CA1207152A - Process for recovering metals of high commercial value contained in a mud - Google Patents
Process for recovering metals of high commercial value contained in a mudInfo
- Publication number
- CA1207152A CA1207152A CA000425047A CA425047A CA1207152A CA 1207152 A CA1207152 A CA 1207152A CA 000425047 A CA000425047 A CA 000425047A CA 425047 A CA425047 A CA 425047A CA 1207152 A CA1207152 A CA 1207152A
- Authority
- CA
- Canada
- Prior art keywords
- solution
- residue
- stage
- antimony
- rich
- 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.)
- Expired
Links
- 238000000034 method Methods 0.000 title claims abstract description 36
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 10
- 239000002184 metal Substances 0.000 title claims abstract description 10
- 150000002739 metals Chemical class 0.000 title claims abstract description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 56
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000007864 aqueous solution Substances 0.000 claims abstract description 29
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 28
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 27
- 239000010949 copper Substances 0.000 claims abstract description 25
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052709 silver Inorganic materials 0.000 claims abstract description 23
- 239000004332 silver Substances 0.000 claims abstract description 23
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052802 copper Inorganic materials 0.000 claims abstract description 19
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 16
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000002347 injection Methods 0.000 claims abstract description 7
- 239000007924 injection Substances 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 51
- 239000011133 lead Substances 0.000 claims description 27
- 238000001914 filtration Methods 0.000 claims description 19
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 claims description 18
- 150000001805 chlorine compounds Chemical class 0.000 claims description 8
- 230000007062 hydrolysis Effects 0.000 claims description 8
- 238000006460 hydrolysis reaction Methods 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 238000005406 washing 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
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 230000003472 neutralizing effect Effects 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
- LIYKJALVRPGQTR-UHFFFAOYSA-M oxostibanylium;chloride Chemical compound [Cl-].[Sb+]=O LIYKJALVRPGQTR-UHFFFAOYSA-M 0.000 claims description 3
- 238000011084 recovery Methods 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
- OEYOHULQRFXULB-UHFFFAOYSA-N arsenic trichloride Chemical class Cl[As](Cl)Cl OEYOHULQRFXULB-UHFFFAOYSA-N 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- 229960000443 hydrochloric acid Drugs 0.000 claims 12
- 235000011167 hydrochloric acid Nutrition 0.000 claims 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims 8
- 235000017550 sodium carbonate Nutrition 0.000 claims 4
- 229940073609 bismuth oxychloride Drugs 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000010908 decantation Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- -1 arsenio, silver Chemical compound 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000007787 solid 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)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (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
"PROCESS FOR RECOVERING METALS OF HIGH COMMERCIAL VALUE CONTAINED
IN A MUD."
Abstract of the disclosure:
A process for recovering metals of high commercial value from a mud containing lead, antimony, silver, arsenic, bismuth and copper by a wet method, by attacking with hydrochloric acid in aqueous solution accompanied by air injection.
IN A MUD."
Abstract of the disclosure:
A process for recovering metals of high commercial value from a mud containing lead, antimony, silver, arsenic, bismuth and copper by a wet method, by attacking with hydrochloric acid in aqueous solution accompanied by air injection.
Description
~2~ 2 "PROCESS FQR RECOVERING METALS OF ~IIGH COMMERCIAL V9LUE CONTAINED
IN A MUD."
This inrention relates to a process for recovering metals of high commercial value from a mud containing lead, antimony and other metals~
Such a mud is treated in known processes by a dried method7 The operations involved in the dry method are very complicated, and lead to both economical and ecological problems.
It has no~r been surprisin~ly found that the dra~rbacks of the known art can be overcome by a process m~inly involving a wet route.
This process has substantial economical advantages, giving higher yields with lower costs, together ~ith substanti~l ecological advantages as it no longer produces fumes.
The process according to the present invention for recovering metals of hig}l commercial value from a mud containing lead~
antimony and possibly other metals, including silver~ arsenic~
bismuth and copper, consists o~ attacking said mud at least once by ~ wet method ~nth hydrochloric acid in aqueous solutionS
possibly accompanied by air in~ection~
More particularly, where the mud besides containing lead and antimon~ also contains silver, arsenicS bismuth and copper in such quantities as to make their recovery also convenient, said process comprises the following operations:
a) attacking the mud with hydrochloric acid in aqueous soIution accompanied by air or oxygen injection;
b) decanting, syphon;ng and possibly filtering the attacked mud of point a) to separate a thickened fraction rich in silver from a solution depleted thereof;
'~ ~
~Z(~7~
c) attacking the thickened fraction of point b) with hydrochloric aGid in aqueous solution, if desired, ~c~Y~ ;Pd by air or oxygen injection;
d) decanting, syphoning and possibly filtering the attacked thickened fraction of point c) to separate an argentiferous residue from an aque~us solution rich in hydrochloric acid and lead chloride;
e) washing and filtering the arg_ntiferous residue of point d) to ~eparate a puriied argen~iferous residue rich in silver chloride from an aqueous solution ~;hich is recycled to sta~e c);
f) cooling and filterin~ the solution of point b) to separate a residue rich in lead chloride from a solution cont~;n;n~
antimony, bismuth, silver~ arsenic~ copper and lead chlorides;
g) co~ling and fil~ering the aqueous solution rich in hydrochloric acid and lead chloride of point d) to separate a residue rich in lead chloride fro~ a solution rich in hydrochloric acid which is recycled to stage a).
