 wherein the added
of Cr(VI) and 3.5 p.p.m. of Zn. The pH was adjusted to heavy metal salt is an iron salt or a manganese salt.
7.7. Then 382 mg. of Fe2SO4 and 333 mg. of N212S-9HO2 6. A method according to claim 1 wherein the soluble
were dissolved in small amounts of water and added sul?de is selected from the group consisting of sodium
simultaneously from separate pipettes. The’ sample was sul?de, sodium hydrosul?de and hydrogen sul?de.
agitated for one minute, 100 p.p.m. of clay and 2 p.p.m. 55 7. A method according to claim 1 wherein the amount
of an anionic polyacrylamide were added and slow agita of sul?de ion added is approximately 2‘ to 10 times the
tion continued for an additional minute. The sample was amount of heavy metal pollutant ions in the solution.
then allowed to stand for one minute. Again, no hydro-gen 8. A method according to claim 1 wherein the heavy
sul?de odors were detected during agitation or settling. metal pollutant ions and the added heavy metal form an
The effluent contained negligible amounts of Cr(VI) and 60 insoluble mixed sul?de compound.
0.03 p.p.m. Zn.
EXAMPLE IVB References Cited
UNITED STATES PATENTS
A 1 liter sample of the same waste as in Example IVA
containing 4.8 p.p.m. of Cr(VI) was adjusted to pH 2.0 65 2,346,320 4/ 1944 Moran et al _________ __ 210—52
with dilute sulfuric acid. A .0195 g. dosage of Na2SO3 1,633,621 6/1927 Blurnenfeld ________ .__ 2l0—53
was added with vigorous agitation. The pH of the reduced 1,908,545 5/1933 Schwab et al ________ __ 210-50
chromium solution was raised to 8.0 with dilute NaOH 1,557,188 10/1925 Newlands __________ ._ 210-63
and the sludge was allowed to settle for 1 hour. A sample 1,276,644 8/ 1918 Goldschmidt _______ __ 210—50
of the supernatant analyzed 0.05 p.p.m. residual Cr(VI) 70 SAMIH N. ZAHARNA, Primary Examiner
and 2.0 p.p.m. residual Zn++. Thus, it can be seen that
precipitation of chromium according to the processes of '1‘. G. WYSE, Assistant Examiner
 w-ww 'UNKTED STATES PATENT OFFICE ‘ 1 5"?
(5/697) " ' " ‘ ' *\ "1 v "*1 7" . "1 w ' '

CER'HFICA'HL 011* CORRILLTKON

Patent No. 31740 #3313} Dated ‘ June 19 , ‘1973
John‘ R, Anderson, chairles O. Weiss ’
I Inventor(s) " - ' I

It is certified that error appears in the above-identified patent '

and that said Letters Patent are ‘hereby corrected as shown below:

i" . J ' - . "3

Column 5 , Line 22 , "0 .‘75g", should be —- 0.0759’ —-.

sign-edema sealed this lzth'aa'y of'Merch 19m. ‘

(SEAL)
Attest:

EDWARD M.FLETCHER,JR; vc1. ‘MARSHALL DANN ,7 ‘ ~

Attesting Officer _ > " _ ‘ Commissioner of Patents

.3