GB2118536A - Metal recovery - Google Patents
Metal recovery Download PDFInfo
- Publication number
- GB2118536A GB2118536A GB08308032A GB8308032A GB2118536A GB 2118536 A GB2118536 A GB 2118536A GB 08308032 A GB08308032 A GB 08308032A GB 8308032 A GB8308032 A GB 8308032A GB 2118536 A GB2118536 A GB 2118536A
- Authority
- GB
- United Kingdom
- Prior art keywords
- solution
- residue
- antimony
- lead
- silver
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002184 metal Substances 0.000 title claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 11
- 238000011084 recovery Methods 0.000 title claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 76
- 239000000243 solution Substances 0.000 claims abstract description 56
- 238000000034 method Methods 0.000 claims abstract description 38
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 35
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 35
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052709 silver Inorganic materials 0.000 claims abstract description 31
- 239000004332 silver Substances 0.000 claims abstract description 31
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 30
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000010949 copper Substances 0.000 claims abstract description 29
- 239000010802 sludge Substances 0.000 claims abstract description 24
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052802 copper Inorganic materials 0.000 claims abstract description 20
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 claims abstract description 20
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 19
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000002347 injection Methods 0.000 claims abstract description 10
- 239000007924 injection Substances 0.000 claims abstract description 10
- 150000001805 chlorine compounds Chemical class 0.000 claims abstract description 9
- 239000011133 lead Substances 0.000 claims description 30
- 238000001914 filtration Methods 0.000 claims description 22
- 239000007864 aqueous solution Substances 0.000 claims description 18
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 16
- 230000003472 neutralizing effect Effects 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 235000017550 sodium carbonate Nutrition 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical class Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 claims description 5
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 4
- OEYOHULQRFXULB-UHFFFAOYSA-N arsenic trichloride Chemical class Cl[As](Cl)Cl OEYOHULQRFXULB-UHFFFAOYSA-N 0.000 claims description 3
- 229940073609 bismuth oxychloride Drugs 0.000 claims description 3
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 claims description 3
- LIYKJALVRPGQTR-UHFFFAOYSA-M oxostibanylium;chloride Chemical compound [Cl-].[Sb+]=O LIYKJALVRPGQTR-UHFFFAOYSA-M 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 abstract description 7
- 229960000443 hydrochloric acid Drugs 0.000 description 22
- 235000011167 hydrochloric acid Nutrition 0.000 description 22
- 229940108928 copper Drugs 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 238000010908 decantation Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- NEIHULKJZQTQKJ-UHFFFAOYSA-N [Cu].[Ag] Chemical compound [Cu].[Ag] NEIHULKJZQTQKJ-UHFFFAOYSA-N 0.000 description 1
- QUQFTIVBFKLPCL-UHFFFAOYSA-L copper;2-amino-3-[(2-amino-2-carboxylatoethyl)disulfanyl]propanoate Chemical compound [Cu+2].[O-]C(=O)C(N)CSSCC(N)C([O-])=O QUQFTIVBFKLPCL-UHFFFAOYSA-L 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B11/00—Obtaining noble metals
- C22B11/04—Obtaining noble metals by wet processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B13/00—Obtaining lead
- C22B13/04—Obtaining lead by wet processes
- C22B13/045—Recovery from waste materials
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
- C22B15/0067—Leaching or slurrying with acids or salts thereof
- C22B15/0069—Leaching or slurrying with acids or salts thereof containing halogen
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
- C22B15/0089—Treating solutions by chemical methods
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B30/00—Obtaining antimony, arsenic or bismuth
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
There is disclosed a process for recovering metals of high commercial value from a sludge (1) containing lead, antimony, silver, arsenic, bismuth and copper, by a wet method, by treating (2) the sludge (1) with aqueous hydrochloric acid (3) accompanied by air injection (4). The treated sludge is separated (5) into a silver-enriched fraction (6) and a silver-depleted solution (7). The fraction (6) is treated (8) with aqueous hydrochloric acid (9) and the treated fraction is separated (11) into an argentiferous residue (12) from which silver is recovered and a solution (13) enriched in hydrochloric acid and lead chloride. The solution (7) is cooled (21) and filtered (22) to obtain a residue (23) enriched in lead chloride from which lead may be recovered and a solution (24) containing chlorides of antimony, bismuth, silver, arsenic, copper and lead from which these elements may be recovered. <IMAGE>
Description
SPECIFICATION
Metal recovery
This invention relates to a process for recovering
metals of high commercial value from a material containing such metals such as a mud or sludge containing lead, antimony and possibly other metals.
