US 4,244,735 AGrant
Chloride Leach Process for Recovering Metal Values in the Presence of Arsenic
Issue Date:1981-01-13
•13 Claims
Abstract
An improvement in the hydrometallurgical recovery of metals, such as, lead, silver, gold, antimony, and bismuth from materials such as flue dust in the presence of arsenic, comprising precipitating arsenic as an insoluble ferric-arsenic compound in the first processing step, carrying the insoluble arsenic compound through a chloride leach step, in which it is insoluble, to recover the metals, and disposing of the residue in which the arsenic has been fixed with ferric ions to render it non-polluting, or alternatively, recovering the arsenic by caustic leach and crystallization.
Metadata
Assignee
- Hazen Research, Inc.
Inventors
- James E. Reynolds
- Enzo L. Coltrinari
Application Information
Application Number:US 0614114
Filing Date:1979-07-27
Priority Date:1979-07-27
Art Unit:111
Classifications
IPC:
C22B 1304C22B 1104C22B 1508C22B 1922
Field of Search:
75423101 R;117;118 R;120;121;104;115;11439;87
Patent Drawings
This patent does not have any drawings.
Description
Disclosure of the Invention
A process is provided for recovering from a material containing arsenic at least one of the metals, lead, silver, gold, antimony, and bismuth which comprises precipitating arsenic in a first stage as a compound insoluble by subsequent processing, and carrying the insoluble arsenic compound through the metal recovery stage with the result that it is isolated as a final insoluble residue which can be disposed of within environmental requirements or processed to produce an arsenic compound which is saleable.
A first selective metal recovery stage may be performed via an acid-oxygen pressure leach in which copper, cadmium and other metals are solubilized in a filtrate from which they are readily recoverable by conventional techniques, enough ferric iron being present in the leach to precipitate substantially all of the arsenic as a ferric-arsenic compound. This compound is insoluble in a chloride leach under oxidizing conditions. The chloride leach solubilizes lead, silver, gold, antimony and bismuth. Lead is recovered by pelletization with coke or other carbonaceous material and lime or other alkaline material such as calcium oxide, using the alkaline material as a fluxing agent for the lead reduction, and recycling the chloride generated during the reaction to the chloride leach. Other metals are cemented out of solution with elemental lead. The ferric-arsenic compound remains in the final residue. Because of its high insolubility it can be disposed of in compliance with the environmental requirements. Alternatively, the ferric-arsenic compound may be converted to a soluble arsenic salt in a final caustic leach. This compound can be recovered as a saleable product by crystallization.
Technical Field
The invention lies in the field of hydrometallurgical recovery of metals from materials containing contaminating substances such as arsenic.
Background Art
A paper, entitled "Hydrometallurgical Recovery or Removal of Arsenic From Copper Smelter By-products" by K. Togawa, Y. Umetsu and T. Nishimura, presented at the 107th A.I.M.E. annual meeting at Denver, Colorado on Feb. 27-Mar. 2, 1978, discusses the problems involved in recovering valuable metals from copper ore refining flue dust, as well as the removal of arsenic as insoluble arsenates and as arsenic sulfide from aqueous solutions, and the hydrometallurgical recovery of arsenic trioxide from arsenic sulfide. The paper recovery from the flue dust of metals uncontaminated with arsenic, or the recovery of arsenic as a saleable product, nor does it disclose the other advantages or objectives of the present process.
An earlier article entitled "Recovery of Metals from the Dusts of Flash Smelting Furnace" by Eikichi Mohri and Minoru Yamada presented at the World Mining and Metals Technology Proceedings of the Denver Joint MMIJ-AIME meeting in 1976 discloses a hydrometallurgical process for treating copper smelter dusts by leaching, precipitating some (but not all) copper with hydrogen sulfide, neutralizing to pH2 with calcium carbonate to prevent precipitation of iron arsenate during subsequent copper cementation with iron powder, and finally oxidizing the solution with blowing air to form a stable iron arsenate. This process does not overcome the necessity for handling arsenic in its dangerous soluble forms during metal recovery steps, as does the present invention, nor does it immobilize arsenic in an insoluble state early enough so that substantially complete copper recovery is possible (H.sub.2 S precipitation must be halted at 2-3 grams of copper per liter of solution to avoid precipitating arsenic with the copper in this process). Neither does it provide for the recovery of arsenic in saleable form as sodium arsenate. The present process overcomes these problems and allows for substantially complete recovery of copper, zinc, cadmium, lead, and other metals, as well as sodium arsenate.
U.S. Pat. No. 4,149,880 to Prater, et al., discloses a copper cementation process following an oxygen pressure leach of the ore wherein some arsenic is insolubilized and about 0.5 to 2.0 grams per liter arsenic remain in solution. In this process, no attempt is made to insolubilize essentially all the arsenic value as is done in the present process.
U.S. Pat. No. 2,686,114 to McGauley, et al., discloses the insolubilization of arsenic values in a high pressure, high temperature ore oxidation leach using air. Arsenic is precipitated with iron in the ore and with alkaline earth metals as arsenates of these metals. The advantages of total insolubilization of arsenic with ferric ions apparently are not known to these inventors.
Best Mode for Carrying Out the Invention
In accordance with the objective of recovering the most valuable metal products first, and processing the arsenic with the least possibility of contamination of recovered products and danger to the environment and to workers handling the materials, copper smelters flue dust is first leached under oxygen pressure with acid, preferably hot sulfuric acid, containing ferric ions to recover one or more of the following: copper, zinc, cadmium, and germanium and to precipitate arsenic as an extremely insoluble ferric-arsenic compound. Next, the residue is leached with hot chloride solution to extract any one or more of the metal values lead, silver, gold, bismuth, and antimony, without solubilizing the arsenic. Finally, the residue is leached with hot caustic to recover arsenic as a saleable product, and the tails, after final arsenic fixation, are safely disposed to the environment. The sequential leaching process is summarized as follows:
The process is effective with a wide range of arsenic bearing materials including flue dusts containing in excess of 10% arsenic and less than 6% iron.
In the first leach of the preferred embodiment, copper, zinc, cadmium, and germanium are solubilized by a sulfuric acid leach, which also solubilizes the arsenic. To avoid carrying the arsenic over into the further processing of the liquor to redeem the metal values, the arsenic is oxidized under oxygen pressure and precipitated out as an extremely insoluble ferric-arsenic compound.
The preferred method for supplying the extra ferric ions when necessary for the stoichiometry of completely insolubilizing all the arsenic present is the addition of ferrous sulfate, preferably in excess of the amounts necessary for combination with all the arsenic. The leach system is maintained in an oxidizing mode. The excess ferric ion generated insures precipitation of virtually all of the arsenic.
Although ferric iron may be present in the system in the form of hematite, the solubility of hematite is not high enough to efficiently produce the required excess of ferric ions.
The metal values to be leached are solubilized within a very short time, but because the arsenic present in the flue dust is also extremely soluble, being 50% soluble in water alone, the materials in the system must be allowed to remain in contact for over an hour: depending on temperature and pressure as well as economic requirements, from 1 to 8 hours, and more preferably from 2 to 3 hours. This extended period of time allows for the formation of the insoluble ferric arsenic compound.
An oxidizing mode is maintained at approximately -400 to approximately -500 mv (satuarated calomel/platinum electrodes) with oxygen at a pressure of approximately 25 to approximately 75 psi, and more preferably, about 45 to about 55 psi, in order to oxidize the ferrous ions to their ferric state, the arsenic to its pentavalent state, and the sulfides to their more soluble sulfates.
The reaction is conducted at a temperature of between about 90.degree. C. and about 130.degree. C., and more preferably between about 105.degree. C. and about 115.degree. C.
The pH is maintained from about 0.1 to about 1.5, preferably with sulfuric acid, to solubilize as much of the metal values as possible without dissolving the ferric-arsenic compound.
As an optical step, in order to increase the filtration rate of the leach slurry, gypsum may be generated as a filter aid in situ by partially neutralizing the slurry (from 100 to 50 g/l sulfuric acid) with calcium carbonate. This partial neutralization was shown to increase the filter rate in gpm/ft.sup.2 by a factor of approximately 10. This step should be omitted if later arsenic recovery from the residue is desired, as the excess sulfate in the residue lowers arsenic recovery.
A liquid-solid separation is performed and the leach filtrate is then neutralized to pH approximately 2 to 4 by the gradual addition, with agitation, of calcium carbonate. During neutralization, the arsenic is precipitated to less than 100 parts per million, and preferably less than 10 parts per million. This arsenic appears in the gypsum cake formed during neutralization. The ferric-arsenic compound solubility product is nearly constant at this pH, and thus arsenic precipitation increases with increased ferric ion concentration in solution.
During neutralization, the temperature is permitted to reduce to between about 50.degree. C. and about 60.degree. C., to decrease arsenic solubility, and the materials are allowed to remain in contact for about 1/2 hour to allow time to aid the precipitation.
Copper, zinc, cadmium, and germanium are recovered from the filtrate by conventional methods, including electro winning of the copper, with sulfuric acid produced in the copper cells being recycled to the sulfate pressure leach. Cadmium and germanium may be recovered by cementation with zinc, and zinc sulfate recovered by evaporation. Because the arsenic has been removed, the filtrate may also be recycled without metal recovery therefrom, to enrich the feed of conventional metallurgical recovery processes for copper and zinc.
Filtered and washed residue from the oxidizing acid leach is advanced to a chloride leach to solubilize lead, silver, gold, bismuth and antimony. A hot chloride solution with an oxidizing agent in the presence of ferric ions extracts the metal values while leaving the arsenic compound undissolved.
Calcium chloride extracts lead as its chloride, which is highly soluble in the chloride solution, from its insoluble sulfate, precipitating gypsum. The chloride solution contains calcium chloride if extraction of lead is desired, and may also contain sodium chloride, hydrogen chloride, magnesium chloride, barium chloride, and/or seawater as the source of the chloride ions necessary to solubilize the desired metal values.
The oxidizing agent may be sodium chlorate, manganese dioxide, ozone, chlorine, hydrogen peroxide or others, and preferably is sodium chlorate or manganese dioxide.
The oxidizing agent, added in amounts required to adjust the emf to at least about -700 mv, solubilizes the gold while preventing re-leaching of the arsenic. If gold recovery is not desired, only slight oxidizing conditions need be maintained. A preferred emf in this case is at least about -450.
If there is insufficient lead in the oxidizing acid leach residue to merit recovery or lead recovery is otherwise not required, the chloride leach may be adjusted by reduction of the calcium chloride and the temperature in order that the lead sulfate will not be solubilized while silver, gold and bismuth values are leached. The chloride level must be sufficient so as to maintain the silver in solution.
The temperature of between about 80.degree. C. and about boiling temperature, preferably between about 80.degree. C. and about 105.degree. C., and more preferably approximately 95.degree. C.-100.degree. C., and the pH, adjusted at between about 0.1 and 1.0 and preferably between about 0.4 and 0.6 with sulfuric acid, allow for maximum solubilization of the metal values with minimum arsenic extraction.
The leach materials are allowed to remain in contact for between about one-half and two hours and preferably about one hour to insure complete dissolution of the lead, in the presence of ferric ions in a concentration of about 2 to about 4 g/l, and preferably about 3 g/l, added if necessary as FeCl.sub.3. These additional ferric ions, in the oxidizing conditions of the leach, insure that the ferric to ferrous ratio will be high enough to prevent formation of gold and prevent re-leaching of the ferric-arsenic compound.
A liquid-solid separation is performed, and the lead crystallized as high purity lead chloride, after which it may be reduced to elemental lead by pelletization with a carbonaceous material such as coke and an alkaline material such as calcium carbonate or calcium oxide at between about 800.degree. C. and about 1000.degree. C. producing a CaCl.sub.2 flux which may be recycled to regenerate the chloride leach and return chloride to the system. Silver, gold, bismuth, and antimony may be cemented out of the solution with elemental lead.
Alternatively, the arsenic-free filtrate may be used to enrich feed material for processing of lead ores.
The chloride leach residue, like the oxidizing acid leach residue, bearing the fixed arsenic, is safe for disposal to the environment. If necessary, additional arsenic fixation with ferric ions can be effected prior to disposal.
If arsenic is to be recovered in saleable form, the brine leach residue is leached in a caustic leach of heated, strong, basic solution, preferably a solution of approximately 50% sodium hydroxide, to extract arsenic as sodium arsenate, according to the generalized reaction--
Excess sodium hydroxide is used. In addition to the stoichiometric amount required for the above reaction, an excess of sodium hydroxide improves the performance of the circuit, and provides for better crystallization of the sodium arsenate.
The caustic leach is conducted for one-half to two hours, and preferably about one hour to insure maximum arsenate solubilization.
It is noteworthy that where the oxidizing acid leach slurry was partially neutralized with calcium carbonate prior to filtration, arsenic recovery during the caustic leach is somewhat reduced, and thus, when arsenic recovery is to be performed on the residue, calcium carbonate neutralization should be performed on the original leach liquor after it has been separated from the arsenic-containing residue so as not to add large quantities of gypsum to the residue.
The caustic leach is performed at least 40.degree. C. in order to solubilize the arsenate. Upper temperature limits are determined by the needs of the crystallizatin step.
After a liquid-solid separation, sodium arsenate of high purity is crystallized from the liquid by vacuum evaporation and cooling to approximately 25.degree. C., while stirring, which concentrates the sodium hydroxide from about 58-79 g/l NaOH to about 154-160 g/l NaOH. The crystals are then filtered, and dried.
The excess sodium hydroxide in the liquid insures that substantially all the arsenic will be crystallized when concentrated to about 154-160 g/l NaOH at room temperature. Further concentration is unnecessary and might result in contamination of the product with crystallized sodium hyroxide.
Due to the high solubility of sodium arsenate in water, the crystals are not washed, but are dried at approximately 80.degree. C.
The excess sodium hydroxide filtrate is recycled to the caustic leach. The caustic leach residue may be treated with additional ferric ions to fix the small amount of remaining arsenic and allow for safe disposal to the environment.
From the foregoing, it may be seen that an integrated process has been provided comprising the inventive steps of (1) a first oxidizing acid leach during which arsenic is precipitated as a highly insoluble ferric-arsenic compound, to be carried inertly through, (2) a second chloride leach, and recovered in, (3) a third caustic leach. No more than 100 parts per million arsenic reports to the neutralized liquor and less than 0.5 percent reports to the leach liquor in the brine leach. The results show that the process recovers essentially all of the arsenic in the feed and that the precipitation of arsenic as a ferric-arsenic compound in the first leach prevents any contamination of the recovered metals with arsenic. All of the metals that are being removed in each leach are removed in one pass.
The chloride leach might also be applied separately to various feed materials bearing lead, silver, gold, bismuth or antimony after arsenic fixation.
The caustic leach with subsequent arsenic fixation may be used to recover saleable arsenic from any feed materials comprised predominantly of ferric-arsenic compounds, at the same time allowing for safe disposal of the tails.
Examples
The following examples are descriptive, but not limiting of the invention.
1. Sulfate pressure leach
Five-hundred (500) gram samples of copper smelter flue dust were leached in a 2-liter Parr autoclave having an impellor speed of 1550 rpm at 100.degree. C. under an oxygen pressure of 50 psig with an oxygen bleed of 300 cc per minute (except for Test 5 where no oxygen bleed was used). The dust contained 13.9% copper, 2.05% zinc, 9.51% arsenic and 5.60% iron. Test results are summarized in Table 1.
2. Neutralization
The autoclave slurry of Example 1 is filtered and the liquor neutralized with calcium carbonate. In Test 1, prior to filtration, partial neutralization (from 100 g/l H.sub.2 SO.sub.4 to 50 g/l H.sub.2 SO.sub.4) is effected with calcium carbonate and in Test 2, this partial neutralization is omitted.
The patial neutralization of Test 1 precipitates gypsum which increases the filtration rate for the leach slurry from 0.013 gpm/ft.sup.2 to 0.17 gpm/ft.sup.2. After filtration of the slurry, the liquor is cooled to 50.degree. to 60.degree. C. and vigorously agitated while calcium carbonate is added in order to neutralize the solution to a pH of about 3. After one-half hour, the material is again filtered. The results of these tests are summarized in Table 2.
3. Brine Leach
250 grams of autoclave residue was leached with 250 g/l NaCl, 25 g/l CaCl.sub.2 and 3 g/l ferric ion as FeCl.sub.3. 6H.sub.2 O, at a temperature of 95.degree. C. to 100.degree. C. and a pH of 0.5, adjusted with HCl in an oxidizing mode using NaClO.sub.3 to achieve an emf of -690 to -700 mv. Test 1 residues were those in which the autoclave leach slurry was partially neutralized before filtration with CaCO.sub.3, as described in Example 2, and Test 2 residues were not previously treated with CaCO.sub.3. Test results are summarized in Table 3.
4. Caustic leach and sodium arsenate crystallization
The residue from the brine leach described in Example 3 was leached in sodium hydroxide at 40.degree. C. to extract arsenic as sodium arsenate. 3 grams of sodium hydroxide were used for each gram of arsenic dissolved plus an excess of 70 g/l. Test 1 residue was the result of the partially neutralized autoclave slurry described in Example 2. Test 2 was as described in Example 2. The leach slurry was then filtered and the liquid evaporated under vacuum to alter the sodium hydroxide concentration from 58-79 to 154-160 g/l NaOH, and cooled to 25.degree. C. while stirring to crystallize sodium arsenate from the liquid. The crystals were then dried on a Buchner funnel without washing, and further dried at 80.degree. C. Test 2 residue was derived from non-neutralized autoclave slurry residue. Test residues are summarized in Table 4. The values for "Liquor" and "Residue" resulted from the caustic leach. The values for "Mother Liquor" and "Crystals" resulted from the sodium arsenate crystallization.
A further test was performed on non-neutralized residue using a leach time of 43/4 hours and an excess sodium hydroxide of 80 g/l, and resulting in 88.3% arsenic extraction.
Sodium arsenate crystals from all tests were of good purity, with only minor amounts of entrained sodium sulfate and co-crystallized tin as impurities. Bismuth and germanium, which tended to report in varying degrees to all prior leach liquors and residues, were substantially not present in the sodium arsenate crystals.
5. Arsenic fixation
Arsenic solubility in the brine and caustic leach residues, for residues initially partially neutralized before filtration of the sulfate pressure leach as described in Example 2 and for non-neutralized residues, was determined after fixing the arsenic by the addition of 2 ml 100 g/l Fe.sup.+3 in the form of Fe.sub.2 (SO.sub.4).sub.3 to 10 grams of residue slurried with 75 ml H.sub.2 O, the emf being adjusted to -500 mv, and the pH being adjusted to approximately 2.0 with sulfuric acid. Calcium carbonate was then added to adjust the pH to 4.0 and the mixture stirred for one hour at 25.degree. C. The solubility of the fixed arsenic was then tested by contacting with demineralized water for up to 5 days. Test results are summarized in Table 5.
These results show extremely low arsenic solubility, even at fairly low pH, thus confirming that the brine and caustic leach residues are environmentally safe for disposal.
Claims
We claim:
1. In a hydrometalurgical process for recovering metal values selected from the group consisting of lead, silver, gold, antimony and bismuth from a material containing arsenates wherein substantially all of the arsenic is present in its pentavalent state, the improvement comprising leaching said metal values with a solution containing sufficient chloride ion concentration, in an amount of 2-4 gpl ferric ions and an oxidizing agent at a pH of at most about 1.0 in order to solubilize a substantial portion of the desired metal values to the exclusion of the arsenates.
2. The process of claim 1 wherein the emf is adjusted to at least about -700 mv.
3. The process of claim 1 wherein the emf is adjusted to at least about -450 mv.
4. The process of claim 1 wherein the pH is adjusted to at between about 0.4 and 0.6.
5. The process of claim 1 wherein the solid residue from the leach is further processed by leaching with hot caustic to recover arsenic as an arsenic salt crystallized from the caustic leach liquor.
6. The process of claim 1 wherein gold is one of the metals to be recovered and the oxidation potential of the leach is maintained at an emf of at least about -700 mv.
7. In a process for recovering at least one of the metals lead, silver, gold, bismuth and antimony from a material containing ferric-arsenic compounds, the improvemet comprising: (a) performing a chloride leach on the material wherein the chloride solution is selected from the group consisting of calcium chloride, sodium chloride, magnesium chloride, barium chloride, hydrogen chloride and sea water to bring the chloride ion concentration of the leach to a value sufficient to solubilize at least one of the metals lead, silver, gold, bismuth and antimony, in the presence of ferric ions in an amount of 2-4 gpl and an oxidizing agent at a pH of between about 0.1 and 1.0; (b) performing a liquid-solid separation on the material of step (a); and (c) recovering at least one of the metals lead, silver, gold, bismuth and antimony from the liquids of step (b).
8. The process of claim 7 wherein lead is one of the metals to be extracted in step (a), and the chloride solution contains sufficient calcium chloride to extract lead from lead sulfate and precipitate calcium sulfate.
9. The process of claim 7 wherein the pH of the leach is adjusted to between about 0.4 and about 0.6 with sulfuric acid.
10. The process of claim 7 wherein the leach is maintained at a potential of at least about -700 mv.
11. In a process for recovering at least one of the metals copper, cadmium, zinc and germanium from arsenic-containing flue dust resulting from the pyrometallurgical processing of copper ores, wherein during leaching of said metal values, arsenic is precipitated as an extremely insoluble ferric-arsenic compound, a liquid-solids separation is performed, and the liquid further processed for recovery of the metal values, and wherein the solid residue contains, in addition to ferric-arsenic compounds, lead and at least one of the metals silver, gold, bismuth and antimony, the improvement comprising: (a) leaching the solid residue with a chloride solution in the presence of ferric ions at a concentration of approximately between about 2 and about 4 grams per liter ferric at a pH of between about 0.4 and 0.6 adjusted with sulfuric acid at a temperature of between about 95.degree. C. and about 100.degree. C. in the presence of an oxidizing agent selected from the group consisting of sodium chlorate, manganese dioxide, ozone, chlorine and hydrogen peroxide to maintain the emf at between about -450 and -700 mv; in order to solubilize at least one of the metals lead, silver, gold bismuth and antimony and leave the ferric-arsenic compound unsolubilized; (b) performing a liquid-solid separation on the leach materials of step (a); and (c) recovering at least one of the metal values from the liquid of step (b).
12. The process of claim 11 wherein the chloride solution comprises brine and calcium chloride.
13. The process of claim 11 wherein the leach of step (a) is performed at a temperature of less than about 80.degree. C., and with sodium chloride and calcium chloride present at a weight ratio to each other of greater than 10:1, in amounts sufficient to solubilize the other metal values, but insufficient to solubilize the lead present in the said solid residue.
Patent Citations (15)
| Patent | Date | Inventor | Cited By |
|---|---|---|---|
| US803472 | 1905-10-01 | Cunnington | |
| US1331334 | 1920-02-01 | Field | |
| US1509688 | 1924-09-01 | Parsons et al. | |
| US2142274 | 1939-01-01 | Kuss | |
| US2283198 | 1942-05-01 | Fink et al. | |
| US2686114 | 1954-08-01 | McGanley et al. | |
| US2835569 | 1958-05-01 | Reynaud et al. | |
| US3687828 | 1972-08-01 | Carpenter et al. | |
| US3689253 | 1972-09-01 | Dorenfeld et al. | |
| US3998628 | 1976-12-01 | Gandon et al. | |
| US4018680 | 1977-04-01 | Kupfer | |
| US4063933 | 1977-12-01 | Peters | |
| US4113471 | 1978-09-01 | Langhorst et al. | |
| US4149880 | 1979-04-01 | Prater et al. | |
| US4166737 | 1979-09-01 | Demarthe et al. |