CN103397189B - A kind of method of recover silver and other metal from Oily wastewater - Google Patents
A kind of method of recover silver and other metal from Oily wastewater Download PDFInfo
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- CN103397189B CN103397189B CN201310317378.XA CN201310317378A CN103397189B CN 103397189 B CN103397189 B CN 103397189B CN 201310317378 A CN201310317378 A CN 201310317378A CN 103397189 B CN103397189 B CN 103397189B
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- 229910052709 silver Inorganic materials 0.000 title claims abstract description 33
- 239000004332 silver Substances 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 29
- 239000002351 wastewater Substances 0.000 title claims abstract description 24
- 239000002184 metal Substances 0.000 title claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 18
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000011084 recovery Methods 0.000 claims abstract description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 19
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000010949 copper Substances 0.000 claims abstract description 14
- 229910052802 copper Inorganic materials 0.000 claims abstract description 14
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 13
- 230000008569 process Effects 0.000 claims abstract description 10
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 9
- 238000000926 separation method Methods 0.000 claims abstract description 8
- 238000000053 physical method Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 230000035484 reaction time Effects 0.000 claims description 25
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 24
- 238000001556 precipitation Methods 0.000 claims description 21
- 238000000605 extraction Methods 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000000706 filtrate Substances 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 15
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 12
- 229910045601 alloy Inorganic materials 0.000 claims description 12
- 239000000956 alloy Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical group OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 8
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 8
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 8
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 8
- DTPQZKZONQKKSU-UHFFFAOYSA-N silver azanide silver Chemical compound [NH2-].[Ag].[Ag].[Ag+] DTPQZKZONQKKSU-UHFFFAOYSA-N 0.000 claims description 8
- CVNKFOIOZXAFBO-UHFFFAOYSA-J tin(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Sn+4] CVNKFOIOZXAFBO-UHFFFAOYSA-J 0.000 claims description 8
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 7
- 239000011521 glass Substances 0.000 claims description 7
- 239000012074 organic phase Substances 0.000 claims description 7
- 230000002829 reductive effect Effects 0.000 claims description 7
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 7
- 238000002386 leaching Methods 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 6
- DKHKTHAFPUYTLR-UHFFFAOYSA-N azane;hydrazine;hydrate Chemical compound N.O.NN DKHKTHAFPUYTLR-UHFFFAOYSA-N 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 238000012216 screening Methods 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000003350 kerosene Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 2
- 238000005649 metathesis reaction Methods 0.000 claims description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 150000002739 metals Chemical class 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract 1
- 229910001312 Amalgam (dentistry) Inorganic materials 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000000448 dental amalgam Substances 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 4
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 4
- 230000008901 benefit Effects 0.000 description 2
- -1 hydrochloric acid tindihydroxide Chemical compound 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- 229910018661 Ni(OH) Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
Classifications
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- 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
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- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a kind of method of recover silver and other metal from Oily wastewater, the method comprises physical method treatment process, nitric acid dissolve operation, Separation and Recovery silver operation, Separation and Recovery tin operation, separating copper operation, reclaims nickel operation.The present invention all adopts wet recycling process process, all metals can also be reclaimed while the shortcoming avoiding traditional recovery process high energy consumption, high pollution, realizes low-cost high-efficiency and reclaims.
Description
Technical field
The present invention relates to metals resources reclaiming field, particularly a kind of method of recover silver and other metal from Oily wastewater.
Background technology
Silver has good electroconductibility and thermal conductivity, is widely used in the fields such as photograph, electric and electronic, plating and health care industry.In silver, add the performance that other alloy element can improve silver, such as, add the hardness that copper can improve silver, reduce fusing point, improve castability, the Application Areas of copper can be further expanded.
Along with increase that is silver-colored and silver alloys consumption, annual generation Oily wastewater is also increasing, and be worth from the regeneration of resource reutilization and silver, from Oily wastewater, recover silver and other metal, have significant economic and social benefit.
Generally pyrometallurgical recovery methods is adopted from recovery at present from Oily wastewater, such as patent (CN1940099A) discloses the treatment process of waste material containing copper, precious metal and/or sludge, and the method is ripe, and processing efficiency is high, but the method energy consumption is large, and environmental pollution is more serious.
Summary of the invention
The invention provides a kind of method of recover silver and other metal from Oily wastewater, achieve silver-colored waste material low cost, the recovery of high benefit.
The present invention discloses a kind of method of recover silver and other metal from Oily wastewater, comprises the following steps:
(1) physical method treatment process: Oily wastewater is pulverized, then sieves, obtaining screen underflow with the screening of 50-70 mesh standard sieve is powdered alloy;
(2) nitric acid leaches operation: step (1) gained powdered alloy is carried out nitric acid leaching, filters, obtains leach liquor;
(3) Separation and Recovery silver operation: the leach liquor obtained to step (2) adds hydrochloric acid and reacts, and react rear filtration and has obtained silver nitride precipitation and filtrate, silver chloride reduces with reductive agent and obtains silver powder after washing, pulp;
(4) Separation and Recovery tin operation: above-mentioned all filtrate is added ammoniacal liquor, filtration after reacting completely, washing obtain tindihydroxide precipitation and filtrate, and tindihydroxide precipitation is added diluted hydrochloric acid dissolution, obtain glass putty after dissolving is complete with zinc dust precipitation;
(5) Separation and Recovery copper process: step (4) gained filtrate is carried out extraction by extraction agent Lix984 and is extracted liquid and raffinate, extraction liquid obtains copper-bath after back extraction, then copper-bath condensing crystal is obtained copper sulfate product;
(6) reclaim nickel operation: step (5) gained raffinate is added sodium hydroxide solution, filter after reacting completely and obtain nickel hydroxide;
In described step (1), pulverized by Oily wastewater, then sieve, obtaining screen underflow with the screening of 50-70 mesh standard sieve is powdered alloy, and described standard sieve is preferably 60 orders.
In described step (2), nitric acid mass concentration is (2.5-1): 1, controls to leach terminal pH value at 0.5-2, and keep certain stirring velocity, temperature of reaction is 50-90 DEG C, and the reaction times is 1-3 hour.
Main chemical reactions is as follows:
3Ag+4HNO
3→3AgNO
3+2H
2O+NO↑
3Sn+8HNO
3→3Sn(NO
3)2+2NO↑+4H
2O
3Cu+8HNO
3→3Cu(NO
3)2+2NO↑+4H
2O
3Ni+8HNO
3→3Ni(NO
3)2+2NO↑+4H
2O
In step (2), the concentration of nitric acid, consumption, temperature of reaction, stirring intensity, in the reaction times, liquid-solid ratio etc. directly can affect silver leaching rate.Test-results shows, when concentration of nitric acid is 1: 1, temperature of reaction is 60 DEG C, and reactor stirring velocity is 110 revs/min, and the reaction times is 3 hours, and liquid-solid ratio is 4: 1, silver leaching yield be 99.7% and more than.
In described step (3), hydrochloric acid add-on is 1.05-1.2 times of theoretical requirement, the slurrying of silver nitride precipitation water is transferred to 9-11 PH, reductive agent is hydrazine hydrate or hydrazine hydrate: ammoniacal liquor: water is (1-2.5): (3-5.5): the ammonia-hydrazine hydrate mixed solution of (8: 15), reduction temperature 30-90 DEG C, recovery time is 1-3 hour, and after reduction, filtration washing obtains silver powder.
Main chemical reactions is as follows:
Ag
++Cl
-→AgCl↓
4AgCl+5N
2H
4+H2O→4Ag↓+4N
2H
5Cl+N
2↑+5H
2O
In step (3), hydrochloric acid add-on, stirring intensity, temperature of reaction, reaction times, the pH value of reduction silver, reductive agent consumption, also the reaction times etc. directly can have influence on the rate of recovery of silver, test-results shows, when 1.05 times that hydrochloric acid add-on is theoretical requirement, stirring velocity is 100 revs/min, temperature of reaction is 60 DEG C, reaction times is 2 hours, the silver nitride precipitation slurrying obtained after filtration washing also adjusts pH value to 10, with hydrazine hydrate or hydrazine hydrate: ammoniacal liquor: water is that the ammonia-hydrazine hydrate mixed solution of 1: 3: 8 is as reductive agent, silver powder part rate of recovery is the highest.
In described step (4), add ammoniacal liquor and make filtrate pH value reach 2.5-3.5, used salt acid concentration is 1-5mol/L, during replacement(metathesis)reaction, keep certain stirring velocity, zinc powder consumption is 1.1-1.3 times of theoretical amount, temperature 30-90 DEG C, time 1-3 hour.
Main chemical reactions is as follows:
2H
++Sn(OH)
2→Sn
2++2H
2O
Sn
2++Zn→Sn↓+Zn
2+
In step (4), zinc powder consumption, stirring intensity, temperature of reaction, the reaction times directly has influence on the rate of recovery of tin, and test-results shows, precipitate with 5.0mol/L dissolving with hydrochloric acid tindihydroxide, go out tin with zinc dust precipitation again, zinc powder consumption is 1.1 times of theoretical amount, and stirring velocity is 80 revs/min, temperature of reaction is 60 DEG C, reaction times is 3 hours, and filtration washing obtains glass putty after drying, and the glass putty rate of recovery is the highest.
In step (5), in lix984 extraction process, organic phase composition, extraction progression, extraction form etc. all directly affect the recovery of copper, test-results shows, organic phase consists of 25%1ix984+75% sulfonated kerosene, adopt 5 stage countercurrents extractions, in solution the percentage extraction of copper reach 99.2% and more than.
In described step (6), add sodium hydroxide solution and make solution pH value reach 10.0-11.0, keep certain stirring intensity, temperature of reaction 30-90 DEG C, reaction times 30-60min.
Main chemical reactions is as follows:
Ni
2++2OH
-→Ni(OH)
2↓
In step (6), stirring intensity temperature of reaction, the reaction times directly has influence on the deposition rate of nickel, and test-results shows, stirring velocity is 120 revs/min, and temperature of reaction is 60 DEG C, and the reaction times is the deposition rate obtaining nickel for 1 hour is 99.5%.
In the present invention, all with wet processing process Oily wastewater, realize high-level efficiency, low cost, low stain reclaims.Wherein the rate of recovery of silver reaches more than 98.2%, and the tin rate of recovery reaches more than 97.5%, and copper recovery reaches more than 98.4%, and nickel recovery reaches more than 98.3%.
Accompanying drawing explanation
Accompanying drawing 1 is process flow sheet of the present invention.
Embodiment
Embodiment 1:
The first step: get 20Kg Oily wastewater and pulverize, with 60 mesh standard sieve screenings after pulverizing, obtains containing alloy for dental amalgam, after testing argentiferous 54.4% in alloy powder, copper 23.1%, tin 11.7%, nickel 10.8%.
Second step: joined in the reactor of liner tetrafluoroethylene of 100 liters containing alloy for dental amalgam by 10Kg, add 40 premium on currency, temperature of reaction is set to 60 DEG C, stirring velocity is 110 revs/min, in still, then constantly adds the nitric acid of 1: 1, carry out nitric acid leaching, reaction times controls at 2 hours, terminal PH controls 2, filters leach liquor, by leach liquor constant volume to 50L, argentiferous 107.71g/L in leach liquor after testing, copper 45.64g/L, tin 23.07g/L, nickel 21.23g/L.
3rd step: leach liquor is joined in the reactor of liner tetrafluoroethylene of 100 liters, temperature of reaction is set to 60 DEG C, and stirring velocity is 100 revs/min, and the add-on of hydrochloric acid is 1.05 times of theoretical amount, reaction times is 2 hours, then filtration washing obtains silver nitride precipitation, prepares silver chloride slurrying with water, and regulates pH value to 10 with ammoniacal liquor, with 40% hydrazine hydrate reduction silver chloride, obtain silver powder, obtain silver ingot after drying founding, the purity of silver is 99.1%.
4th step: filtrate obtained in the previous step is added ammoniacal liquor and regulate PH to 3, filtration washing obtains tindihydroxide precipitation, with the anti-molten tindihydroxide of 5mol/L hydrochloric acid, obtain tin chloride solution, join in tin chloride solution with the zinc powder of theoretical amount 1.1 times, stirring velocity is 80 revs/min, and temperature of reaction is 60 DEG C, reaction times is 3 hours, and the glass putty purity through zinc dust precipitation gained is 99.2%.
5th step: filtrate obtained in the previous step and Lix984 organic phase are extracted, wherein organic phase consists of 25%lix984+75% sulfonated kerosene, adopts 5 stage countercurrent extractions, in solution, the percentage extraction of copper reaches 99.6%, copper sulfate is obtained after the back extraction of 2.0mol/L sulfuric acid, again copper-bath condensing crystal is obtained copper sulfate product, copper sulfate purity is 99.7%.
6th step: filtrate obtained in the previous step is added sodium hydroxide solution and regulate PH to 10, stirring velocity is 120 revs/min, and temperature of reaction is 60 DEG C, and the reaction times is 1 hour, and the deposition rate obtaining nickel hydroxide is 99.5%.
Embodiment 2:
The first step: get 20Kg Oily wastewater and pulverize, with 70 mesh standard sieve screenings after pulverizing, obtains containing alloy for dental amalgam, after testing argentiferous 50.6% in alloy powder, copper 23.5%, tin 11.6%, nickel 11.8%, and other materials.
Second step: 10Kg is joined in the reactor of liner tetrafluoroethylene of 100 liters containing alloy for dental amalgam, add 40 premium on currency, temperature of reaction is set to 80 DEG C, stirring velocity is 110 revs/min, in still, then constantly adds the nitric acid of 2.5: 1, carry out nitric acid leaching, reaction times controls at 1.5 hours, terminal PH controls 1.5, filters leach liquor, by leach liquor constant volume to 50L.
3rd step: will join in the reactor of liner tetrafluoroethylene of 100 liters in leach liquor, temperature of reaction is set to 80 DEG C, stirring velocity is 100 revs/min, hydrochloric acid add-on is 1.2 times of theoretical amount, reaction times is 3 hours, then filtration washing obtains silver nitride precipitation, silver chloride slurrying is prepared with water, and regulate pH value to 10 with ammoniacal liquor, with hydrazine hydrate: ammoniacal liquor: water is the ammonia-hydrazine hydrate mixed solution Reduction of Silver Chloride of 1: 3: 8, obtain silver powder, obtain silver ingot after drying founding, the purity of silver is 99.2%.
4th step: filtrate obtained in the previous step is added ammoniacal liquor and regulate PH to 3.5, filtration washing obtains tindihydroxide precipitation, with the anti-molten tindihydroxide of 3mol/L hydrochloric acid, obtain tin chloride solution, join in tin chloride solution with the zinc powder of theoretical amount 1.2 times, stirring velocity is 80 revs/min, and temperature of reaction is 80 DEG C, reaction times is 2 hours, and the glass putty purity through zinc dust precipitation gained is 99.1%.
5th step: filtrate obtained in the previous step and Lix984 organic phase are extracted, wherein organic phase consists of 25%lix984+75% sulfonated kerosene, adopts 5 stage countercurrent extractions, in solution, the percentage extraction of copper reaches 99.6%, copper sulfate is obtained after the back extraction of 2.0mol/L sulfuric acid, again copper-bath condensing crystal is obtained copper sulfate product, copper sulfate purity is 99.7%.
6th step: filtrate obtained in the previous step is added sodium hydroxide solution and regulate PH to 11.0, stirring velocity is 120 revs/min, and temperature of reaction is 90 DEG C, and the reaction times is 50min, and the deposition rate obtaining nickel hydroxide is 99.6%.
In sum; although the specific embodiment of the present invention is to invention has been detailed description; but persons skilled in the art should be understood that; above-described embodiment is only the description to the preferred embodiments of the present invention; but not limiting the scope of the invention; persons skilled in the art are in the technical scope disclosed by the present invention, and the change that can expect easily, all within protection scope of the present invention.
Claims (9)
1. the method for recover silver and other metal from Oily wastewater, is characterized in that comprising the following steps:
(1) physical method treatment process: Oily wastewater is pulverized, then sieves, obtaining screen underflow with the screening of 50-70 mesh standard sieve is powdered alloy;
(2) nitric acid leaches operation: step (1) gained powdered alloy is carried out nitric acid leaching, filters, obtains leach liquor;
(3) Separation and Recovery silver operation: the leach liquor obtained to step (2) adds hydrochloric acid and reacts, react rear filtration and obtain silver nitride precipitation and filtrate, silver chloride obtains silver powder with reductive agent reduction filtration washing after washing, pulp, wherein hydrochloric acid add-on is 1.05-1.2 times of theoretical requirement, precipitation reaction temperature 30-90 DEG C, the precipitin reaction time is 1-3 hour, the slurrying of silver nitride precipitation water is transferred to 9-11 PH, and reductive agent is hydrazine hydrate: ammoniacal liquor: water is (1-2.5): (3-5.5): the ammonia-hydrazine hydrate mixed solution of (8-15);
(4) Separation and Recovery tin operation: above-mentioned all filtrate is added ammoniacal liquor, filtration after reacting completely, washing obtain tindihydroxide precipitation and filtrate, and tindihydroxide precipitation is added diluted hydrochloric acid dissolution, obtain glass putty after dissolving is complete with zinc dust precipitation;
(5) Separation and Recovery copper process: step (4) gained filtrate is carried out extraction by Lix984 extraction agent and is extracted liquid and raffinate, extraction liquid obtains copper-bath after back extraction, then copper-bath condensing crystal is obtained copper sulfate product;
(6) reclaim nickel operation: step (5) gained raffinate is added sodium hydroxide solution, filter after reacting completely and obtain nickel hydroxide.
2. the method for recover silver and other metal from Oily wastewater as claimed in claim 1, it is characterized in that: in described step (1), described standard sieve is 60 orders.
3. the method for recover silver and other metal from Oily wastewater as claimed in claim 1, it is characterized in that: in described step (2), nitric acid mass concentration is (2.5-1): 1, control to leach terminal pH value at 0.5-2, keep certain stirring velocity, temperature of reaction is 50-90 DEG C, and the reaction times is 1-3 hour.
4. the method for recover silver and other metal from Oily wastewater as claimed in claim 3, it is characterized in that: in step (2), temperature of reaction is 60 DEG C, and stirring velocity is 110 revs/min, and the reaction times is 3 hours.
5. the method for recover silver and other metal from Oily wastewater as claimed in claim 1, it is characterized in that: in step (3), hydrochloric acid add-on is 1.05 times of theoretical requirement, precipitation reaction temperature is 60 DEG C, the precipitin reaction time is 2 hours, the slurrying of silver nitride precipitation water is transferred to 10 PH, with hydrazine hydrate: ammoniacal liquor: water is that the ammonia-hydrazine hydrate mixed solution of 1:3:8 is as reductive agent.
6. the method for recover silver and other metal from Oily wastewater as claimed in claim 1, it is characterized in that: in described step (4), adding ammoniacal liquor makes filtrate pH value reach 2.5-3.5, used salt acid concentration is 1-5mol/L, during replacement(metathesis)reaction, keep certain stirring velocity, zinc powder consumption is 1.1-1.3 times of theoretical amount, temperature 30-90 DEG C, time 1-3 hour.
7. the method for recover silver and other metal from Oily wastewater as claimed in claim 6, it is characterized in that: in step (4), regulate filtrate pH value to 3.0 with ammoniacal liquor, used salt acid concentration is 5mol/L, zinc powder consumption is 1.1 times of theoretical amount, and stirring velocity is 80 revs/min, and temperature of reaction is 60 DEG C, reaction times is 3 hours, and filtration washing obtains glass putty after drying.
8. the method for recover silver and other metal from Oily wastewater as claimed in claim 1, is characterized in that: in step (5), and organic phase consists of 25%lix984+75% sulfonated kerosene, adopts 5 stage countercurrent extractions.
9. the method for recover silver and other metal from Oily wastewater as claimed in claim 1, it is characterized in that: in described step (6), adding sodium hydroxide solution makes solution pH value reach 10.0-11.0, keep certain stirring intensity, temperature of reaction 30-90 DEG C, reaction times 30-60min.
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| CN106702166A (en) * | 2017-02-06 | 2017-05-24 | 温州中希电工合金有限公司 | Method for recycling silver in high oil-bearing sludge |
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| CN108480647B (en) * | 2018-01-23 | 2022-01-18 | 珠海纳金科技有限公司 | Recycling method of nano-silver particle waste liquid |
| CN109536726A (en) * | 2019-01-14 | 2019-03-29 | 北京科技大学 | A kind of recovery method of argentiferous dead catalyst |
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| CN111455182A (en) * | 2020-04-24 | 2020-07-28 | 金川集团股份有限公司 | Method for separating and extracting silver, palladium and ruthenium from waste catalyst |
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| CN101126129A (en) * | 2007-09-07 | 2008-02-20 | 金川集团有限公司 | Method for removing copper from nickel chloride leachate |
| CN102775197B (en) * | 2012-08-13 | 2014-06-11 | 深圳市危险废物处理站有限公司 | Method for preparing fertilizer-grade ammonium nitrate concentrated solution by use of mother liquid after immersion tin of tin-stripping waste liquid of circuit board |
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