The puxified ar~entiferous residue ~:ithdr~wn from stage e) can subsequently be converted to silver by reacting it with zinc dust,
IN A MUD."
This inrention relates to a process for recovering metals of high commercial value from a mud containing lead, antimony and other metals~
Such a mud is treated in known processes by a dried method7 The operations involved in the dry method are very complicated, and lead to both economical and ecological problems.
It has no~r been surprisin~ly found that the dra~rbacks of the known art can be overcome by a process m~inly involving a wet route.
This process has substantial economical advantages, giving higher yields with lower costs, together ~ith substanti~l ecological advantages as it no longer produces fumes.
The process according to the present invention for recovering metals of hig}l commercial value from a mud containing lead~
antimony and possibly other metals, including silver~ arsenic~
bismuth and copper, consists o~ attacking said mud at least once by ~ wet method ~nth hydrochloric acid in aqueous solutionS
possibly accompanied by air in~ection~
More particularly, where the mud besides containing lead and antimon~ also contains silver, arsenicS bismuth and copper in such quantities as to make their recovery also convenient, said process comprises the following operations:
a) attacking the mud with hydrochloric acid in aqueous soIution accompanied by air or oxygen injection;
b) decanting, syphon;ng and possibly filtering the attacked mud of point a) to separate a thickened fraction rich in silver from a solution depleted thereof;
'~ ~
~Z(~7~
c) attacking the thickened fraction of point b) with hydrochloric aGid in aqueous solution, if desired, ~c~Y~ ;Pd by air or oxygen injection;
d) decanting, syphoning and possibly filtering the attacked thickened fraction of point c) to separate an argentiferous residue from an aque~us solution rich in hydrochloric acid and lead chloride;
e) washing and filtering the arg_ntiferous residue of point d) to ~eparate a puriied argen~iferous residue rich in silver chloride from an aqueous solution ~;hich is recycled to sta~e c);
f) cooling and filterin~ the solution of point b) to separate a residue rich in lead chloride from a solution cont~;n;n~
antimony, bismuth, silver~ arsenic~ copper and lead chlorides;
g) co~ling and fil~ering the aqueous solution rich in hydrochloric acid and lead chloride of point d) to separate a residue rich in lead chloride fro~ a solution rich in hydrochloric acid which is recycled to stage a).
The puxified ar~entiferous residue ~:ithdr~wn from stage e) can subsequently be converted to silver by reacting it with zinc dust,
2~ ammonium hydroxide and water, or alternatively by direct reduction.
The lead chloride residue withdrawn from stages f) and g) can be fed for lead recovery as a pure salt~ or alterl~tively if the attacked a mud origin~tes from industrial le~d electrorefini~g, it can be fed tQ a main lead treatment cycle.
The process o~ the present invention also comprises the selectiYe ~eparation of the elements present ir the solution containing antimony~ bismuth, sil~er, arsenic, coppe- and lead chlorides .. ,.
:
....
1207~52
The lead chloride residue withdrawn from stages f) and g) can be fed for lead recovery as a pure salt~ or alterl~tively if the attacked a mud origin~tes from industrial le~d electrorefini~g, it can be fed tQ a main lead treatment cycle.
The process o~ the present invention also comprises the selectiYe ~eparation of the elements present ir the solution containing antimony~ bismuth, sil~er, arsenic, coppe- and lead chlorides .. ,.
:
....
1207~52
- 3 -formed in stage f~ by the following operations:
i) hydrolysing the 601ution;
ii) cooling and filtering the hydrolysed solution to separate a residue cont~;n;n~ antimony from a solution depleted of 6aid antimony;
iii) w~h;ng the antimony-cont~;n;ng residue with hydrochloric acid in aqueous solution and then ~iltering to separate a residue cont~;n;nz antimony oxychloride from an aqueous solution wh.ich is recycled to stage i);
iiii) nsutrRl;~;n~ the depleted solution of point ii) with NA2CO3 or another neutr~l;s;ng agent and then filtering to separaie a residue, which i5 recycled to stage i)7 from an antimony_ depleted solutinn cont~;n;ng bismuth~ ar6enic, sil~er~
copper, lead and antimony chlorides.
~he process of the present invention also comprises treating the antimony~depleted solution cont~;n;ng bismuth~ arsenic~ 6ilver, copper9 lead and antimony chlorides formed in stage iiii) by the following operations:
j) neutr~ ;ng the solution with ~a~C03 or another neutralising agent and then filtering to separate a residue containing bismuth from a bismuth-depleted solution which is rich in copper ~nd arsenic chlorides;
jj) ~h;n~ the bismuth-cont~;n;n~ residue with hydrochloric acid and then filtering to separate a residue consisting of bismuth ox~chloride from an aqueous 601ution which is recycled to the hydrolysis stag~
The mud may be attacked in stage al at a temperature of between ` 12(~7~
i) hydrolysing the 601ution;
ii) cooling and filtering the hydrolysed solution to separate a residue cont~;n;n~ antimony from a solution depleted of 6aid antimony;
iii) w~h;ng the antimony-cont~;n;ng residue with hydrochloric acid in aqueous solution and then ~iltering to separate a residue cont~;n;nz antimony oxychloride from an aqueous solution wh.ich is recycled to stage i);
iiii) nsutrRl;~;n~ the depleted solution of point ii) with NA2CO3 or another neutr~l;s;ng agent and then filtering to separaie a residue, which i5 recycled to stage i)7 from an antimony_ depleted solutinn cont~;n;ng bismuth~ ar6enic, sil~er~
copper, lead and antimony chlorides.
~he process of the present invention also comprises treating the antimony~depleted solution cont~;n;ng bismuth~ arsenic~ 6ilver, copper9 lead and antimony chlorides formed in stage iiii) by the following operations:
j) neutr~ ;ng the solution with ~a~C03 or another neutralising agent and then filtering to separate a residue containing bismuth from a bismuth-depleted solution which is rich in copper ~nd arsenic chlorides;
jj) ~h;n~ the bismuth-cont~;n;n~ residue with hydrochloric acid and then filtering to separate a residue consisting of bismuth ox~chloride from an aqueous 601ution which is recycled to the hydrolysis stag~
The mud may be attacked in stage al at a temperature of between ` 12(~7~
- 4 -50 and 80C for a time of between 0O5 and ~.0 hours~ while the thickened fraction attack of stage c~ may be carried out at a temperature again of between 50 and 80 C but for a time of between 0O5 and 2.0 hours.
The molar concentration of the hydrochloric acid in aqueous solu-tion may be chosen between 3 and 8 M in the anode mud attack stage a)~ and between 4 and 8 H in the thickened fraction attack stage c), In sta~e f~ and stage g), both the silver-depleted solution and the solution rich in hydrochloric acia and lead chloride may be cooled to a temperature of between 15 and 25 C~
Tha solution cont~;n;n~ antimony, bismuth, silver, arsenic, copper and lead chlorides may be hydrolysed in stage i~ at a temperature of between 65 and 75 C~ and the hydrolysed solutio~ may be ~ooled to a temperature o~ between 15 and 25 C.
Neutralisation with Na2C03 may be carried out in the case of the antimony~depleted solution of 6tag~ iiii) to gi~e a final pH chosen between 1.2 and 2, and in the case of the ~olution of stage j) to give a fi~al pH chosen between 2.0 and 2.8.
Ths ~olar concentration of the hydrochloric acid in aqueous ~olution must be chosen in stage iii) involving ~.r~.sh;ng o~ the antimony-cont~in;n~ residue at a value o~ between 0~5 and 0O7 M
~o as to ha~e a final pH of between 1 ana 1.2, and must be chosen ~ stage jj) invol~ing the ~ h;n~ of the bismuth-cont~;n;nE residue at a value of between 0.01 and 0.1 M so as to have a final pH of betwePn 2.2 and 2.5~
- The invention will be more apparent with reference to the diaO~rams . ~ , ~2~7~i2 -- 5 ~
of the accompanying figures which are not however to be considered as limitative of the invention itself;
Figure 1 represents a block flow diagram of a process in accordance with the present invention.
Figures 2 and 3 represent block flow ~;Agr~ms illustrating the selective separation of elements in accordance with the present invention.
The mud 1 (Figure 1~, either in the wet state or precalcined in order to eliminate organic residues, is attacked at 2 with hydrochloric acid in a~eous solution 3, accompanied by aix or oxygen injection 4.
The attacked mud undergoes decantation, syphoning and possibly hot filtration at 5, by means of which a silver-rich thickened fraction 6 is separated from a silver-depleted solution 7.
The silver-rich thickened fraction 6 undergoes a second attack at 8 with hydrochloric acid in aqueous solution 9, possibly accompanied by air or oxygen injection 10~
The attacked thickened fraction is itself subjected to decantation, syphoning and possibly hot filtration at 11, in order to separate an argentierous residue 12 from an aqueous solution 13 rich in hydrochloric acid and lead chloride.
The aqueous solution is cooled and filtered at 14 in order to separate a residue rich in lead chloride 15 fxom an aqueous solution rich in hydxochloric acid 3, which is recycled to the 1st attack 2.
The argentiferous residue 12 is washed with water 16 at 17, and subsequently filtered at 18 to separate a purified argentiferous residue 19 from an aqueous solution 20 which is recycled to the 2nd attack 8.
The silver-depleted solution 7 is cooled at 21 and ~,,s ~2~ Si2 subsequently filtered at 22 to separate a residue rich in lead chloride 23 from a solution 24 containing antimony, bismuth, sil~er, arsenic, copper and lead chlorides.
3L5i2 If the mud originates from industrial lead electrore~i.ning, the residue rich in lead chloride (streams 15 and 23) can be fed to the main lead treatment cycle, or otherwise the lead can be recovered as the pure salt.
The subsequent selective separation of the elements from solution 24 is shown aiagran~atisally in Figures 2 and 3~
The solution containin2 antimony, bismuth~ silver~ arsenic, copper and lead chlorides is fed to a hydrolysis stage at 25, cooled at 26 and then filtered at 27 to thus separate a residue 28 containing a high percentage o~ antimony from an antimony-depleted solution 29 ~he residue 28 is washed at 30 with nydrochloric acid in aqueous solutio~ 31, and ~iltered at 32 to thus separate a residue 33, containing mainly antimony oxychloride~ ~rom an aqueous solution 34 ~Yhich is recycled to the hydrolysis stage 25.
- 15 The nntimony_depleted solution 29 is neutralised at 35 with Na2CO~
or another neutrAl;c;n~ agent 36, and ~iltered at 37 to separate a residue 38, which is recycled to the hydrolysis sta~e 25, from a solution 39 cont~;n;n~ bismuth~ arsenio, silver; copper~ lead ~ and antimony chlorides~in which the bismuth, arsenic and possibly the copper are present in hi~h percentage.
The antimony-depleted solution 39 is neutralised at 40 with Na2C03 or another neutr~l;s;n~ a~ent 417 and ~iltered at 42 to separate a residue 43 containing bismuth ~rom a bismuth-depleted solution 44 which is rich in copper and arsenic chloridesO
The bismuth-cont~;n;nr residue 43 is washed at 45 with hydrochloric acid in aqueous solution 46~ and filtered at 47 to separate a residue 48 containing mainly bisn~lth oxychloride, from an aqueous 1~C17~52 solution 49 which is recycled to the hydrolysis stage 25~
One example is given hereinafter with reference to the accompanying figures.
EXAM~LE
The feed is an anode mud originating from lsad electrorefining, having a weight in the wet state (w.w.) of 10000 g, and a soJids content (s.w.) of 7936 g, of composition: -S~ 4103~ % 3280.7 g Bi 8~64 % 685.7 ~
Ag 7~86 sb 623.7 g ~s 6.18 % 490.4 g Cu 2.49 % 197~6 g Pb 8.10 ,~ 642~8 g 7~.61 ,' 5~20 9 g The remainder of ~he solias content to 100% (i.e. 25~39~o) consist~
of combined o~ygen, combin~d sulphur, halogenæ~ silica and organic substances.
The 1st attack is carried out nt Goc for 3 hours with a 6 M
aqueous solution of hydrochloric acid, accompanied by air inj~ction~
The 2nd attack is carried out again at 60 C but for 2 hours with a 7,5 M aqueous solution of hydrochloric acid.
The washed argentiferous residue 19, having a w.w. of 1793 g and a s.w. of 1201 g is composed of:
Sb 0.19 % 2.3 g Bi o.o4~,b o.5 g Ag 48~61 ,~ 583.8 g As 0~0~5~ 0.4 g ~2~ 52 cu . o.ol~sb 0~1 g Pb 13.25 ~ 159.1 g The remainder of the solids content to lOKP~ comprises combined oxygen, combined sulphur, halogens, silica and organic substances.
The residue 23 containing essentially lead chloride and having a w.w. of 721 g and a s.w. of 582.2 g is composed of:
Sb lr43 % 8~3 g Bi 0~31 % 1~8 g Ag 5.41 % 31~5 1~ ~s 0.24 ~ 104 g cu o.og6% o.6 g Pb 63.07 7~ 367.2 g The chloride solution 24 to be fed to the stage for separating the metals contained in i~ and having a volume of 43.400 litres is composed of:
Sb 75.35 ~/1 3270.2 g Bi 15.79 ~1 685~3 g Ag 0.20 g/l 8.7 g .
~s 11.26 g/l 488~7 g Cu 4054 ~/1 197.0 g Pb 2.69 æ/l 116~7 g The hydrolysis is carried out at a temperature of 70 C, followed by cooling to 20Co The neutralisation 35 is carried out with a M nal pH of 1.79 whereas the w~sh;n~ in 30 attains a final pH of 1~
The residue 33 having a w.w. of ~578~7 g and a s.w. of 4300.6 g is composed of:
31 20~
Sb 66~62 % 2865.0 g Bi 0.25 %10.7 g Ag 0.092% 3.9 g As 2.30 %98.9 g Cu 0.02 % o.8 g Pb . 0.28 %12.0 g The antimony-depleted solution 39 of 235.59 litres is composed of: .
Sb o.46 ~1108.4 æ
Bi 2.21 g/l520.6 g Ag 0.0081~/11.9 g As 1.35 g/l313.0 g Cu 0.82 ~/1193.2 0 . Pb 0.26 ~/161.2 g : ~ 15 The mud stream 38 which is recycled to the hydrolysis stage~ and has a w.w. of 3179.6 g and a s.w. o~ 1012.47 g~ contains:
Sb 29.39 %297~5 g Bi . 15.13 ~153~2 g Ag ~0.277~ 2.8 g As 7-5 % 71,4 g Cu 0.~2 562.2 ~
Pb 4.27 ~43.2 g The antimony~depleted solution 39 is neutralised at 40 to a fi~l p~ ~ 2~3.
~he subsequent ~lash 44 is carried out to a final pH of 2.3.
The residue 48 having a w~w. of 2269 g and a s~w. of 926 g contains:
7~2 Sb 6~82 ~0 6301 g Bi 55~89 % 517~5 g Ag o.o630~' oO6 g As 1~05 % 9~7 g cu O~0g7% Oo9 g Pb 6~27 % 5801 g The bismuth_depleted solution 44 of 228.506 litres contains.
Sb 0.193g/1 44.1 g Bi 0.0175g/1 4~0 g A 0.0057g~1 1.3 g As 1~35 ~1 308~5 g Cu o.84 g/l 192.0 g pb 0.015 g/l 3~4 g .,
The molar concentration of the hydrochloric acid in aqueous solu-tion may be chosen between 3 and 8 M in the anode mud attack stage a)~ and between 4 and 8 H in the thickened fraction attack stage c), In sta~e f~ and stage g), both the silver-depleted solution and the solution rich in hydrochloric acia and lead chloride may be cooled to a temperature of between 15 and 25 C~
Tha solution cont~;n;n~ antimony, bismuth, silver, arsenic, copper and lead chlorides may be hydrolysed in stage i~ at a temperature of between 65 and 75 C~ and the hydrolysed solutio~ may be ~ooled to a temperature o~ between 15 and 25 C.
Neutralisation with Na2C03 may be carried out in the case of the antimony~depleted solution of 6tag~ iiii) to gi~e a final pH chosen between 1.2 and 2, and in the case of the ~olution of stage j) to give a fi~al pH chosen between 2.0 and 2.8.
Ths ~olar concentration of the hydrochloric acid in aqueous ~olution must be chosen in stage iii) involving ~.r~.sh;ng o~ the antimony-cont~in;n~ residue at a value o~ between 0~5 and 0O7 M
~o as to ha~e a final pH of between 1 ana 1.2, and must be chosen ~ stage jj) invol~ing the ~ h;n~ of the bismuth-cont~;n;nE residue at a value of between 0.01 and 0.1 M so as to have a final pH of betwePn 2.2 and 2.5~
- The invention will be more apparent with reference to the diaO~rams . ~ , ~2~7~i2 -- 5 ~
of the accompanying figures which are not however to be considered as limitative of the invention itself;
Figure 1 represents a block flow diagram of a process in accordance with the present invention.
Figures 2 and 3 represent block flow ~;Agr~ms illustrating the selective separation of elements in accordance with the present invention.
The mud 1 (Figure 1~, either in the wet state or precalcined in order to eliminate organic residues, is attacked at 2 with hydrochloric acid in a~eous solution 3, accompanied by aix or oxygen injection 4.
The attacked mud undergoes decantation, syphoning and possibly hot filtration at 5, by means of which a silver-rich thickened fraction 6 is separated from a silver-depleted solution 7.
The silver-rich thickened fraction 6 undergoes a second attack at 8 with hydrochloric acid in aqueous solution 9, possibly accompanied by air or oxygen injection 10~
The attacked thickened fraction is itself subjected to decantation, syphoning and possibly hot filtration at 11, in order to separate an argentierous residue 12 from an aqueous solution 13 rich in hydrochloric acid and lead chloride.
The aqueous solution is cooled and filtered at 14 in order to separate a residue rich in lead chloride 15 fxom an aqueous solution rich in hydxochloric acid 3, which is recycled to the 1st attack 2.
The argentiferous residue 12 is washed with water 16 at 17, and subsequently filtered at 18 to separate a purified argentiferous residue 19 from an aqueous solution 20 which is recycled to the 2nd attack 8.
The silver-depleted solution 7 is cooled at 21 and ~,,s ~2~ Si2 subsequently filtered at 22 to separate a residue rich in lead chloride 23 from a solution 24 containing antimony, bismuth, sil~er, arsenic, copper and lead chlorides.
3L5i2 If the mud originates from industrial lead electrore~i.ning, the residue rich in lead chloride (streams 15 and 23) can be fed to the main lead treatment cycle, or otherwise the lead can be recovered as the pure salt.
The subsequent selective separation of the elements from solution 24 is shown aiagran~atisally in Figures 2 and 3~
The solution containin2 antimony, bismuth~ silver~ arsenic, copper and lead chlorides is fed to a hydrolysis stage at 25, cooled at 26 and then filtered at 27 to thus separate a residue 28 containing a high percentage o~ antimony from an antimony-depleted solution 29 ~he residue 28 is washed at 30 with nydrochloric acid in aqueous solutio~ 31, and ~iltered at 32 to thus separate a residue 33, containing mainly antimony oxychloride~ ~rom an aqueous solution 34 ~Yhich is recycled to the hydrolysis stage 25.
- 15 The nntimony_depleted solution 29 is neutralised at 35 with Na2CO~
or another neutrAl;c;n~ agent 36, and ~iltered at 37 to separate a residue 38, which is recycled to the hydrolysis sta~e 25, from a solution 39 cont~;n;n~ bismuth~ arsenio, silver; copper~ lead ~ and antimony chlorides~in which the bismuth, arsenic and possibly the copper are present in hi~h percentage.
The antimony-depleted solution 39 is neutralised at 40 with Na2C03 or another neutr~l;s;n~ a~ent 417 and ~iltered at 42 to separate a residue 43 containing bismuth ~rom a bismuth-depleted solution 44 which is rich in copper and arsenic chloridesO
The bismuth-cont~;n;nr residue 43 is washed at 45 with hydrochloric acid in aqueous solution 46~ and filtered at 47 to separate a residue 48 containing mainly bisn~lth oxychloride, from an aqueous 1~C17~52 solution 49 which is recycled to the hydrolysis stage 25~
One example is given hereinafter with reference to the accompanying figures.
EXAM~LE
The feed is an anode mud originating from lsad electrorefining, having a weight in the wet state (w.w.) of 10000 g, and a soJids content (s.w.) of 7936 g, of composition: -S~ 4103~ % 3280.7 g Bi 8~64 % 685.7 ~
Ag 7~86 sb 623.7 g ~s 6.18 % 490.4 g Cu 2.49 % 197~6 g Pb 8.10 ,~ 642~8 g 7~.61 ,' 5~20 9 g The remainder of ~he solias content to 100% (i.e. 25~39~o) consist~
of combined o~ygen, combin~d sulphur, halogenæ~ silica and organic substances.
The 1st attack is carried out nt Goc for 3 hours with a 6 M
aqueous solution of hydrochloric acid, accompanied by air inj~ction~
The 2nd attack is carried out again at 60 C but for 2 hours with a 7,5 M aqueous solution of hydrochloric acid.
The washed argentiferous residue 19, having a w.w. of 1793 g and a s.w. of 1201 g is composed of:
Sb 0.19 % 2.3 g Bi o.o4~,b o.5 g Ag 48~61 ,~ 583.8 g As 0~0~5~ 0.4 g ~2~ 52 cu . o.ol~sb 0~1 g Pb 13.25 ~ 159.1 g The remainder of the solids content to lOKP~ comprises combined oxygen, combined sulphur, halogens, silica and organic substances.
The residue 23 containing essentially lead chloride and having a w.w. of 721 g and a s.w. of 582.2 g is composed of:
Sb lr43 % 8~3 g Bi 0~31 % 1~8 g Ag 5.41 % 31~5 1~ ~s 0.24 ~ 104 g cu o.og6% o.6 g Pb 63.07 7~ 367.2 g The chloride solution 24 to be fed to the stage for separating the metals contained in i~ and having a volume of 43.400 litres is composed of:
Sb 75.35 ~/1 3270.2 g Bi 15.79 ~1 685~3 g Ag 0.20 g/l 8.7 g .
~s 11.26 g/l 488~7 g Cu 4054 ~/1 197.0 g Pb 2.69 æ/l 116~7 g The hydrolysis is carried out at a temperature of 70 C, followed by cooling to 20Co The neutralisation 35 is carried out with a M nal pH of 1.79 whereas the w~sh;n~ in 30 attains a final pH of 1~
The residue 33 having a w.w. of ~578~7 g and a s.w. of 4300.6 g is composed of:
31 20~
Sb 66~62 % 2865.0 g Bi 0.25 %10.7 g Ag 0.092% 3.9 g As 2.30 %98.9 g Cu 0.02 % o.8 g Pb . 0.28 %12.0 g The antimony-depleted solution 39 of 235.59 litres is composed of: .
Sb o.46 ~1108.4 æ
Bi 2.21 g/l520.6 g Ag 0.0081~/11.9 g As 1.35 g/l313.0 g Cu 0.82 ~/1193.2 0 . Pb 0.26 ~/161.2 g : ~ 15 The mud stream 38 which is recycled to the hydrolysis stage~ and has a w.w. of 3179.6 g and a s.w. o~ 1012.47 g~ contains:
Sb 29.39 %297~5 g Bi . 15.13 ~153~2 g Ag ~0.277~ 2.8 g As 7-5 % 71,4 g Cu 0.~2 562.2 ~
Pb 4.27 ~43.2 g The antimony~depleted solution 39 is neutralised at 40 to a fi~l p~ ~ 2~3.
~he subsequent ~lash 44 is carried out to a final pH of 2.3.
The residue 48 having a w~w. of 2269 g and a s~w. of 926 g contains:
7~2 Sb 6~82 ~0 6301 g Bi 55~89 % 517~5 g Ag o.o630~' oO6 g As 1~05 % 9~7 g cu O~0g7% Oo9 g Pb 6~27 % 5801 g The bismuth_depleted solution 44 of 228.506 litres contains.
Sb 0.193g/1 44.1 g Bi 0.0175g/1 4~0 g A 0.0057g~1 1.3 g As 1~35 ~1 308~5 g Cu o.84 g/l 192.0 g pb 0.015 g/l 3~4 g .,
Claims (19)
1. A process for recovering metals of high commercial value from a mud, characterised in that said anode mud contains silver, arsenic, bismuth, copper, lead and antimony in the form of elements or compounds thereof and in that said process comprises the following operations;
a) attacking the mud with hydrochloric acid in aqueous solution accompanied by air or oxygen injection;
b) decanting, syphoning and, if desired, filtering the attacked mud of point a) to separate a thickened fraction rich in silver from a solution depleted thereof;
c) attacking the thickened fraction of point by with hydro-chloric acid in aqueous solution, if desired, accompanied by air or oxygen injection;
d) decanting, syphoning and,if desired,filtering the attacked thickened fraction of point 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 point d) to separate a purified argentiferous residue rich in silver chloride from an aqueous solution which is recycled to stage c);
f) cooling and filtering the solution of point b) to separate a residue rich in lead chloride from a solution containing antimony, bismuth, silver, arsenic, copper and lead chlorides;
g) cooling and filtering the aqueous solution rich in hydro-chloric acid and lead chloride of point d) to separate a residue rich in lead chloride from a solution rich in hydrochloric acid which is recycled to stage a).
a) attacking the mud with hydrochloric acid in aqueous solution accompanied by air or oxygen injection;
b) decanting, syphoning and, if desired, filtering the attacked mud of point a) to separate a thickened fraction rich in silver from a solution depleted thereof;
c) attacking the thickened fraction of point by with hydro-chloric acid in aqueous solution, if desired, accompanied by air or oxygen injection;
d) decanting, syphoning and,if desired,filtering the attacked thickened fraction of point 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 point d) to separate a purified argentiferous residue rich in silver chloride from an aqueous solution which is recycled to stage c);
f) cooling and filtering the solution of point b) to separate a residue rich in lead chloride from a solution containing antimony, bismuth, silver, arsenic, copper and lead chlorides;
g) cooling and filtering the aqueous solution rich in hydro-chloric acid and lead chloride of point d) to separate a residue rich in lead chloride from a solution rich in hydrochloric acid which is recycled to stage a).
2. A process as claimed in claim 1, wherein the solution containing antimony, bismuth, silver, arsenic, copper and lead chlorides of point f) is subjected to the following operations:
i) hydrolysing said solution;
ii) cooling and filtering the hydrolysed solution to separate a residue containing antimony from a solution depleted of said antimony, iii) washing the antimony-containing residue with hydrochloric acid in aqueous solution and then filtering to separate a residue containing antimony oxychloride from an aqueous solution which is recycled to stage i);
iiii) neutralising the depleted solution of point ii) with Na2CO3 or another neutralising agent and then filtering to separate a residue, which is recycled to stage i), from an antimony-depleted solution containing bismuth, arsenic, silver, copper, lead and antimony chlorides.
i) hydrolysing said solution;
ii) cooling and filtering the hydrolysed solution to separate a residue containing antimony from a solution depleted of said antimony, iii) washing the antimony-containing residue with hydrochloric acid in aqueous solution and then filtering to separate a residue containing antimony oxychloride from an aqueous solution which is recycled to stage i);
iiii) neutralising the depleted solution of point ii) with Na2CO3 or another neutralising agent and then filtering to separate a residue, which is recycled to stage i), from an antimony-depleted solution containing bismuth, arsenic, silver, copper, lead and antimony chlorides.
3. A process as claimed in claim 2, wherein the antimony-depleted solution containing bismuth, arsenic, silver, copper, lead and antimony chlorides of point iiii) is subjected to the following operations:
j) neutralising said solution with Na2CO3 or another neutralising agent and then filtering to separate a residue containing bismuth from a bismuth-depleted solu-tion which is rich in copper and arsenic chlorides;
jj) washing the bismuth-containing residue with hydrochloric acid and then filtering to separate a residue consisting of bismuth oxychloride from an aqueous solution which is recycled to the hydrolysis stage i).
j) neutralising said solution with Na2CO3 or another neutralising agent and then filtering to separate a residue containing bismuth from a bismuth-depleted solu-tion which is rich in copper and arsenic chlorides;
jj) washing the bismuth-containing residue with hydrochloric acid and then filtering to separate a residue consisting of bismuth oxychloride from an aqueous solution which is recycled to the hydrolysis stage i).
4. A process as claimed in claim 1, wherein the purified argentiferous residue of stage e) rich in silver chloride is converted to silver by reacting it with zinc dust, ammonium hydroxide and water.
5. A process as claimed in claim 1, wherein the purified argentiferous residue of stage e) rich in silver chloride is converted to silver by direct reduction.
6. A process as claimed in claim 1, wherein the residue rich in lead chloride of points f) and g) is fed to a main lead treatment cycle.
7. A process as claimed in claim 1, wherein the residue rich in lead chloride of points f) and g) is fed for recovery of the lead in the form of the pure salt.
8. A process as claimed in claim 1, wherein the anode mud is attacked in stage a) at a temperature of between 50° and 80°C for a period of between 0.5 and 3.0 hours.
9. A process as claimed in claim 1, wherein the thickened fraction is attacked in stage c) at a temperature of between 50° and 80°C for a period of between 0.5 and 2 hours.
10. A process as claimed in claim 1, wherein the silver-depleted solution is cooled in stage f) to a tempera-ture of between 15 and 25°C.
11. A process as claimed in claim 1 t wherein the solution rich in hydrochloric acid and lead chloride is cooled in stage g) to a temperature of between 15 and 25°C.
12. A process as claimed in claim 1, wherein the molar concentration of the hydrochloric acid in aqueous solution in the anode mud attack stage a) is chosen between 3 and 8 M.
13. A process as claimed in claim 1, wherein the molar concentration of the hydrochloric acid in aqueous solution in the thickened fraction attack stage c) is chosen between 4 and 8 M.
14. A process as claimed in claim 2, wherein the solution containing antimony, bismuth, silver, arsenic, copper and lead chlorides is hydrolysed in stage i) at a temperature of between 65 and 75°C.
15. A process as claimed in claim 2, wherein the hydrolysed solution is cooled in stage ii) to a temperature of between 15 and 25°C.
16. A process as claimed in claim 2, wherein the antimony-depleted solution is neutralised in stage iiii) with Na2CO3 to a final pH of between 1.2 and 2.
17. A process as claimed in claim 2, wherein in stage iii) involving the washing of the antimony-containing residue, the molar concentration of the hydrochloric acid in aqueous solution is chosen between 0.5 and 0.7 M in order to attain a final pH of between 1 and 1.2.
18. A process as claimed in claim 3, wherein the solution is neutralised in stage j) with Na2CO3 to a final pH of between 2.0 and 2.8.
19. A process as claimed in claim 3, wherein in stage jj) involving the washing of the bismuth-containing residue, the molar concentration of the hydrochloric acid in aqueous solution is chosen between 0.01 and 0.1 in order to attain a final pH of between 2.2 and 2.5.
Applications Claiming Priority (2)
| 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 |
| IT20565A/82 | 1982-04-05 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1207152A true CA1207152A (en) | 1986-07-08 |
Family
ID=11168868
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000425047A Expired CA1207152A (en) | 1982-04-05 | 1983-03-31 | Process for recovering metals of high commercial value contained in a mud |
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) |
Families Citing this family (8)
| 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 |
| FI115535B (en) * | 2002-10-11 | 2005-05-31 | Outokumpu Oy | A method for removing 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 |
| 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 |
| 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 |
| 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 |
Family Cites Families (8)
| 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 |
| DE490304C (en) * | 1925-07-21 | 1930-01-31 | Stanley Cochran Smith | Extraction of lead from complex lead sulfide ores and processed products |
| 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 |
| 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 BE BE0/210486A patent/BE896374A/en not_active IP Right Cessation
- 1983-04-05 DE DE19833312247 patent/DE3312247A1/en active Granted
- 1983-04-05 JP JP58058819A patent/JPS58189339A/en active Pending
- 1983-04-11 RO RO110522A patent/RO86750B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| IT8220565A0 (en) | 1982-04-05 |
| FR2524488A1 (en) | 1983-10-07 |
| JPS58189339A (en) | 1983-11-05 |
| RO86750B (en) | 1985-05-31 |
| IT1190758B (en) | 1988-02-24 |
| BE896374A (en) | 1983-10-05 |
| DE3312247A1 (en) | 1983-10-20 |
| FR2524488B1 (en) | 1986-04-25 |
| GB2118536A (en) | 1983-11-02 |
| AU566442B2 (en) | 1987-10-22 |
| RO86750A (en) | 1985-05-20 |
| GB8308032D0 (en) | 1983-04-27 |
| GB2118536B (en) | 1985-06-05 |
| DE3312247C2 (en) | 1988-08-18 |
| AU1262883A (en) | 1983-10-13 |
| DD210311A5 (en) | 1984-06-06 |
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