CN115181857B - Method for recovering copper, zinc and cadmium from copper ash leaching solution - Google Patents
Method for recovering copper, zinc and cadmium from copper ash leaching solution Download PDFInfo
- Publication number
- CN115181857B CN115181857B CN202210825361.4A CN202210825361A CN115181857B CN 115181857 B CN115181857 B CN 115181857B CN 202210825361 A CN202210825361 A CN 202210825361A CN 115181857 B CN115181857 B CN 115181857B
- Authority
- CN
- China
- Prior art keywords
- cadmium
- copper
- zinc
- organic phase
- extraction
- 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.)
- Active
Links
- 229910052793 cadmium Inorganic materials 0.000 title claims abstract description 97
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 95
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 94
- 239000010949 copper Substances 0.000 title claims abstract description 94
- 239000011701 zinc Substances 0.000 title claims abstract description 91
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 84
- 238000000034 method Methods 0.000 title claims abstract description 33
- 238000002386 leaching Methods 0.000 title claims abstract description 31
- 239000012074 organic phase Substances 0.000 claims abstract description 73
- 238000000605 extraction Methods 0.000 claims abstract description 72
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000002184 metal Substances 0.000 claims abstract description 27
- 229910052751 metal Inorganic materials 0.000 claims abstract description 27
- GLRNFEKUXLEZRE-UHFFFAOYSA-N [Cd].[Cu].[Zn] Chemical compound [Cd].[Cu].[Zn] GLRNFEKUXLEZRE-UHFFFAOYSA-N 0.000 claims abstract description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 238000011084 recovery Methods 0.000 claims abstract description 13
- 230000001105 regulatory effect Effects 0.000 claims abstract description 10
- PLLZRTNVEXYBNA-UHFFFAOYSA-L cadmium hydroxide Chemical compound [OH-].[OH-].[Cd+2] PLLZRTNVEXYBNA-UHFFFAOYSA-L 0.000 claims abstract description 8
- 150000002739 metals Chemical class 0.000 claims abstract description 7
- 239000002244 precipitate Substances 0.000 claims abstract description 6
- 230000001276 controlling effect Effects 0.000 claims abstract description 5
- 239000012452 mother liquor Substances 0.000 claims abstract description 5
- 239000000460 chlorine Substances 0.000 claims description 14
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 13
- 229910052801 chlorine Inorganic materials 0.000 claims description 13
- 238000007127 saponification reaction Methods 0.000 claims description 10
- 239000004071 soot Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 6
- 238000000658 coextraction Methods 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- 239000003085 diluting agent Substances 0.000 claims description 4
- 239000012071 phase Substances 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 4
- 229960001763 zinc sulfate Drugs 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 125000003158 alcohol group Chemical group 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical group 0.000 claims description 2
- 238000005660 chlorination reaction Methods 0.000 claims description 2
- 239000010815 organic waste Substances 0.000 claims description 2
- 150000003141 primary amines Chemical group 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- 150000003512 tertiary amines Chemical class 0.000 claims description 2
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 claims 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims 1
- 239000000284 extract Substances 0.000 abstract description 6
- 238000004064 recycling Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 abstract 5
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 239000010413 mother solution Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 14
- 238000000926 separation method Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- RZLVQBNCHSJZPX-UHFFFAOYSA-L zinc sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Zn+2].[O-]S([O-])(=O)=O RZLVQBNCHSJZPX-UHFFFAOYSA-L 0.000 description 4
- 238000004070 electrodeposition Methods 0.000 description 3
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000003849 aromatic solvent Substances 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 102000003712 Complement factor B Human genes 0.000 description 1
- 108090000056 Complement factor B Proteins 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- PLZFHNWCKKPCMI-UHFFFAOYSA-N cadmium copper Chemical compound [Cu].[Cd] PLZFHNWCKKPCMI-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000011549 displacement method Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000009853 pyrometallurgy Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000002699 waste material 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
- 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
- C22B7/02—Working-up flue dust
-
- 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
-
- 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
- C22B17/00—Obtaining cadmium
- C22B17/04—Obtaining cadmium 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
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
-
- 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
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/30—Obtaining zinc or zinc oxide from metallic residues or scraps
-
- 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
- C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
- C22B3/3846—Phosphoric acid, e.g. (O)P(OH)3
-
- 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
-
- 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
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for recycling copper zinc cadmium from copper ash leaching solution, which adopts a cyclic extraction flow, extracts copper, extracts zinc, co-extracts and extracts cadmium, and concretely comprises the following steps: regulating the pH value of the copper ash leaching solution to 1-2 for copper extraction, and obtaining copper extraction residual liquid and a loaded copper organic phase; controlling the zinc concentration in the loaded organic phase, extracting zinc in the copper-extracted raffinate, and then co-extracting the zinc-extracted raffinate to obtain a metal-loaded organic phase and an externally discharged raffinate, wherein the metal-loaded organic phase is subjected to sulfuric acid back extraction to obtain a copper-zinc-cadmium enriched liquid; extracting cadmium from the copper-zinc-cadmium enriched solution to obtain a loaded cadmium organic phase and a cadmium extraction residual solution; the cadmium-loaded organic phase is back extracted by sodium hydroxide to obtain cadmium hydroxide precipitate, and the cadmium hydroxide precipitate and mother liquor are filtered and separated; the copper zinc cadmium contained in the mother solution and the cadmium extraction raffinate is merged into the copper ash leaching solution to return to the main process for recovering metals, and the metal recovery rate is high and the loss rate of each metal is less than or equal to 0.05 percent.
Description
Technical Field
The invention relates to the field of metal separation, in particular to a method for recovering copper, zinc and cadmium from a polluted acid leaching solution of copper soot.
Background
During the copper pyrometallurgy process, a large amount of copper soot and flue gas water absorption liquid, known as dirty acid, is produced. Wherein the copper ash contains copper 3.3-11.9%, zinc 1.6-9.8%, cadmium 0.3-1.9%, the dirty acid contains copper 0.3-2 g/L, zinc 0.25-1.5 g/L, cadmium 0.01-0.5 g/L and sulfuric acid 50-200 g/L. At present, enterprises often adopt waste acid to leach copper ash to obtain sulfuric acid system leaching solution containing copper, zinc and cadmium, and then the copper, zinc and cadmium are recovered from the leaching solution. The method for recovering copper, zinc and cadmium from the copper-zinc-cadmium-containing leaching solution can be an extraction method, an adsorption method, a vulcanization method, a displacement method, an electrodeposition method, a combination method thereof and the like.
As in CN202110699436.4, a method for recovering arsenic and valuable metals from arsenic-containing ash is disclosed, which comprises introducing hydrogen sulfide gas into the leaching solution containing copper and zinc to obtain copper-rich slag and zinc-containing solution, adding zinc powder into the zinc-containing solution to displace copper and cadmium simultaneously, and concentrating and crystallizing the purified zinc solution to obtain zinc sulfate heptahydrate product. The cadmium recovered by the method contains copper, the purity of the cadmium product is not high, and copper loss is caused. According to the method, a cadmium-containing zinc-rich copper solution is subjected to turbulent electrodeposition to obtain cathode copper and a cadmium-containing zinc-poor copper solution, the filtrate obtained after the copper powder is added into the cadmium-containing zinc-poor copper solution and filtered is subjected to turbulent electrodeposition to obtain coarse copper powder and zinc-rich cadmium solution with copper content not higher than 2g/L, zinc powder with cadmium mass of 50% is added into the zinc-containing cadmium-rich solution to replace cadmium, cadmium sponge is obtained, and alkali fusion casting ingot is carried out on the cadmium sponge to obtain coarse cadmium ingot. The method has strict requirements on copper content when cadmium is recovered, otherwise, copper in the crude cadmium ingot exceeds standard. For example, CN201210169116.9 discloses a method for separating and enriching copper, cadmium and zinc in copper-cadmium slag, which comprises extracting copper from leaching solution, and then adsorbing cadmium by adsorption material, wherein the pH of the solution is required to be 4-6 when cadmium is adsorbed.
Disclosure of Invention
The invention aims to provide a method for recycling copper, zinc and cadmium, which can improve the metal recycling rate and obtain a pure cadmium product.
The invention is realized by adopting the following technical scheme:
a method for recovering copper zinc cadmium from copper soot leaching solution, comprising the following steps:
and (2) recovering copper in the step (1): regulating the pH value of the copper ash leaching solution to 1-2 for copper extraction, and obtaining copper extraction residual liquid and a loaded copper organic phase; carrying out sulfuric acid back extraction on the loaded copper organic phase to obtain a copper sulfate solution;
and (2) recovering zinc: adjusting the pH value of the copper extraction raffinate to 1.2-1.5 for extracting zinc, controlling the concentration of zinc in the loaded organic phase to obtain zinc extraction raffinate and a loaded zinc organic phase, and carrying out sulfuric acid back extraction on the loaded zinc organic phase to obtain a zinc sulfate solution; wherein the zinc concentration in the organic phase is controlled according to the following formula:
P 1 ＝A 1 ×B 1 ×M 1
A 1 ＝(C 1 ×η)÷2
p in the formula 1 Is the concentration of zinc in the organic phase, g/L, A 1 The saturated capacity, mol/L and B of zinc extracted by the theory of zinc extractant 1 The operation capacity coefficient of the zinc extractant is 75-90 percent, M 1 65g/mol of zinc molar mass, C 1 The molar concentration of the zinc extractant is mol/L, and eta is the saponification rate of the zinc extractant;
and (3) metal enrichment: regulating the pH value of the zinc extraction raffinate to 1.5-2.0 for co-extraction to obtain a metal-loaded organic phase and an outward-discharged raffinate, and carrying out sulfuric acid back extraction on the metal-loaded organic phase to obtain a copper-zinc-cadmium enrichment solution;
and (4) recovering cadmium: extracting cadmium from the copper-zinc-cadmium enriched solution to obtain a cadmium-loaded organic phase and a cadmium extraction residual solution; the cadmium-loaded organic phase is back extracted by sodium hydroxide to obtain cadmium hydroxide precipitate, and the cadmium hydroxide precipitate and mother liquor are filtered and separated; the mother liquor and the raffinate of cadmium are merged into the copper ash leaching liquor, and the copper ash leaching liquor returns to the main process to recover metals.
The cadmium extraction process comprises the following steps:
a) Chlorination: the chlorine receiver, the phase regulator and the diluent are mixed according to the volume ratio of (5-20): (10-20): (60-85) preparing an organic phase, then chloridizing with hydrochloric acid, and separating out a chloridized organic phase and waste acid; the chlorine receiver is primary amine, tertiary amine or quaternary ammonium salt, the phase regulator is alcohol or ether, and the diluent is alkane solvent oil;
b) Washing: washing the chlorinated organic phase with pure water, and separating the washed chlorinated organic phase;
c) Extracting cadmium: extracting the washed chloridized organic phase and sulfuric acid medium solution containing zinc and cadmium in proportion, and controlling the concentration of cadmium in the loaded organic phase to obtain low-cadmium raffinate and a loaded cadmium organic phase; wherein the cadmium concentration in the organic phase is controlled according to the following formula:
P 2 ＝A 2 ×B 2 ×M 2
A 2 ＝α×C 2
p in the formula 2 For loading cadmium concentration in organic phase, g/L, A 2 Saturated capacity, mol/L, B of cadmium extracted by chlorine receiver theory 2 The extraction operation coefficient of the chlorine receiver is 35-45%, M 2 Cadmium molar mass, 112g/mol, alpha as extraction coefficient, 1/3, C 2 Is the mole concentration of the chlorine receiver and the mole/L.
In the method for recovering copper zinc cadmium from the copper soot leaching solution, in particular to the method in the step (1), the copper extractant is one or more of ZJ988 series copper extractants, and the volume percentage of the copper extractant in an organic phase is 20% -40%.
In the method for recovering copper, zinc and cadmium from the copper soot leaching solution, in particular, in the step (2), the zinc extractant is P204 or P507, the volume percentage of the zinc extractant in an organic phase is 5-15%, and the saponification rate of the extractant is 40-60%.
In the method for recovering copper, zinc and cadmium from the copper ash leaching solution, in particular, in the step (3), the extractant is P204 or P507, the volume percentage of the extractant in an organic phase is 5-15%, the saponification rate of the extractant is 40-60%, and Cu in the externally discharged raffinate is controlled to be less than or equal to 0.5mg/L, zn and less than or equal to 1.0mg/L, cd and less than or equal to 0.05mg/L during extraction.
The method for recovering copper, zinc and cadmium from the copper ash leaching solution has the following beneficial effects:
(1) The invention adopts a circulating extraction flow, copper extraction, zinc extraction, co-extraction and cadmium extraction, and the copper zinc cadmium contained in the raffinate after cadmium extraction is incorporated into the copper ash leaching liquid to return to the main flow for recovering metals, thereby avoiding metal loss, and the loss rate of each metal is less than or equal to 0.05 percent.
(2) When zinc is recovered, the operation coefficient is controlled to be 75% -90% when the zinc extractant extracts zinc, and a near-saturation extraction method is adopted, so that cadmium co-extraction is avoided, and a pure zinc product is obtained; when cadmium is recovered, the operation coefficient is controlled to be 35-45% when the chlorine receiver extracts cadmium, namely, a low-capacity extraction method is adopted, so that zinc co-extraction can be avoided, and a pure cadmium product is obtained.
(2) The pH value of the solution is not required to be regulated when cadmium is extracted, and only the organic phase is required to be chlorinated in advance, so that Cl is prevented from being introduced into the solution - The raffinate can be maintained to be a sulfuric acid system, and the copper, zinc and cadmium in the raffinate can be recovered in the main process.
(3) The copper, zinc and cadmium in the zinc raffinate are enriched by adopting a co-extraction method, so that not only is the metal enriched, but also the metal in the raffinate can meet the emission standard of industrial pollutants of copper, nickel and cobalt of GB 25467-2010.
The invention is further described below with reference to the drawings and detailed description.
Drawings
FIG. 1 is a flow chart of the copper-zinc-cadmium recovery process of the invention.
Detailed Description
The present invention will be described in detail with reference to the following examples. The following examples will assist those skilled in the art in further understanding the present invention, but are not intended to limit the invention in any way.
Example 1: the copper ash leaching solution contains 21225mg/L of copper, 4380mg/L of zinc and 985mg/L of cadmium, the pH value is regulated to 1.3, the three-stage countercurrent extraction is carried out by 25% ZJ988N+75%260# solvent oil according to O/A=2/1, the copper raffinate and the loaded copper organic phase are obtained, and the loaded copper organic phase is carried out by 200g/L sulfuric acid according to O/A=4/1, and the copper sulfate stripping solution is obtained. Regulating the pH value of the copper raffinate to 1.5, carrying out four-stage countercurrent extraction by using 10% P204+90%260# solvent oil with 50% saponification rate according to O/A=1/1 to obtain zinc raffinate and a zinc-loaded organic phase, and carrying out two-stage countercurrent stripping on the zinc-loaded organic phase by using 100g/L sulfuric acid according to O/A=2/1 to obtain zinc sulfate strip liquor. The zinc raffinate is subjected to two-stage countercurrent extraction by using 10% P204+90%260# solvent oil with 50% saponification rate according to O/A=1/2 to obtain an external raffinate and a metal-loaded organic phase, and the metal-loaded organic phase is subjected to two-stage countercurrent extraction by using 100g/L sulfuric acid according to O/A=10/1 to obtain a copper-zinc-cadmium enriched liquid. And (3) carrying out four-stage countercurrent extraction on the copper zinc cadmium enrichment liquid by using chlorinated 20% N235+15% isooctyl alcohol+65% 260# low aromatic solvent oil according to O/A=3/1 to obtain a cadmium raffinate and a cadmium-loaded organic phase, returning the cadmium raffinate into the copper soot leaching liquid to the main process for recovering metals, and carrying out two-stage countercurrent back extraction on the cadmium-loaded organic phase by using 40g/L sodium hydroxide solution according to O/A=1/1 to obtain cadmium hydroxide precipitation. The specific data are shown in Table 1.
Comparative example 1: comparative example 1 differs from example 1 in that the four-stage countercurrent extraction at O/a=3.5/1, i.e. the control of the chlorine receiver extraction operating factor B, is carried out in the recovery of cadmium extraction 2 After extraction, extraction separation coefficient β=33 Cd/Zn Down to 9362.
TABLE 1 recovery Effect of example 1
TABLE 2 recovery Effect of comparative example 1
TABLE 3 control parameters of Zinc concentration in loaded organic phase when Zinc is recovered from case 1 and comparative example 1
| Name of the name | B 1 | P 1 (g/L) | η | C 1 (mol/L) | M 1 (g/mol) | Extraction separation coefficient beta Zn/Cd |
| Case 1 | 77％ | 3.768 | 50％ | 0.3 | 65 | 3021 |
| Comparative example 1 | 77％ | 3.768 | 50％ | 0.3 | 65 | 3021 |
TABLE 4 control parameters of cadmium concentration in loaded organic phase during recovery of cadmium for case 1 and comparative example 1
| Name of the name | B 2 | P 2 (g/L) | α | C 2 (mol/L) | M 2 (g/mol) | Extraction separation coefficient beta Cd/Zn |
| Case 1 | 38％ | 6.417 | 33％ | 0.45 | 112 | 13389 |
| Comparative example 1 | 33％ | 5.502 | 33％ | 0.45 | 112 | 9362 |
Example 2: copper ash leaching liquid contains copper 22695mg/L, zinc 6743mg/L and cadmium 438mg/L, the pH value is regulated to 1.2, 25% ZJ988N+75%260# solvent oil is used for three-stage countercurrent extraction according to O/A=2/1, a copper raffinate and a copper loaded organic phase are obtained, and 200g/L sulfuric acid is used for four-stage countercurrent back extraction according to O/A=4/1 of the copper loaded organic phase, so that copper sulfate back extraction liquid is obtained. Regulating the pH value of the raffinate to 1.4, carrying out four-stage countercurrent extraction by using 10% P204+90%260# solvent oil with 50% saponification rate according to O/A=1.4/1 to obtain raffinate and a zinc-loaded organic phase, and carrying out two-stage countercurrent stripping on the zinc-loaded organic phase by using 100g/L sulfuric acid according to O/A=2/1 to obtain zinc sulfate strip liquor. The zinc raffinate is subjected to two-stage countercurrent extraction by using 10% P204+90%260# solvent oil with 50% saponification rate according to O/A=1/3 to obtain an external raffinate and a metal-loaded organic phase, and the metal-loaded organic phase is subjected to two-stage countercurrent extraction by using 100g/L sulfuric acid according to O/A=10/1 to obtain a copper-zinc-cadmium enriched liquid. And (3) carrying out four-stage countercurrent extraction on the copper zinc cadmium enrichment liquid by using chlorinated 20% N235+15% isooctyl alcohol+65% 260# low aromatic solvent oil according to O/A=2/1 to obtain a cadmium raffinate and a cadmium-loaded organic phase, returning the cadmium raffinate into the copper soot leaching liquid to the main process for recovering metals, and carrying out two-stage countercurrent back extraction on the cadmium-loaded organic phase by using 40g/L sodium hydroxide solution according to O/A=1/1 to obtain cadmium hydroxide precipitation. The specific data are shown in Table 5.
Comparative example 2: comparative example 2 differs from example 2 in that the four-stage countercurrent extraction at O/a=2/1 is performed in the recovery of zinc extraction, i.e. the extraction operation coefficient B of the zinc extractant is controlled 1 After extraction, extraction separation coefficient β=64 Zn/Cd Down to 798.
The extraction operation coefficient B of the chlorine receiver is controlled according to the four-stage countercurrent extraction of O/A=1.5/1 during the recovery of cadmium 2 After extraction, extraction separation coefficient β=47 Cd/Zn Down to 1422.
TABLE 5 recovery effect in example 2
TABLE 6 recovery Effect in comparative example 2
TABLE 7 control parameters of Zinc concentration in loaded organic phase during Zinc recovery from case 2 and comparative example 2
| Name of the name | B 1 | P 1 (g/L) | η | C 1 (mol/L) | M 1 (g/mol) | Extraction separation coefficient beta Zn/Cd |
| Case 2 | 90％ | 4.392 | 50％ | 0.3 | 65 | 2256 |
| Comparative example 2 | 64％ | 3.13 | 50％ | 0.3 | 65 | 798 |
TABLE 8 control parameters of cadmium concentration in loaded organic phase for cadmium recovery for case 2 and comparative example 2
| Name of the name | B 2 | P 2 (g/L) | α | C 2 (mol/L) | M 2 (g/mol) | Extraction separation coefficient beta Cd/Zn |
| Case 2 | 39％ | 6.533 | 33％ | 0.45 | 112 | 85079 |
| Comparative example 2 | 47％ | 7.855 | 33％ | 0.45 | 112 | 1422 |
Claims (4)
1. A method for recovering copper zinc cadmium from copper ash leaching solution, which is characterized by comprising the following steps:
(1) Recovering copper: regulating the pH value of the copper ash leaching solution to 1-2 for copper extraction, and obtaining copper extraction residual liquid and a loaded copper organic phase; carrying out sulfuric acid back extraction on the loaded copper organic phase to obtain a copper sulfate solution;
(2) Recovering zinc: adjusting the pH value of the copper extraction raffinate to 1.2-1.5 for extracting zinc, controlling the concentration of zinc in the loaded organic phase to obtain zinc extraction raffinate and a loaded zinc organic phase, and carrying out sulfuric acid back extraction on the loaded zinc organic phase to obtain a zinc sulfate solution; wherein the zinc concentration in the organic phase is controlled according to the following formula:
P 1 ＝A 1 ×B 1 ×M 1
A 1 ＝(C 1 ×η)÷2
p in the formula 1 Is the concentration of zinc in the organic phase, g/L, A 1 The saturated capacity, mol/L and B of zinc extracted by the theory of zinc extractant 1 The operation capacity coefficient of the zinc extractant is 75-90 percent, M 1 65g/mol of zinc molar mass, C 1 The molar concentration of the zinc extractant is mol/L, and eta is the saponification rate of the zinc extractant;
(3) Metal enrichment: regulating the pH value of the zinc extraction raffinate to 1.5-2.0 for co-extraction to obtain a metal-loaded organic phase and an outward-discharged raffinate, and carrying out sulfuric acid back extraction on the metal-loaded organic phase to obtain a copper-zinc-cadmium enrichment solution;
(4) And (3) cadmium recovery: extracting cadmium from the copper-zinc-cadmium enriched solution to obtain a cadmium-loaded organic phase and a cadmium extraction residual solution; the cadmium-loaded organic phase is back extracted by sodium hydroxide to obtain cadmium hydroxide precipitate, and the cadmium hydroxide precipitate and mother liquor are filtered and separated; the mother liquor and the raffinate of the cadmium extraction are merged into copper ash leaching liquor, and the copper ash leaching liquor returns to the main process to recover metals;
the cadmium extraction process comprises the following steps:
a) Chlorination: the chlorine receiver, the phase regulator and the diluent are mixed according to the volume ratio of (5-20): (10-20): (60-85) preparing an organic phase, then chloridizing with hydrochloric acid, and separating out a chloridized organic phase and waste acid; the chlorine receiver is primary amine, tertiary amine or quaternary ammonium salt, the phase regulator is alcohol or ether, and the diluent is alkane solvent oil;
b) Washing: washing the chlorinated organic phase with pure water, and separating the washed chlorinated organic phase;
c) Extracting cadmium: extracting the washed chloridized organic phase and sulfuric acid medium solution containing zinc and cadmium in proportion, and controlling the concentration of cadmium in the loaded organic phase to obtain low-cadmium raffinate and a loaded cadmium organic phase; wherein the cadmium concentration in the organic phase is controlled according to the following formula:
P 2 ＝A 2 ×B 2 ×M 2
A 2 ＝α×C 2
p in the formula 2 For loading cadmium concentration in organic phase, g/L, A 2 Saturated capacity, mol/L, B of cadmium extracted by chlorine receiver theory 2 The extraction operation coefficient of the chlorine receiver is 35-45%, M 2 Cadmium molar mass, 112g/mol, alpha is extraction coefficient 1/3, C 2 Is the mole concentration of the chlorine receiver and the mole/L.
2. The method for recovering copper zinc and cadmium from copper soot leaching solution according to claim 1, wherein in the step (1), the copper extractant is one or more of ZJ988 series copper extractants, and the volume percentage of the copper extractant in the organic phase is 20% -40%.
3. The method for recovering copper, zinc and cadmium from copper soot leaching solution according to claim 1, wherein in the step (2), the zinc extractant is P204 or P507, the volume percentage of the extractant in the organic phase is 5% -15%, and the saponification rate of the extractant is 40% -60%.
4. The method for recovering copper, zinc and cadmium from copper soot leaching solution according to claim 1, wherein in the step (3), the extractant is P204 or P507, the volume percentage of the extractant in the organic phase is 5-15%, the saponification rate of the extractant is 40-60%, and Cu in the externally discharged raffinate is controlled to be less than or equal to 0.5mg/L, zn and less than or equal to 1.0mg/L, cd and less than or equal to 0.05mg/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210825361.4A CN115181857B (en) | 2022-07-14 | 2022-07-14 | Method for recovering copper, zinc and cadmium from copper ash leaching solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210825361.4A CN115181857B (en) | 2022-07-14 | 2022-07-14 | Method for recovering copper, zinc and cadmium from copper ash leaching solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115181857A CN115181857A (en) | 2022-10-14 |
| CN115181857B true CN115181857B (en) | 2023-12-22 |
Family
ID=83518959
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210825361.4A Active CN115181857B (en) | 2022-07-14 | 2022-07-14 | Method for recovering copper, zinc and cadmium from copper ash leaching solution |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115181857B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116395779B (en) * | 2023-06-07 | 2023-09-26 | 赛恩斯环保股份有限公司 | Method for inhibiting cadmium and extracting fluorine from waste acid vulcanized liquid |
| CN118241047B (en) * | 2024-03-28 | 2024-11-29 | 科立鑫(阳江)新能源有限公司 | A process for separating nickel and cobalt from cobalt raffinate |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008266774A (en) * | 2007-03-29 | 2008-11-06 | Nikko Kinzoku Kk | Zinc recovery method |
| CN102212701A (en) * | 2011-05-31 | 2011-10-12 | 江西南城鑫业环保处置有限公司 | Method for recovering metallic copper and zinc from copper smelting ash |
| KR20120055365A (en) * | 2010-11-23 | 2012-05-31 | 한국지질자원연구원 | Metal extracting and separating method of cu, zn, cd and ni from the leach liquor of the secondary metal resources by solvent extraction |
| CN108977669A (en) * | 2018-09-13 | 2018-12-11 | 中南大学 | A method of cadmium in high-concentration sulfuric acid cobalt liquor is removed in depth and recycles cadmium |
| CN109777958A (en) * | 2019-01-02 | 2019-05-21 | 江西思远再生资源有限公司 | A kind of technique of the comprehensive reutilization valuable metal from material containing zinc |
| CN112080641A (en) * | 2020-09-25 | 2020-12-15 | 郴州市裕弘冶化环保设备有限公司 | Method for comprehensively recovering valuable metals from byproduct copper sludge of zinc hydrometallurgy |
| CN112981121A (en) * | 2021-02-05 | 2021-06-18 | 江西思远再生资源有限公司 | Method for treating cadmium-containing waste residue and preparing high-purity metal cadmium by precipitation method |
| CN112981104A (en) * | 2021-02-05 | 2021-06-18 | 桐乡市思远环保科技有限公司 | Method for treating cadmium-containing waste residues and recovering metal cadmium |
| CN115141940A (en) * | 2022-07-14 | 2022-10-04 | 赛恩斯环保股份有限公司 | Method for separating zinc and cadmium from sulfuric acid medium |
-
2022
- 2022-07-14 CN CN202210825361.4A patent/CN115181857B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008266774A (en) * | 2007-03-29 | 2008-11-06 | Nikko Kinzoku Kk | Zinc recovery method |
| KR20120055365A (en) * | 2010-11-23 | 2012-05-31 | 한국지질자원연구원 | Metal extracting and separating method of cu, zn, cd and ni from the leach liquor of the secondary metal resources by solvent extraction |
| CN102212701A (en) * | 2011-05-31 | 2011-10-12 | 江西南城鑫业环保处置有限公司 | Method for recovering metallic copper and zinc from copper smelting ash |
| CN108977669A (en) * | 2018-09-13 | 2018-12-11 | 中南大学 | A method of cadmium in high-concentration sulfuric acid cobalt liquor is removed in depth and recycles cadmium |
| CN109777958A (en) * | 2019-01-02 | 2019-05-21 | 江西思远再生资源有限公司 | A kind of technique of the comprehensive reutilization valuable metal from material containing zinc |
| CN112080641A (en) * | 2020-09-25 | 2020-12-15 | 郴州市裕弘冶化环保设备有限公司 | Method for comprehensively recovering valuable metals from byproduct copper sludge of zinc hydrometallurgy |
| CN112981121A (en) * | 2021-02-05 | 2021-06-18 | 江西思远再生资源有限公司 | Method for treating cadmium-containing waste residue and preparing high-purity metal cadmium by precipitation method |
| CN112981104A (en) * | 2021-02-05 | 2021-06-18 | 桐乡市思远环保科技有限公司 | Method for treating cadmium-containing waste residues and recovering metal cadmium |
| CN115141940A (en) * | 2022-07-14 | 2022-10-04 | 赛恩斯环保股份有限公司 | Method for separating zinc and cadmium from sulfuric acid medium |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115181857A (en) | 2022-10-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN115181857B (en) | Method for recovering copper, zinc and cadmium from copper ash leaching solution | |
| US11459636B2 (en) | Method and system for comprehensive recovery and utilization of copper-nickel sulfide ore | |
| EP1159461B1 (en) | Recovery of nickel and cobalt from ore | |
| NO158106B (en) | PROCEDURE FOR TREATING Aqueous SOLUTION CONTAINING Precious Metals and Undesirable Elements. | |
| KR102041294B1 (en) | Method for recovering covalt from solution comprising covalt, nickel and iron | |
| CN101798639B (en) | Method for recovering indium from indium-containing neutralized dregs directly leached from zinc concentrate | |
| CN112410568A (en) | A kind of method for preparing cobalt ferrite from cobalt-containing slag | |
| CN112575200A (en) | Method for replacing and separating copper, zinc and manganese in inverse copper-manganese solution by using sulfide precipitation controlled electric position | |
| CN114058845A (en) | Method for combined extraction in nickel chloride solution by utilizing P204 and N235 | |
| US11560609B2 (en) | Method of extracting metals from polymetallic sulphide ores or concentrates | |
| CN111826525B (en) | Method for producing metal cobalt by sulfuric acid system electrodeposition | |
| CN115141940B (en) | Method for separating zinc and cadmium from sulfuric acid medium | |
| CN116397102A (en) | Method for harmless recovery of copper and germanium from high-iron high-copper solution | |
| CN113462898B (en) | Oxygen pressure leaching zinc smelting purification impurity removal process | |
| CN109280772B (en) | Method for leaching and gradient separating enriched antimony, bismuth and arsenic from copper anode slime | |
| Bautista | Processing to obtain high-purity gallium | |
| CN103031444B (en) | Method for recovering indium from indium-contained sulfuric acid solution and copper ash | |
| CN116574908B (en) | Process for jointly recycling zinc and indium by means of open-circuit impurity removal of electrolyte in zinc smelting process | |
| CN109943720B (en) | Method for comprehensively recovering zinc and indium from zinc-containing solution with low indium content and high iron content | |
| CN102234722A (en) | Process for separating copper in nickel-cobalt-copper system by solvent extraction method | |
| US20150104362A1 (en) | Methods and apparatus for recovering molybdenum in uranium in-situ recovery process | |
| CN116607173A (en) | Production method of electrodeposited nickel chloride | |
| Gotfryd et al. | The selective recovery of cadmium (II) from sulfate solutions by a counter-current extraction–stripping process using a mixture of diisopropylsalicylic acid and Cyanex® 471X | |
| CN108486390B (en) | Process for separating germanium and gallium from germanium and gallium material | |
| JP2010248043A (en) | Method for refining aqueous nickel chloride solution |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |