CN112520790A - Method for producing cobalt sulfate by using organic cobalt slag of zinc smelting plant - Google Patents
Method for producing cobalt sulfate by using organic cobalt slag of zinc smelting plant Download PDFInfo
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 239000010941 cobalt Substances 0.000 title claims abstract description 89
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 89
- 239000002893 slag Substances 0.000 title claims abstract description 88
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 57
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 title claims abstract description 53
- 229910000361 cobalt sulfate Inorganic materials 0.000 title claims abstract description 46
- 229940044175 cobalt sulfate Drugs 0.000 title claims abstract description 46
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 42
- 239000011701 zinc Substances 0.000 title claims abstract description 42
- 238000003723 Smelting Methods 0.000 title claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 54
- 238000005406 washing Methods 0.000 claims abstract description 25
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical group [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 23
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims abstract description 20
- 229910000368 zinc sulfate Inorganic materials 0.000 claims abstract description 20
- 229960001763 zinc sulfate Drugs 0.000 claims abstract description 20
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims abstract description 17
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 claims abstract description 13
- 239000011667 zinc carbonate Substances 0.000 claims abstract description 13
- 235000004416 zinc carbonate Nutrition 0.000 claims abstract description 13
- 229910000010 zinc carbonate Inorganic materials 0.000 claims abstract description 13
- 239000013078 crystal Substances 0.000 claims abstract description 12
- 239000003513 alkali Substances 0.000 claims abstract description 11
- 238000000605 extraction Methods 0.000 claims abstract description 11
- 239000012535 impurity Substances 0.000 claims abstract description 10
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 9
- QCUOBSQYDGUHHT-UHFFFAOYSA-L cadmium sulfate Chemical compound [Cd+2].[O-]S([O-])(=O)=O QCUOBSQYDGUHHT-UHFFFAOYSA-L 0.000 claims abstract description 9
- 229910000331 cadmium sulfate Inorganic materials 0.000 claims abstract description 9
- 238000002425 crystallisation Methods 0.000 claims abstract description 8
- 230000008025 crystallization Effects 0.000 claims abstract description 8
- 238000001704 evaporation Methods 0.000 claims abstract description 8
- 230000008020 evaporation Effects 0.000 claims abstract description 8
- 238000002386 leaching Methods 0.000 claims abstract description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 36
- 239000007789 gas Substances 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 27
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 24
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 22
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 18
- 239000006227 byproduct Substances 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 15
- 238000003825 pressing Methods 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 15
- 230000035484 reaction time Effects 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 235000010265 sodium sulphite Nutrition 0.000 claims description 12
- 238000003837 high-temperature calcination Methods 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 9
- 239000003638 chemical reducing agent Substances 0.000 claims description 8
- 239000003085 diluting agent Substances 0.000 claims description 7
- 239000012074 organic phase Substances 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000007865 diluting Methods 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 6
- 239000003350 kerosene Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 4
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 claims description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000001117 sulphuric acid Substances 0.000 claims 1
- 235000011149 sulphuric acid Nutrition 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 13
- 239000002184 metal Substances 0.000 abstract description 13
- 239000002253 acid Substances 0.000 abstract description 8
- 238000009854 hydrometallurgy Methods 0.000 abstract description 8
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000001914 filtration Methods 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000005554 pickling Methods 0.000 description 3
- 238000007127 saponification reaction Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000008399 tap water Substances 0.000 description 3
- 235000020679 tap water Nutrition 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 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
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- RZFBEFUNINJXRQ-UHFFFAOYSA-M sodium ethyl xanthate Chemical compound [Na+].CCOC([S-])=S RZFBEFUNINJXRQ-UHFFFAOYSA-M 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- VRRFSFYSLSPWQY-UHFFFAOYSA-N sulfanylidenecobalt Chemical compound [Co]=S VRRFSFYSLSPWQY-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/10—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/003—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
-
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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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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- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Metallurgy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a method for producing cobalt sulfate by using organic cobalt slag of a zinc smelting plant, belonging to the field of non-ferrous metal hydrometallurgy. Firstly, washing organic cobalt slag of a zinc smelting plant with dilute acid to react zinc and cadmium in the organic cobalt slag with dilute sulfuric acid to generate zinc sulfate and cadmium sulfate, adding the zinc sulfate and the cadmium sulfate into a solution, then filtering, and recovering the solution to obtain cadmium powder and zinc carbonate; roasting filter residues at low temperature, roasting organic tail gas obtained by roasting at low temperature at high temperature, decomposing the organic tail gas at high temperature, circularly absorbing the tail gas by alkali liquor, roasting at low temperature to obtain cobalt oxide residues, leaching by sulfuric acid to obtain a solution containing cobalt sulfate, deeply removing impurities by P204 extraction, completely removing impurities, extracting cobalt by P507 to obtain a high-purity cobalt sulfate solution, and obtaining a battery-grade cobalt sulfate crystal product by an evaporation, concentration and crystallization mode. The application of the process develops a new cobalt raw material source for the field of non-ferrous metal hydrometallurgy, and has obvious economic value and social value.
Description
Technical Field
The invention belongs to the field of non-ferrous metal hydrometallurgy, and particularly relates to a method for producing cobalt sulfate by using organic cobalt slag of a zinc smelting plant.
Background
The cobalt resource in China is relatively deficient, and most of the cobalt resource in China depends on import, including cobalt ore, cobalt slag, various cobalt-containing waste materials and the like. With the rapid popularization of the application of the ternary lithium battery in the new energy electric automobile industry, China becomes the country with the fastest increase of cobalt consumption in recent years. Meanwhile, export restriction of high-grade cobalt ore is strengthened recently by the major export countries of cobalt ore. Therefore, to solve the problem of shortage of cobalt resources in China, the method actively participates in the development and utilization of the cobalt resources at home and abroad on one hand, and enhances the recycling of the cobalt resources on the other hand.
In the past, most of the cobalt in China is extracted from cobalt-sulfur concentrate, and since Gansu Jinchuan, Sichuan Union, Jilin Pan stone cupronite and nickel ore are developed, the cobalt is recovered from smelting systems of nickel, copper, zinc and the like, and becomes an important source of cobalt metal. At present, the enterprises of zinc hydrometallurgy in China mainly adopt a three-stage purification method to purify and remove impurities from neutral leachate, and the produced purified copper-cadmium slag and cobalt slag are leached after being mixed by three stages of slag due to high zinc content, mutual content and other reasons, and then the actual production adopts the processes of copper removal, cadmium removal, iron removal and cobalt removal respectively. The copper slag is used for producing cathode copper, the cadmium slag is used for producing refined cadmium, and the cobalt slag with the highest value is always lack of an economic, effective and feasible treatment process, and is generally stacked for a long time or directly calcined, so that valuable metal resources such as zinc, cobalt and the like cannot be recycled, and the benefits of enterprises are difficult to create. Meanwhile, the cobalt slag which belongs to dangerous waste is piled up in large quantity to pose serious threat to the environment, and the direct calcination causes great pollution to the environment. Therefore, in order to solve the problems of enterprises, a process technology capable of economically recovering valuable metals in cobalt slag is urgently needed.
In the deep cobalt removal process, a wet zinc smelting plant generally adopts a process method of adding an organic reagent, carrying out a complex reaction between anions of the organic reagent and cobalt ions in a solution to generate an organic compound which is extremely difficult to dissolve in water, and then filtering and removing the organic compound. The organic reagents adopted by different zinc smelting plants are different, but are generally sodium xanthate, and the material has good stability.
The organic cobalt slag generated in the production process of the zinc hydrometallurgy enterprise is metallurgical solid waste rich in cobalt resources, according to research and statistics, about 20 million tons of the organic cobalt slag are generated in China every year, and the organic cobalt slag contains 2-10% of cobalt, 5-30% of zinc, 0.05-2.5% of cadmium and a small amount of metals such as copper, iron, manganese and the like. In addition, the material also contains organic cobalt removal substances, belongs to dangerous waste, is stable at normal temperature, and is difficult to perform decomposition reaction with acid at normal temperature and normal pressure. However, the organic cobalt slag can be washed by dilute acid to remove zinc and cadmium, and then is roasted at low temperature to release organic gas, the structure of the organic cobalt slag is destroyed by high-temperature calcination, tail gas is recycled, and valuable metal cobalt in the cobalt slag after low-temperature roasting is recycled.
Disclosure of Invention
Aiming at the problems that organic cobalt slag generated in the production process of zinc hydrometallurgy is difficult to treat and valuable metals cannot be fully utilized, the invention provides a method for producing cobalt sulfate by using organic cobalt slag of a zinc smelting plant, which comprises the following steps: firstly, washing and filter-pressing zinc smelting organic cobalt slag by using dilute sulfuric acid to obtain zinc sulfate, cadmium sulfate filtrate and washing slag, replacing the zinc sulfate and cadmium sulfate filtrate by using zinc powder to obtain a byproduct cadmium powder, and preparing a byproduct zinc carbonate by using sodium carbonate in a zinc sulfate solution after filter-pressing; after washing, cobalt is separated from organic matters through low-temperature roasting of the cobalt residues, the organic matters are roasted at low temperature to become organic gas, the organic gas can be split into small molecular gas through high-temperature roasting, tail gas can be treated through liquid alkali absorption, the cobalt oxide residues after low-temperature roasting are leached by sulfuric acid and a reducing agent to obtain a solution containing cobalt sulfate, impurities can be completely removed through P204 extraction and deep impurity removal, cobalt is extracted by P507 to obtain a high-purity cobalt sulfate solution, and a battery-grade cobalt sulfate crystal product can be obtained through an evaporation, concentration and crystallization mode. The method can purify and remove impurities from the organic cobalt slag to produce pure battery-grade cobalt sulfate crystals, so that valuable metals in the organic cobalt slag are fully recycled, the aim of changing waste into valuable is fulfilled, a new cobalt raw material source is developed for the field of non-ferrous metal hydrometallurgy by applying the process technology, and the method has obvious economic value and social value.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
the invention provides a method for producing cobalt sulfate by using organic cobalt slag of a zinc smelting plant, which comprises the following steps:
a. washing and filter-pressing organic cobalt slag of a zinc smelting plant by using dilute sulfuric acid to obtain zinc sulfate, cadmium sulfate filtrate and washing slag;
b. b, replacing the zinc sulfate and cadmium sulfate filtrate obtained in the step a by using zinc powder to obtain a byproduct cadmium powder, and preparing a byproduct zinc carbonate from a zinc sulfate solution after filter pressing by using sodium carbonate;
c. b, roasting the washing slag obtained in the step a at a low temperature by using a rotary kiln to realize the separation of cobalt and organic matters, wherein cobalt is obtained as cobalt oxide slag in the roasting process, and the organic matters are changed into organic tail gas;
d. c, calcining the organic tail gas obtained in the step c at high temperature by using a high-temperature calciner to calcine and decompose the organic gas into micromolecular gas, and absorbing and treating the tail gas by using liquid caustic soda;
e. c, firstly, slurrying the cobalt oxide slag obtained in the step c with water, and then adding concentrated sulfuric acid and a reducing agent to carry out leaching reaction to obtain a solution containing cobalt sulfate;
f. and e, deeply removing impurities from the cobalt sulfate-containing solution obtained in the step e by using a P204 extracting agent, extracting cobalt by using a P507 extracting agent to obtain a high-purity cobalt sulfate solution, and obtaining a battery-grade cobalt sulfate crystal product by an evaporation, concentration and crystallization mode.
Further, in the step a, the mass fraction of the dilute sulfuric acid is 10-35%, the temperature range of the dilute sulfuric acid washing is 20-60 ℃, and the reaction time is 1-5 hours; the liquid-solid mass ratio of the dilute sulfuric acid to the organic cobalt slag is 2-6: 1.
Further, in the step a, the removal rate of zinc and cadmium in the organic cobalt slag after being washed by dilute sulfuric acid is higher than 95%.
Furthermore, the purity of the zinc powder in the step b is more than 96%, and the actual adding amount of the zinc powder is 1.0-1.2 times of the theoretical using amount of the zinc powder; the temperature of the replacement reaction is controlled to be 20-80 ℃, and the reaction time is 1-4 h.
Further, in the step b, in the step of preparing the by-product zinc carbonate by using sodium carbonate, the sodium carbonate is industrial sodium carbonate, the purity of the sodium carbonate is more than 98%, the pH value of the zinc sulfate solution is adjusted to 8.0-12.0 by using the sodium carbonate, the reaction temperature is controlled to be 30-60 ℃, and the reaction time is 1-5 hours.
Further, the temperature of the low-temperature roasting in the step c is controlled to be 300-800 ℃, and the time of the low-temperature roasting is 1-6 hours; and the organic gas generated by low-temperature roasting is introduced to the high-temperature calciner through the adjustable high-temperature fan.
Further, the temperature of the high-temperature calcination in the step d is controlled to be 1000-1800 ℃, and the high-temperature calcination time is 1-6 hours; the mass fraction of the liquid caustic soda is 5-20%.
Further, the liquid-solid mass ratio of the water to the cobalt oxide slag in the step e is 2-6: 1; the mass fraction of the concentrated sulfuric acid is 98%, and the liquid-solid mass ratio of the actual addition amount of the concentrated sulfuric acid to the cobalt oxide slag is 1-4: 1; the reducing agent comprises one or more of sodium sulfite, hydrogen peroxide, hydrogen and carbon monoxide.
Preferably, the reducing agent is sodium sulfite, the actual addition amount of the sodium sulfite is 55-85% of the mass of the cobalt oxide slag, the leaching reaction temperature is controlled at 60-85 ℃, and the reaction time is 2-8 hours.
Further, in the step f, diluting the extracting agent by using a diluent to a concentration of 12-25%, wherein the diluent is sulfonated kerosene; and (3) diluting the organic phase, and then saponifying with 10-20% liquid alkali, wherein the organic phase is saponified according to the following ratio of 1:1, carrying out 8-18 grade countercurrent extraction on the cobalt sulfate solution.
Compared with the prior art, the technical scheme of the invention at least comprises the following beneficial effects:
(1) the organic cobalt slag of the zinc smelting plant belongs to dangerous waste, is difficult to treat, and has a low sales coefficient according to the cobalt price, and by adopting the technical scheme of the invention, the organic cobalt slag can be purified to produce pure battery-grade cobalt sulfate crystals, so that valuable metals in the organic cobalt slag are fully recycled, and the aim of changing waste into valuable is fulfilled;
(2) the method is characterized in that the method utilizes organic cobalt slag of a zinc smelting plant to produce cobalt sulfate by combining the characteristics of enterprises and market demands, so as to obtain pure battery-grade cobalt sulfate crystals, and the cobalt sulfate crystals can be sold directly or matched with battery-grade nickel sulfate and battery-grade manganese sulfate for synthesizing the ternary battery anode precursor material.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is a process flow chart of a method for producing cobalt sulfate by using organic cobalt slag of a zinc smelting plant according to an embodiment of the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples. It should be understood that the scope of the above-described subject matter is not limited to the following examples, and any techniques implemented based on the disclosure of the present invention are within the scope of the present invention.
The invention provides a method for producing cobalt sulfate by using organic cobalt slag of a zinc smelting plant, wherein the process flow schematic diagram of the method is shown in figure 1: the method comprises the steps of removing more than 95% of zinc and cadmium from organic cobalt slag during washing with dilute sulfuric acid, recovering zinc sulfate and cadmium sulfate solution as washing liquid to obtain cadmium powder and zinc carbonate byproducts, separating cobalt and organic matters from the washed cobalt slag through low-temperature roasting, roasting the organic matters at low temperature to obtain organic gas, cracking the organic gas into small molecular gas through high-temperature roasting, treating tail gas through liquid alkali absorption, leaching the cobalt oxide slag after low-temperature roasting with sulfuric acid and a reducing agent to obtain a solution containing cobalt sulfate, deeply removing impurities through P204 extraction to remove the impurities, extracting cobalt with P507 to obtain a high-purity cobalt sulfate solution, and obtaining a battery-grade cobalt sulfate crystal product through an evaporation, concentration and crystallization mode. Based on long-term research and development tests on organic cobalt slag in zinc smelting plants, the invention discloses a green and environment-friendly process for comprehensively recovering the material, and the application of the technology develops a new cobalt raw material source for the field of non-ferrous metal hydrometallurgy, and has great economic value and social value.
Example 1
The invention relates to a method for producing cobalt sulfate by using organic cobalt slag of a zinc smelting plant, which comprises the following detailed steps:
a. firstly, stirring and washing dilute sulfuric acid and organic cobalt slag according to a liquid-solid ratio of 2:1, wherein the mass fraction of the dilute sulfuric acid is 10%, and carrying out dilute acid washing at a reaction temperature of 20 ℃ for 1 h;
b. b, adding zinc powder into the pickling solution obtained in the step a for replacement reaction, wherein the actual addition amount of the zinc powder is 1.0 time of the theoretical amount, the reaction temperature is 30 ℃, the reaction time is 2 hours, carrying out filter pressing to obtain cadmium powder, adding industrial sodium carbonate into the zinc sulfate solution after filter pressing to prepare a byproduct zinc carbonate, adding the industrial sodium carbonate to adjust the pH of the zinc sulfate solution to 9.0, the reaction temperature is 40 ℃, the reaction time is 2 hours, and carrying out filter pressing to obtain a byproduct zinc carbonate;
c. b, roasting the washing slag obtained in the step a at a low temperature in a rotary kiln, wherein the roasting temperature is controlled at 400 ℃, the roasting time is 3 hours, and cobalt oxide slag and organic gas are obtained after low-temperature roasting;
d. c, high-temperature calcination is carried out on the organic gas obtained in the step c, the high-temperature calcination temperature is 1200 ℃, the calcination time is 3 hours, and the micromolecule gas generated after calcination is absorbed by liquid alkali with the mass fraction of 5%;
e. c, carrying out slurrying reaction on tap water and the cobalt oxide slag obtained in the step c according to a liquid-solid ratio of 2:1, adding 98% of concentrated sulfuric acid by mass according to a liquid-solid ratio of the concentrated sulfuric acid to the cobalt oxide slag, adding 98% of sodium sulfite by mass, adding 60% of sodium sulfite by mass, introducing steam to control the reaction temperature to be 60 ℃, and reacting for 3 hours;
f. diluting the organic phases P204 and P507 to 12% by using a diluent sulfonated kerosene, then saponifying by using 10% liquid alkali, respectively carrying out 10-grade countercurrent extraction on the cobalt sulfate solution obtained in the step e according to the ratio of 1:1 after saponification, carrying out phase splitting after extraction to obtain high-concentration pure cobalt sulfate solution, and obtaining battery-grade cobalt sulfate crystals by an evaporation, concentration and crystallization mode.
Example 2
The invention relates to a method for producing cobalt sulfate by using organic cobalt slag of a zinc smelting plant, which comprises the following detailed steps:
a. firstly, stirring and washing dilute sulfuric acid and organic cobalt slag according to a liquid-solid ratio of 4:1, wherein the mass fraction of the dilute sulfuric acid is 20%, introducing steam to maintain the reaction temperature at 40 ℃ for dilute acid washing, and the acid washing time is 3 hours;
b. b, adding zinc powder into the pickling solution obtained in the step a for replacement reaction, wherein the actual addition amount of the zinc powder is 1.1 times of the theoretical amount, the reaction temperature is 50 ℃, the reaction time is 3 hours, carrying out filter pressing to obtain cadmium powder, adding industrial sodium carbonate into the zinc sulfate solution after filter pressing to prepare a byproduct zinc carbonate, adding the industrial sodium carbonate to adjust the pH of the zinc sulfate solution to 10.0, the reaction temperature is 50 ℃, the reaction time is 3 hours, and carrying out filter pressing to obtain a byproduct zinc carbonate;
c. b, roasting the washing slag obtained in the step a at a low temperature in a rotary kiln, wherein the roasting temperature is controlled at 500 ℃, the roasting time is 4 hours, and cobalt oxide slag and organic gas are obtained after low-temperature roasting;
d. c, high-temperature calcination is carried out on the organic gas obtained in the step c, the high-temperature calcination temperature is 1400 ℃, the calcination time is 4 hours, and the micromolecule gas generated after calcination is absorbed by liquid alkali with the mass fraction of 10%;
e. c, carrying out slurrying reaction on tap water and the cobalt oxide slag obtained in the step c according to a liquid-solid ratio of 4:1, adding 98% of concentrated sulfuric acid by mass according to a liquid-solid ratio of the concentrated sulfuric acid to the cobalt oxide slag of 3:1, adding 98% of sodium sulfite by mass, adding 70% of sodium sulfite by mass of the cobalt oxide slag, introducing steam to control the reaction temperature to be 70 ℃, and reacting for 4 hours;
f. diluting the organic phases P204 and P507 to be 15% in concentration by using a diluent sulfonated kerosene, then saponifying by using 15% liquid alkali, respectively carrying out 12-grade countercurrent extraction on the cobalt sulfate solution obtained in the step e according to the ratio of 1:1 after saponification, carrying out phase splitting after extraction to obtain high-concentration pure cobalt sulfate solution, and obtaining battery-grade cobalt sulfate crystals by an evaporation, concentration and crystallization mode.
Example 3
The invention relates to a method for producing cobalt sulfate by using organic cobalt slag of a zinc smelting plant, which comprises the following detailed steps:
a. firstly, stirring and washing dilute sulfuric acid and organic cobalt slag according to a liquid-solid ratio of 6:1, wherein the mass fraction of the dilute sulfuric acid is 30%, introducing steam to maintain the reaction temperature at 60 ℃ for dilute acid washing, and the acid washing time is 5 hours;
b. b, adding zinc powder into the pickling solution obtained in the step a for replacement reaction, wherein the actual addition amount of the zinc powder is 1.2 times of the theoretical amount, the reaction temperature is 70 ℃, the reaction time is 4 hours, carrying out filter pressing to obtain cadmium powder, adding industrial sodium carbonate into the zinc sulfate solution after filter pressing to prepare a byproduct zinc carbonate, adding the industrial sodium carbonate to adjust the pH of the zinc sulfate solution to 11.0, the reaction temperature is 60 ℃, the reaction time is 4 hours, and carrying out filter pressing to obtain a byproduct zinc carbonate;
c. b, roasting the washing slag obtained in the step a at a low temperature in a rotary kiln, wherein the roasting temperature is controlled at 600 ℃, the roasting time is 5 hours, and cobalt oxide slag and organic gas are obtained after low-temperature roasting;
d. c, high-temperature calcination is carried out on the organic gas obtained in the step c, the high-temperature calcination temperature is 1600 ℃, the calcination time is 5 hours, and the micromolecule gas generated after calcination is absorbed by liquid alkali with the mass fraction of 15%;
e. c, carrying out slurrying reaction on tap water and the cobalt oxide slag obtained in the step c according to a liquid-solid ratio of 5:1, adding 98% of concentrated sulfuric acid by mass according to a liquid-solid ratio of 4:1 to the cobalt oxide slag, adding 98% of sodium sulfite by mass, adding 80% of sodium sulfite by mass of the cobalt oxide slag, introducing steam to control the reaction temperature to be 80 ℃, and reacting for 5 hours;
f. diluting the organic phases P204 and P507 to 20% by using a diluent sulfonated kerosene, then saponifying by using 20% liquid alkali, respectively carrying out 16-grade countercurrent extraction on the cobalt sulfate solution obtained in the step e according to the ratio of 1:1 after saponification, carrying out phase splitting after extraction to obtain high-concentration pure cobalt sulfate solution, and obtaining battery-grade cobalt sulfate crystals by an evaporation, concentration and crystallization mode.
The above description is only for the specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. A method for producing cobalt sulfate by using organic cobalt slag of a zinc smelting plant is characterized by comprising the following steps:
a. washing and filter-pressing organic cobalt slag of a zinc smelting plant by using dilute sulfuric acid to obtain zinc sulfate, cadmium sulfate filtrate and washing slag;
b. b, replacing the zinc sulfate and cadmium sulfate filtrate obtained in the step a by using zinc powder to obtain a byproduct cadmium powder, and preparing a byproduct zinc carbonate from a zinc sulfate solution after filter pressing by using sodium carbonate;
c. b, roasting the washing slag obtained in the step a at a low temperature by using a rotary kiln to realize the separation of cobalt and organic matters, wherein cobalt is obtained as cobalt oxide slag in the roasting process, and the organic matters are changed into organic tail gas;
d. c, calcining the organic tail gas obtained in the step c at high temperature by using a high-temperature calciner to calcine and decompose the organic gas into micromolecular gas, and absorbing and treating the tail gas by using liquid caustic soda;
e. c, firstly, slurrying the cobalt oxide slag obtained in the step c with water, and then adding concentrated sulfuric acid and a reducing agent to carry out leaching reaction to obtain a solution containing cobalt sulfate;
f. and e, deeply removing impurities from the cobalt sulfate-containing solution obtained in the step e by using a P204 extracting agent, extracting cobalt by using a P507 extracting agent to obtain a high-purity cobalt sulfate solution, and obtaining a battery-grade cobalt sulfate crystal product by an evaporation, concentration and crystallization mode.
2. The method for producing cobaltous sulfate by using organic cobalt slag of a zinc smelting plant according to claim 1, wherein the liquid-solid mass ratio of the dilute sulfuric acid to the organic cobalt slag in the step a is 2-6: 1; the mass fraction of the dilute sulfuric acid is 10-35%, the temperature range of the dilute sulfuric acid washing is 20-60 ℃, and the reaction time is 1-5 h.
3. The method for producing cobaltous sulfate by using organic cobalt slag of a zinc smelting plant as claimed in claim 1, wherein the removal rate of zinc and cadmium in the organic cobalt slag washed by dilute sulphuric acid in the step a is higher than 95%.
4. The method for producing cobaltous sulfate by using organic cobalt slag of a zinc smelting plant according to claim 1, wherein the purity of the zinc powder in the step b is more than 96%, and the actual adding amount of the zinc powder is 1.0-1.2 times of the theoretical using amount of the zinc powder; the temperature of the replacement reaction is controlled to be 20-80 ℃, and the reaction time is 1-4 h.
5. The method of claim 1, wherein in the step of preparing the byproduct zinc carbonate from the organic cobalt slag of the zinc smelting plant, sodium carbonate is industrial sodium carbonate, the purity of the sodium carbonate is more than 98%, the pH of the zinc sulfate solution is adjusted to 8.0-12.0 by the sodium carbonate, the reaction temperature is controlled to 30-60 ℃, and the reaction time is 1-5 hours.
6. The method for producing cobaltous sulfate by using organic cobalt slag of a zinc smelting plant according to claim 1, wherein the temperature of the low-temperature roasting in the step c is controlled to be 300-800 ℃, and the time of the low-temperature roasting is 1-6 hours; and the organic gas generated by low-temperature roasting is introduced to the high-temperature calciner through the adjustable high-temperature fan.
7. The method for producing cobaltous sulfate by using organic cobalt slag of a zinc smelting plant according to claim 1, wherein the high-temperature calcination temperature in the step d is controlled to be 1000-1800 ℃, and the high-temperature calcination time is 1-6 hours; the mass fraction of the liquid caustic soda is 5-20%.
8. The method for producing cobalt sulfate by using organic cobalt slag of a zinc smelting plant according to claim 1, wherein the liquid-solid mass ratio of water to cobalt oxide slag in the step e is 2-6: 1; the mass fraction of the concentrated sulfuric acid is 98%, and the liquid-solid mass ratio of the actual addition amount of the concentrated sulfuric acid to the cobalt oxide slag is 1-4: 1; the reducing agent comprises one or more of sodium sulfite, hydrogen peroxide, hydrogen and carbon monoxide.
9. The method for producing cobaltous sulfate by using organic cobalt slag of a zinc smelting plant according to claim 8, wherein the reducing agent in the step e is sodium sulfite, the actual addition amount of the sodium sulfite is 55-85% of the mass of the cobalt oxide slag, the leaching reaction temperature is controlled at 60-85 ℃, and the reaction time is 2-8 h.
10. The method for producing cobaltous sulfate by using organic cobalt slag of zinc smelting plant according to claim 1, wherein in step f, the extracting agent is diluted to a concentration of 12-25% by using a diluent, and the diluent is sulfonated kerosene; and (3) diluting the organic phase, and then saponifying with 10-20% liquid alkali, wherein the organic phase is saponified according to the following ratio of 1:1, carrying out 8-18 grade countercurrent extraction on the cobalt sulfate solution.
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