Such a sludge is treated in known processes by a dried method. The operations involved in this dry method are very complicated, and lead to both economical and ecological problems.
It has now been surprisingly found that the drawbacks of the known art can be overcome by a process mainly involving a wet route. This process has substantially economical advantages, giving higher yields with lower costs, together with substantial ecological advantages as it no longer produced fumes.
The process according to the present invention for recovering metals of high commercial value from a sludge containing lead and/or antimony, and possibly other metals, including silver and/or arsenic and/or bismuth and/or copper, each in elemental and/or combined form, comprises treating the sludge at least once by a wet method with hydrochloric acid in aqueous solution, optionally accompanied by air injection.
More particularly, where the sludge, besides containing lead and antimony, also contains silver, arsenic, bismuth and copper in such quantities as to make their recovery also convenient, the process preferably comprises the following steps:
(a) treating the sludge with aqueous hydrochloric acid accompanied by air or oxygen injection;
(b) decanting, syphoning and optionally filtering the treated sludge of step (a) to separate a thickened fraction enriched in silver from a solution depleted thereof;
(c) treating the thickened fraction of step (b) with aqueous hydrochloric acid, possibly accompanied by air or oxygen injection;
(d) decanting, syphoning and optionally filtering the treated thickened fraction of step (c) to separate an argentiferous residue from an aqueous solution rich in hydrochloric acid and lead chloride;;
(e) washing and filtering the argentiferous residue of stap (d) to separate a purified argentiferous residue enriched in silver chloride from an aqueous solution, which latter is recycled to step (c);
(f) cooling and filtering the solution of step (b) to separate a residue enriched in lead chloride from a solution containing antimony, bismuth, silver, arsenic, copper and lead chlorides;
(g) cooling and filtering the aqueous solution enriched in hydrochloric acid and lead chloride of step (d) to separate a residue enriched in lead chloride from a solution enriched in hydrochloric acid, which latter is recycled to step (a).
The purified argentiferous residue withdrawn from step (e) can subsequently be converted to silver by reacting it with zinc dust, ammonium hydroxide and water, or alternatively by direct reduction.
The lead chloride residues withdrawn from steps (f) dnd (g) can be subjected to lead recovery as a pure salt, or alternatively, if the sludge emanates from industrial lead electrorefining, they can be fed to the main lead treatment cycle.
The process of the present invention preferably includes the selective separation of the elements present in the solution containing antimony, bismuth, silver, arsenic, copper and lead chlorides formed in step (f) by the following steps:
(i) hydrolysing the solution;
(ii) cooling and filtering the hydrolysed solution to separate a residue containing antimony from a solution depleted of antimony;
(iii) washing the antimony-containing residue with aqueous hydrochloric acid and then filtering it to separate a residue containing antimony oxychloride from an aqueous solution, which latter is recycled to step (i);;
(iv) neutralising the depleted solution of step (ii) with Na2CO3 or another neutralising agent and then filtering it to separate a residue, which is recycled to step (i), from an antimony-depleted solution containing bismuth, arsenic, silver, copper, lead and antimony chlorides.
The process of the present invention preferably includes treating the antimony-depleted solution containing bismuth, arsenic, silver copper, lead and antimony chlorides formed in step (iv) by the following steps.
(v) neutralising the solution with Na2CO3 or another neutralising agent and then filtering it to separate a residue containing bismuth from a bismuth-depleted solution which is enriched in copper and arsenic chlorides;
(vi) washing the bismuth-containing residue with hydrochloric acid and then filtering it to separate a residue comprising bismuth oxychloride from an aqueous solution, which latter is recycled to the hydrolysis step (i).
The sludge is preferably treated in step (a) at a temperature of from 50 to 80"C and for a time of from 0.5 to 3.0 hours, while the thickened fraction is preferably treated in step (c) at a temperature again of from 50 to 800C but for a time of from 0.5 to 2.0 hours.
The molar concentration of the aqueous hydrochloric acid is preferably from 3 to 8M in step (a), and preferably from 4 to 8M in step (c).
In step (f) and step (g), both the silver-depleted solution and the solution enriched in hydrochloric acid and lead chloride are preferably cooled to a temperature of from 15" to 25"C.
The solution containing antimony, bismuth, silver, arsenic, copper and lead chlorides is hydrolysed in step (i) at a preferred temperature of from 65 to 75"C, and the hydrolysed solution is preferably cooled to a temperature of from 15to 250C.
Neutralisation with Na2Co3 is preferably carried
out in the case of the antimony-depleted solution of
step (iv) to give a final pH of from 1.2 to 2, and in the
case of the solution of step (v) to give a final pH of
from 2.0 to 2.8.
The molar concentration of the aqueous hydroch
loric acid used in step (iii) to wash the antimony-containing residue is preferably from 0.5 to 0.7 M so as to attain a final pH of from 1 to 1.2, and that of the aqueous hydrochloric acid used in step (vi) to wash the bismuth-containing residue is preferably from 0.01 to 0.1 M so as to attain a final pH of from 2.2 to 2.5.
The invention will now be described, by way of example, with reference to the flow diagrams shown in Figures 1,2 and 3 of the drawings.
Referring to Figure 1, a sludge 1, either in the wet state or precalcined in order to eliminate organic residues, is treated at point 2 with aqueous hydrochloric acid 3, accompanied by air or oxygen injection 4.
The treated sludge is subjected to decantation, syphoning and possibly hot filtration at point 5, by means of which a silver-enriched thickened fraction 6 is separated from a silver-depleted solution 7. The silver-enriched thickened fraction 6 is subjected to a second treatment at point 8 with aqueous hydrochloric acid 9, possible accompanied by air or oxygen injection 10. The treated thickened fraction is itself subjected to decantation, syphoning and possibly hot filtration at point 11, in order to separate an argentiferous residue 12 from an aqueous solution
13 enriched in hydrochloric acid and lead chloride.
The aqueous solution 13 is cooled and filtered at point 14 in order to separate a residue 15 enriched in lead chloride from an aqueous solution 3 enriched in hydrochloric acid, which is recycled to point 2. The argentiferous residue 12 is washed with water 16 at point 17, and subsequently filtered at point 18 to separate a purified argentiferous residue 19 from an aqueous solution 20 which is recycled to point 8.
The silver-depleted solution 7 is cooled at point 21 and subsequently filtered at point 22 to separate a residue 23 enriched in lead chloride from a solution 24 containing antimony, bismuth, silver, arsenic, copper and lead chlorides.
If the sludge emanates from industrial lead electrorefining, the residues 15 and 23 enriched in lead chloride can be fed to the main lead treatment cycle, or alternatively the lead can be recovered as the pure salt.
The subsequent selective separation of the elements from solution 24 is shown diagrammatically in Figures 2 and 3.
The solution 24 containing antimony, bismuth, silver, arsenic, copper and lead chlorides is subjected to hydrolysis at point 25, cooled at point 26 and then filtered at point 27 to thus separate a residue 28 containing a high percentage of antimony from an antimony-depleted solution 29. The residue 28 is washed at point 30 with aqueous hydrochloric acid 31, and filtered at point 32 to thus separate a residue 33, containing mainly antimony oxychloride, from an aqueous solution 34 which is recycled to point 25.
The antimony-depleted solution 29 is neutralised
at point 35 with Na2CO3 or another neutralising
agent 36, and filtered at point 37 to separate a
residue 38, which is recycled to point 25, from a
solution 39 containing bismuth, arsenic, silver, cop
per, lead and antimony chlorides, in which the
bismuth, arsenic and possibly the copper are present
in high amounts.
The antimony-depleted solution 39 is neutralised
at point 40 with Na2CO3 or another neutralising
agent 41, and filtered at point 42 to separate a
residue 43 containing bismuth from a bismuth-de
pleted solution 44 which is rich in copper and arsenic chlorides.
The bismuth-containing residue 43 is washed at point 45 with hydrochloric acid in aqueous solution 46, and filtered at point 47 to separate a residue 48 containing mainly bismuth oxychloride, from an aqueous solution 49 which is recycled to point 25.
The invention will now be illustrated by the following Example in which reference is made to the
Figures.
EXAMPLE
The feed used was an anodic sludge emanating from lead electrorefining, having a weight in the wet state (w.w.) of 10000 g, a solids content (s.w.) of 7936 g, and the following composition;
Sb ........................................ 41.34% (3280.79)
Bi ....................................... 8.64% (685.79)
Ag ........................................ 7.86% (623.79)
As...................................................6.28% (490.4g)
Cu ....................................... 2.49% (197.69)
Pb ........................................ 8.10% (642.89)
74.61% (5920.99).
The remainder of the solids content to 100% (i.e.
25.39%) consisted of combined oxygen, combined sulphur, halogens, silica and organic material.
The first treatment with hydrochloric acid was carried out at 60 C for 3 hours with 6M aqueous hydrochloric acid, accompanied by air injection. The second treatment with hydrochloric acid was carried out again at 60 C but for 2 hours with 7.5M aqueous hydrochloric acid.
The washed argentiferous residue 19, having a w.w. of 1793 g and a s.w. of 1201 g, consisted of:
Sb.......................................................0.19% (2.3g)
Bi ........................................ 0.042% (0.5g) Ag ....................................... 48.61% (583.89) As ....................................... 0.035% (0.49) Cu .................................... 0.012% (0.1g) Pb................................................. 13.25% (159.1g)
The remainder of the solids content to 100% consisted of combined oxygen, combined sulphur, halogens, silica and organic material.
The residue 23, containing essentially lead chloride and having a w.w. of 721 9 and a s.w. of 582.29, consisted of:
Sb ....................................... 1.43% (8.39)
Bi................................................. 0.31% (1.8g)
Ag ....................................... 5.41% (31.5g)
As................................................. 0.24% (1.4g)
Cu ....................................... 0.096% (0.6g)
Pb ....................................... 63.07% (367.29)
The chloride solution 24, to be fed to the stage for separating the metals contained in it and having a volume of 43.400 litres, consisted of::
Sb ....................................... 75.35 g/litre (3270.29)
Bi ..................................... 15.79 g/litre (685.39)
Ag ........................................ 0.20 g/litre (8.79)
As.......................................... 11.26 g/litre (488.7g) Cu ....................................... 4.54 g/litre (197.09) Pb................................................. 2.69 g/litre (116.7g).
The hydrolysis was carried out at a temperature of 70 C, followed by cooling to 20 C.
The neutralisation at point 35 was carried out to a final pH of 1.7, whereas the washing at point 30 resulted in a final pH of 1.
The residue 33, having a w.w. of 7578.79 and a s.w. of 4300.6 g, consisted of:
Sb ....................................... 66.62% (2865.09)
Bi ...................................... 0.25% (10.79)
Ag ........................................ 0.092% (3.9g)
As ........................................ 2.30% (98.99)
Cu ....................................... 0.02% (0.89) Pb ...................................... 0.28% (12.09).
The antimony-depleted solution 39, having a volume of 235.59 litres, consisted of: Sb ........................................ 0.46 g/litre (108.49) Bi ........................................ 2.21 g/litre (520.69)
Ag............................................. 0,0081g/litre (1.9g)
As............................................ 1.35 g/litre (318.0g) Cu ...................................... 0.82 g/litre (193.29) Pb ........................................ 0.26 g/litre (61.29).
The sludge residue 38, which was recycled to the hydrolysis stage and had a w.w. of 3179.69 and a s.w. of 1012.479, consisted of;
Sb ........................................ 29.39% (297.59)
Bi ....................................... 15.13% (153.29)
Ag ...................................... 0.277% (2.8g)
As ........................................ 7.05% (71.49)
Cu ........................................ 0.22% (2.29)
Pb...................................................... 4.27% (43.2g).
The antimony-depleted solution 39 was neutralised at point 40 to a final pH of 2.3. The subsequent wash 44 was carried out to a final pH of 2.3.
The residue 48, having a w.w. of 2269 g and a s.w.
of 9269, consisted of:
Sb...................................................... 6.82% (63.1g)
Bi.................................................... 55.89% (517.5g)
Ag ....................................... 0.063% (0.6g)
As ..................................... 1.05% (9.7g)
Cu ..................................... 0.097% (0.9g) Pb ...................................... 6.27% (58.19).
The bismuth-depleted solution 44 having a volume of 228.506 litres, consisted of: Sb ....................................... 0.193 g/litre (44.1g) Bi ..................................... 0.0175 g/litre (4.0g)
Ag ..................................... 0.0057 g/litre (1.39) As ...................................... 1.35 g/litre (308.59)
Cu.......................................... 0.84 g/litre (192,0g) Pb ....................................... 0.015 g/litre (3.49).
Claims (24)
1. A process for recovering metal from a sludge containing lead and antimony, which comprises treating the sludge at least once by a wet method with aqueous hydrochloric acid optionally accompa
nied by air or oxygen injection.
2. A process as claimed in claim 1, wherein the sludge contains silver, arsenic, bismuth, copper, lead and antimony, in elemental and/or combined form.
3. A process as claimed in claim 2, wherein the sludge is subjected to the following steps:
(a) treating the sludge with aqueous hydrochloric acid optionally accompanied by air or oxygen injection;
(b) separating (for example by decanting, syphoning and optionally filtering) the treated sludge of step (a) into a thickened fraction enriched in silver and a solution depleted thereof;
(c) treating the thickened fraction of step (b) with aqueous hydrochloric acid optionally accompanied by air or oxygen injection;
(d) separating (for example by decanting, syphoning and optionally filtering) the treated thickened fraction of step (c) into an argentiferous residue and an aqueous solution enriched in hydrochloric acid and lead chloride;;
(e) washing and filtering the argentiferous residue of step (d) to separate a purified argentiferous residue enriched in silver chloride from an aqueous solution, which latter is recycled to step (c);
(f) cooling and filtering the solution of step (b) to separate a residue enriched in lead chloride from a solution containing antimony, bismuth, silver, arsenic, copper and lead chlorides; and
(g) cooling and filtering the aqueous solution enriched in hydrochloric acid and lead chloride of step (d) to separate a residue enriched in lead chloride from a solution enriched in hydrochloric acid, which latter is recycled to step (a).
4. A process as claimed in claim 3, wherein the purified argentiferous residue of step (e) enriched in silver chloride is converted to silver by reacting it with zinc dust, ammonium hydroxide and water.
5. A process as claimed in claim 3, wherein the purified argentiferous residue of step (e) enriched in silver chloride is converted to silver by direct reduction.
6. A process as claimed in any of claims 3 to 5, wherein the residues enriched in lead chloride of steps (f) and (g) are fed to a main lead treatment cycle.
7. A process as claimed in any of claims 3 to 5, wherein the residues enriched in lead chloride of steps (f) and (g) are subjected to recovery of lead in the form of a pure salt.
8. A process as claimed in any of claims 3 to 7, wherein the sludge is treated in step (a) at a temperature of from 50 to 80 C for a period of from 0.5 to 3.0 hours.
9. A process as claimed in any of claims 3 to 8, wherein the thickened fraction is treated in step (c) at a temperature of from 50 to 80 C for a period of from 0.5 to 2 hours.
10. A process as claimed in any of claims 3 to 9, wherein the silver-depleted solution is cooled in step (f) to a temperature of from 15 to 250C.
11. A process as claimed in any of claims 3 to 10, wherein the solution enriched in hydrochloric acid and lead chloride is cooled in step (g) to a temperature of from 15 to 25 C.
12. A process as claimed in any of claims 3 to 11, wherein the molar concentration of the aqueous hydrochloric acid used in step (a) is from 3 to 8 M.
13. A process as claimed in any of claims 3 to 12, wherein the molar concentration of the aqueous hydrochloric acid used in step (c) is from 4 to 8 M.
14. A process as claimed in any of claims 3 to 13, wherein the solution containing antimony, bismuth, silver, arsenic, copper and lead chlorides of step (f) is subjected to the following steps:
(i) hydrolysing the solution;
(ii) colling and filtering the hydrolysed solution to separate a residue containing antimony from a solution depleted of antimony;
(iii) washing the antimony-containing residue with aqueous hydrochloric acid and then filtering it to separate a residue containing antimony oxychloride from an aqueous solution, which latter is recycled to step (i); and
(iv) neutralising the depleted solution of step (ii) with Na2CO3 or another neutralising agent and then filtering it to separate a residue, which is recycled to step (i), from an antimony-depleted solution containing bismuth, arsenic, silver, copper, lead and antimony chlorides.
15. A process as claimed in claim 14, wherein the solution containing antimony, bismuth, silver, arsenic, copper and lead chlorides is hydrolysed in step (i) at a temperature of from 65 to 75"C.
16. A process as claimed in claim 14 or 15, wherein the hydrolysed solution is cooled in step (ii) to a temperature of from 15 to 25"C.
17. A process as claimed in any of claims 14 to 16, wherein the antimony-depleted solution is neutralised in step (iv) with Na2CO3 to a final pH of from 1.2to2.
18. A process as claimed in any of claims 14to
17, wherein the molar concentration of the aqueous
hydrochloric acid used in step (iii) for washing the antimony-containing residue is from 0.5 to 0.7 M in order to attain a final pH of from 1 to 1.2.
19. A process as claimed in any of claims 14to 18, wherein the antimony-depleted solution containing bismuth, arsenic, silver, copper, lead and antimony chlorides of step (iv) is subjected to the following steps:
(v) neutralising the solution with Na2CO3 or another neutralising agent and then filtering itto separate a residue containing bismuth from a bismuth-depleted solution which is enriched in copper and arsenic chlorides; and
(vi) washing the bismuth-containing residue with hydrochloric acid and then filtering it to separate a residue comprising bismuth oxychloride from an aqueous solution, which latter is recycled to step (i).
20. A process as claimed in claim 19, wherein the solution is neutralised in step (v) with Na2CO3 to a final pH of from 2.0 to 2.8.
21. A process as claimed in claim 19 or 20, wherein the molar concentration of the aqueous hydrochloric acid used in step (vi) for washing the bismuth-containing residue is from 0.01 to 0.1 in order to attain a final pH of from 2.2 to 2.5.
22. A process as claimed in claim 1, substantially as hereinbefore described with reference to Figures 1,2 and 3 of the drawings.
23. A process as claimed in claim 1, substantially as described in the foregoing Example.
24. A metal recovered by a process as claimed in any of claims 1 to 23.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT2056582A IT1190758B (en) | 1982-04-05 | 1982-04-05 | PROCEDURE FOR THE RECOVERY OF HIGH COMMERCIAL METALS CONTAINED IN THE SLUDGE |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB8308032D0 GB8308032D0 (en) | 1983-04-27 |
| GB2118536A true GB2118536A (en) | 1983-11-02 |
| GB2118536B GB2118536B (en) | 1985-06-05 |
Family
ID=11168868
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08308032A Expired GB2118536B (en) | 1982-04-05 | 1983-03-23 | Metal recovery |
Country Status (10)
| Country | Link |
|---|---|
| JP (1) | JPS58189339A (en) |
| AU (1) | AU566442B2 (en) |
| BE (1) | BE896374A (en) |
| CA (1) | CA1207152A (en) |
| DD (1) | DD210311A5 (en) |
| DE (1) | DE3312247A1 (en) |
| FR (1) | FR2524488B1 (en) |
| GB (1) | GB2118536B (en) |
| IT (1) | IT1190758B (en) |
| RO (1) | RO86750B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7559971B2 (en) * | 2002-10-11 | 2009-07-14 | Outotec Oyj | Method for removal of silver from a copper chloride solution |
| CN102305843A (en) * | 2011-03-11 | 2012-01-04 | 肇庆理士电源技术有限公司 | Method for quickly identifying whether plumbum or plumbum and calcium alloy contains antimony |
| CN107058746A (en) * | 2017-04-27 | 2017-08-18 | 郴州市金贵银业股份有限公司 | A kind of method that antimony is separated from silver-colored smelting ash |
| CN107130115A (en) * | 2017-04-27 | 2017-09-05 | 郴州市金贵银业股份有限公司 | It is a kind of that arsenic, the method for antimony are separated from silver-colored smelting ash |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3732242A1 (en) * | 1987-09-24 | 1989-04-06 | Zweckverband Sondermuellplaetz | Process for treating residues containing non-ferrous metals |
| CN1051114C (en) * | 1996-10-25 | 2000-04-05 | 昆明贵金属研究所 | Pretreatment method before wet method acid immersion for lead anode mud |
| CN103954524B (en) * | 2013-12-11 | 2017-02-15 | 西部矿业股份有限公司 | Simple and rapid method for accurate determination of silver in lead anode mud |
| CN113481371A (en) * | 2021-07-07 | 2021-10-08 | 江西理工大学 | Method for efficiently recovering antimony, bismuth, copper and silver from silver separating slag of lead anode slime |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB260451A (en) * | 1926-01-11 | 1926-11-04 | Arthur Gordon | Improvements in the recovery and refining of precious metals |
| GB264569A (en) * | 1925-07-21 | 1927-01-21 | Stanley Cochran Smith | Improvements relating to the extraction of lead from materials containing it or its compounds |
| GB288049A (en) * | 1927-05-23 | 1928-04-05 | Franz Bischitzky | Process for the separation of tin from alloys and mechanical mixtures |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE490304C (en) * | 1925-07-21 | 1930-01-31 | Stanley Cochran Smith | Extraction of lead from complex lead sulfide ores and processed products |
| US3658510A (en) * | 1970-04-14 | 1972-04-25 | American Metal Climax Inc | Recovery of silver from electrolytic copper refinery slimes |
| FR2325723A1 (en) * | 1975-09-26 | 1977-04-22 | Asturienne Mines Comp Royale | PROCESS FOR RECOVERY OF ZINC ELECTROLYTIC METALLURGY RESIDUES BY RECOVERY OF THE METALS CONTAINED |
| FR2336484A1 (en) * | 1975-12-23 | 1977-07-22 | Von Roll Ag | PROCESS AND DEVICE FOR SEPARATING IRON, ZINC AND LEAD FROM GUEULARD DUST OR GUEULARD SLUDGE |
| US4018680A (en) * | 1976-02-24 | 1977-04-19 | Vol Roll A.G. | Process for separating iron, zinc and lead from flue dust and/or flue sludge |
-
1982
- 1982-04-05 IT IT2056582A patent/IT1190758B/en active
-
1983
- 1983-03-21 AU AU12628/83A patent/AU566442B2/en not_active Ceased
- 1983-03-23 GB GB08308032A patent/GB2118536B/en not_active Expired
- 1983-03-30 FR FR8305244A patent/FR2524488B1/en not_active Expired
- 1983-03-31 CA CA000425047A patent/CA1207152A/en not_active Expired
- 1983-04-04 DD DD83249468A patent/DD210311A5/en unknown
- 1983-04-05 DE DE19833312247 patent/DE3312247A1/en active Granted
- 1983-04-05 JP JP58058819A patent/JPS58189339A/en active Pending
- 1983-04-05 BE BE0/210486A patent/BE896374A/en not_active IP Right Cessation
- 1983-04-11 RO RO110522A patent/RO86750B/en unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB264569A (en) * | 1925-07-21 | 1927-01-21 | Stanley Cochran Smith | Improvements relating to the extraction of lead from materials containing it or its compounds |
| GB260451A (en) * | 1926-01-11 | 1926-11-04 | Arthur Gordon | Improvements in the recovery and refining of precious metals |
| GB288049A (en) * | 1927-05-23 | 1928-04-05 | Franz Bischitzky | Process for the separation of tin from alloys and mechanical mixtures |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7559971B2 (en) * | 2002-10-11 | 2009-07-14 | Outotec Oyj | Method for removal of silver from a copper chloride solution |
| CN102305843A (en) * | 2011-03-11 | 2012-01-04 | 肇庆理士电源技术有限公司 | Method for quickly identifying whether plumbum or plumbum and calcium alloy contains antimony |
| CN107058746A (en) * | 2017-04-27 | 2017-08-18 | 郴州市金贵银业股份有限公司 | A kind of method that antimony is separated from silver-colored smelting ash |
| CN107130115A (en) * | 2017-04-27 | 2017-09-05 | 郴州市金贵银业股份有限公司 | It is a kind of that arsenic, the method for antimony are separated from silver-colored smelting ash |
| CN107130115B (en) * | 2017-04-27 | 2018-12-07 | 郴州市金贵银业股份有限公司 | A method of separating arsenic, antimony from silver-colored smelting ash |
| CN107058746B (en) * | 2017-04-27 | 2018-12-07 | 郴州市金贵银业股份有限公司 | A method of separating antimony from silver-colored smelting ash |
Also Published As
| Publication number | Publication date |
|---|---|
| IT1190758B (en) | 1988-02-24 |
| FR2524488B1 (en) | 1986-04-25 |
| CA1207152A (en) | 1986-07-08 |
| JPS58189339A (en) | 1983-11-05 |
| DE3312247A1 (en) | 1983-10-20 |
| FR2524488A1 (en) | 1983-10-07 |
| GB8308032D0 (en) | 1983-04-27 |
| DD210311A5 (en) | 1984-06-06 |
| DE3312247C2 (en) | 1988-08-18 |
| AU1262883A (en) | 1983-10-13 |
| IT8220565A0 (en) | 1982-04-05 |
| AU566442B2 (en) | 1987-10-22 |
| RO86750B (en) | 1985-05-31 |
| GB2118536B (en) | 1985-06-05 |
| RO86750A (en) | 1985-05-20 |
| BE896374A (en) | 1983-10-05 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |