CN116903051A - Method for producing cobalt chloride by using low-grade cobalt slag - Google Patents
Method for producing cobalt chloride by using low-grade cobalt slag Download PDFInfo
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- CN116903051A CN116903051A CN202310856934.4A CN202310856934A CN116903051A CN 116903051 A CN116903051 A CN 116903051A CN 202310856934 A CN202310856934 A CN 202310856934A CN 116903051 A CN116903051 A CN 116903051A
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- cobalt
- liquor
- cobalt chloride
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- low
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- 239000010941 cobalt Substances 0.000 title claims abstract description 106
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 106
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 106
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 title claims abstract description 63
- 239000002893 slag Substances 0.000 title claims abstract description 44
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 28
- 239000007788 liquid Substances 0.000 claims abstract description 78
- 238000000605 extraction Methods 0.000 claims abstract description 43
- 238000005406 washing Methods 0.000 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 238000007127 saponification reaction Methods 0.000 claims abstract description 20
- 239000003513 alkali Substances 0.000 claims abstract description 18
- 238000012216 screening Methods 0.000 claims abstract description 13
- 238000007885 magnetic separation Methods 0.000 claims abstract description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 88
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 72
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 50
- 239000000463 material Substances 0.000 claims description 40
- 239000000243 solution Substances 0.000 claims description 39
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 39
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 34
- 235000010265 sodium sulphite Nutrition 0.000 claims description 25
- 239000011259 mixed solution Substances 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 229910052759 nickel Inorganic materials 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 15
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 claims description 13
- 239000000696 magnetic material Substances 0.000 claims description 12
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 239000007921 spray Substances 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 239000003350 kerosene Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000012074 organic phase Substances 0.000 claims description 5
- 238000009853 pyrometallurgy Methods 0.000 claims description 5
- 238000004064 recycling Methods 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 159000000000 sodium salts Chemical class 0.000 claims description 5
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 16
- 239000000126 substance Substances 0.000 abstract description 5
- 239000012535 impurity Substances 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 238000013461 design Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 150000002739 metals Chemical class 0.000 abstract description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000003723 Smelting Methods 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910001608 iron mineral Inorganic materials 0.000 description 1
- 238000009996 mechanical pre-treatment Methods 0.000 description 1
- 230000004630 mental health Effects 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/08—Halides
- C01G51/085—Chlorides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/04—Solvent extraction of solutions which are liquid
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C21/00—Disintegrating plant with or without drying of the material
-
- 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
-
- 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
Abstract
The invention relates to a method for producing cobalt chloride by using low-grade cobalt slag, belonging to the technical field of cobalt chloride production. The method for producing the cobalt chloride from the low-grade cobalt slag comprises the steps of firstly carrying out pretreatment such as crushing, screening, magnetic separation and the like on the low-grade cobalt slag, then carrying out chemical treatment, and separating and removing impurities, metals and the like in the low-grade cobalt slag after the pretreatment, so that the interference of reaction in the subsequent cobalt chloride production process can be reduced, and the purity of the cobalt chloride is improved; in chemical treatment, the invention strictly regulates and controls the pH value, the temperature and the extraction technology in the process, the cobalt washing liquid, the back extraction liquid A and the back extraction liquid B are continuously and circularly used in a tank by carrying out special design, the finally obtained back extraction liquid can be returned to the initial starting point of the process for saponification and reutilization, the utilization rate of the whole process flow is high, and the cobalt content in the obtained cobalt chloride is high. In addition, the invention uses the alkali absorption liquid to absorb the pollution in the reaction process, and considers the environmental problem on the premise of considering the yield and purity of the finished product.
Description
Technical Field
The invention belongs to the technical field of cobalt chloride production, and particularly relates to a method for producing cobalt chloride by using low-grade cobalt slag.
Background
Cobalt is an important strategic metal and is widely used in the fields of industry, military, medicine, new energy sources and the like. Along with the continuous and stable growth of Chinese economy, cobalt is widely applied to various departments of national economy, the demand of the domestic and foreign markets for cobalt is increasingly large, and the supply pressure of cobalt resources is gradually increased. However, cobalt resources in China are lean and rich, most of cobalt smelting raw materials of some domestic factories are imported from abroad, and in recent years, the cobalt raw materials are more difficult to supply and the price is increased, so that further cobalt product preparation by utilizing various cobalt slag waste materials has important significance for effectively utilizing resources, reducing cost and protecting environment, and particularly, the cobalt product is prepared by utilizing low-grade cobalt slag. The low-grade cobalt slag is a waste product and consists of slag with lower content of residual cobalt in the cobalt smelting process, and is characterized by containing a large amount of impurities, quartz, iron minerals and other non-cobalt components, and the components tend to interfere, so that the reaction efficiency and purity are reduced, and the reagent cost in the production process is increased. Therefore, it is a difficult task to directly use low-grade cobalt slag to produce high-purity cobalt chloride.
In addition, in the market, although factories capable of producing cobalt chloride by using low-grade cobalt slag exist at present, most production processes are complex, manpower and material resources are required to be consumed, in addition, the cobalt content of the produced cobalt chloride and the purity of the cobalt chloride are low, and the quality requirement of various industries on the cobalt chloride is difficult to meet. Therefore, a method for producing cobalt chloride with high cobalt content and purity by utilizing low-grade cobalt slag is sought, which is favorable for further improving the efficiency and sustainability of related processes, promotes the high-efficiency utilization and the circular economy development of low-grade cobalt slag resources, and has excellent practical significance.
Disclosure of Invention
The invention aims to provide a method for producing cobalt chloride by using low-grade cobalt slag, which comprises the steps of firstly carrying out pretreatment such as crushing, screening, magnetic separation and the like on the low-grade cobalt slag, then carrying out chemical treatment, and separating and removing impurities, metals and the like in the low-grade cobalt slag after the pretreatment, so that the interference of the reaction in the subsequent cobalt chloride process can be reduced, and the purity of the cobalt chloride is improved; in chemical treatment, the invention strictly regulates and controls the pH value, the temperature and the extraction technology in the process, the cobalt washing liquid, the back extraction liquid A and the back extraction liquid B are continuously and circularly used in a tank by carrying out special design, the finally obtained back extraction liquid can be returned to the initial starting point of the process for saponification and reutilization, the utilization rate of the whole process flow is high, and the cobalt content in the obtained cobalt chloride is high. In addition, the invention uses the alkali absorption liquid to absorb the pollution in the reaction process, considers the environmental problem on the premise of considering the yield and purity of the finished product, and solves the problems of low cobalt content and low purity of the cobalt chloride in the prepared cobalt chloride in the prior art.
The aim of the invention can be achieved by the following technical scheme:
a method for producing cobalt chloride by using low-grade cobalt slag specifically comprises the following steps:
s1, saponifying the P-204 extractant to obtain saponified P-204; pretreating cobalt slag to obtain a magnetic material and pretreated cobalt material;
s2, adding deionized water into the pretreated cobalt material, uniformly mixing to obtain a mixture, adding concentrated sulfuric acid and sodium sulfite into the mixture, performing primary temperature control reaction to obtain a mixed solution A, adding sodium chlorate and sodium sulfite into the mixed solution A, performing secondary temperature control reaction, controlling pH, filtering to obtain filter residues and a mixed solution B, and performing pyrometallurgy on the filter residues;
s3, extracting the mixed liquor B by using saponified P-204 to obtain nickel-containing cobalt liquor and raffinate A, adding hydrochloric acid into the raffinate A to reflux and wash cobalt to obtain cobalt-washing liquor, adding hydrochloric acid into the cobalt-washing liquor to perform primary stripping to obtain copper-containing liquor and strip liquor A, adding hydrochloric acid into the strip liquor A to perform secondary stripping to obtain iron-containing liquor and strip liquor B, performing countercurrent extraction on the strip liquor B and saponified liquor to obtain cobalt chloride solution and extract, and recycling the extract in step S1 and the P-204 extractant for saponification;
s4, extracting the nickel-cobalt-containing liquid by using a C272 extractant to obtain a nickel-containing liquid and a raffinate B, adding sulfuric acid-washed nickel into the raffinate B to obtain a nickel-washing liquid, adding hydrochloric acid into the nickel-washing liquid to perform three times of back extraction to obtain a cobalt chloride solution and a back extraction liquid C, adding deionized water and sodium hydroxide into the back extraction liquid C to obtain a treated liquid, and introducing the treated liquid into the starting point of the step S4 and the C272 extractant to perform extraction of the nickel-cobalt-containing liquid;
and S5, evaporating, crystallizing and centrifuging the cobalt chloride solution obtained in the steps S3 and S4 to obtain a cobalt chloride product.
As a further preferable scheme of the invention, the cobalt content in the cobalt slag in the step S1 is not more than 0.5%.
As a further preferred embodiment of the present invention, the saponification in step S1 is specifically: and (3) saponifying the P-204 extractant into sodium salt with the saponification rate of 90-93% by adopting sodium hydroxide.
As a further preferable embodiment of the present invention, the pretreatment in step S1 specifically includes: sequentially crushing and screening cobalt slag to obtain oversize materials and undersize materials, carrying out re-crushing and screening treatment on the oversize materials, carrying out magnetic separation on the undersize materials to obtain magnetic materials and pretreated cobalt materials, and carrying out resource utilization on the magnetic materials.
As a further preferable scheme of the invention, the mass ratio of the cobalt material, deionized water, concentrated sulfuric acid and sodium sulfite after pretreatment in the step S2 is 100:200-300:1-1.8:0.5-1.6; the temperature of the primary temperature control reaction is 75-85 ℃ and the time is 2-3h; the mass fraction of the concentrated sulfuric acid is 80%.
As a further preferable scheme of the invention, the mass ratio of the mixed solution A, sodium chlorate and sodium sulfite in the step S2 is 250-300:0.7-1.2:0.5-1.2; the temperature of the secondary temperature control reaction is 93-98 ℃ and the time is 2-3.5h; the pH control is specifically to add sodium carbonate to control the pH value to be 1.5-2.0.
As a further preferable scheme of the invention, the adding of the concentrated sulfuric acid and the sodium sulfite into the mixture in the step S2 is performed in an alkali liquor spray washing tower, wherein the alkali liquor in the alkali liquor spray washing tower comprises any one of sodium hydroxide with the concentration of 2-5mol/L and calcium hydroxide with the concentration of 2-5.5 mol/L.
As a further preferable scheme of the invention, the concentration of hydrochloric acid added in the reflux cobalt washing, the primary back extraction and the secondary back extraction in the step S3 is 10mol/L, and the volume ratio of the raffinate A to the hydrochloric acid is 1:1-2; the volume ratio of the cobalt washing liquid to the hydrochloric acid is 1:1-1.5; the volume ratio of the back extraction liquid A to the hydrochloric acid is 1:1-2.
As a further preferable mode of the invention, the saponified solution in the step S3 is a saponified solution obtained by saponifying a P-204 sulfonated kerosene solution with an organic phase of 25% with sodium hydroxide to obtain a saponified solution with a saponification rate of 80-90%.
As a further preferable scheme of the invention, the volume ratio of the raffinate B to the sulfuric acid in the step S4 is 1:1.5-2; the volume ratio of the nickel washing liquid to the hydrochloric acid is 1:1.5-2.5; the volume ratio of the stripping solution C to the deionized water to the sodium hydroxide is 1:1-2:2-3.
As a further preferable mode of the invention, the concentration of the sulfuric acid is 40-45g/L; the concentration of the hydrochloric acid is 80-85g/L.
The invention has the beneficial effects that:
(1) The method for producing cobalt chloride from low-grade cobalt slag is characterized in that the special design is carried out by multiple mechanical pretreatment, strict regulation and control of the pH value, temperature and extraction technology, the cobalt washing liquid, the back extraction liquid A and the back extraction liquid B are continuously recycled in a tank, the finally obtained back extraction liquid can be returned to the initial starting point of the process for saponification and reutilization, the utilization rate of the whole process flow is high, and the cobalt content in the obtained cobalt chloride is high.
(2) According to the method, the low-grade cobalt slag is subjected to pretreatment such as crushing, screening, magnetic separation and the like, and then is subjected to chemical treatment, so that impurities, metals and the like in the low-grade cobalt slag can be separated and removed after the pretreatment, the interference of reactions in the subsequent cobalt chloride production process can be reduced, and the purity of the cobalt chloride is improved.
(3) The invention absorbs pollution such as sulfur dioxide, chlorine and sulfuric acid mist generated in the process of reaction by the alkali absorption liquid, thereby reducing the pollution degree to the environment, being beneficial to physical and mental health of operators and taking the environmental problem into consideration on the premise of considering the yield and purity of finished products.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
A method for producing cobalt chloride by using low-grade cobalt slag specifically comprises the following steps:
s1, saponifying a P-204 extractant into sodium salt with a saponification rate of 90% by adopting sodium hydroxide to obtain saponified P-204;
sequentially crushing and screening cobalt slag with the cobalt content of 0.3% to obtain oversize materials and undersize materials, carrying out re-crushing and screening treatment on the oversize materials, carrying out magnetic separation on the undersize materials to obtain magnetic materials and pretreated cobalt materials, and sending the magnetic materials into a recovery plant for further resource utilization;
s2, adding deionized water into the pretreated cobalt material, uniformly mixing to obtain a mixture, adding concentrated sulfuric acid with the mass fraction of 80% and sodium sulfite into the mixture, controlling the temperature to be 75 ℃ for reaction for 3 hours to obtain a mixed solution A, adding sodium chlorate and sodium sulfite into the mixed solution A, controlling the temperature to be 93 ℃ for reaction for 3.5 hours, simultaneously adding sodium carbonate to control the pH value to be 1.5, filtering to obtain filter residues and a mixed solution B, and carrying out pyrometallurgy on the filter residues;
the mass ratio of the pretreated cobalt material to the deionized water to the concentrated sulfuric acid to the sodium sulfite is 100:250:1.4:0.5;
the mass ratio of the mixed solution A to the sodium chlorate to the sodium sulfite is 275:0.7:0.8;
the adding of the concentrated sulfuric acid and the sodium sulfite into the mixture is performed in an alkali liquor spray washing tower, and alkali liquor in the alkali liquor spray washing tower is sodium hydroxide solution with the concentration of 2 mol/L.
S3, extracting the mixed liquor B by using saponified P-204 to obtain nickel-containing cobalt liquor and raffinate A, adding hydrochloric acid into the raffinate A to reflux and wash cobalt to obtain cobalt-washing liquor, adding hydrochloric acid into the cobalt-washing liquor to perform primary stripping to obtain copper-containing liquor and strip liquor A, adding hydrochloric acid into the strip liquor A to perform secondary stripping to obtain iron-containing liquor and strip liquor B, performing countercurrent extraction on the strip liquor B and saponified liquor to obtain cobalt chloride solution and extract, and recycling the extract in step S1 and the P-204 extractant for saponification;
the volume ratio of the mixed solution B to the saponified P-204 is 1:2; the volume ratio of the raffinate A to the hydrochloric acid is 1:1.5; the volume ratio of the cobalt washing liquid to the hydrochloric acid is 1:1; the volume ratio of the back extraction liquid A to the hydrochloric acid is 1:2;
the saponified solution is a saponified solution obtained by saponifying a P-204 sulfonated kerosene solution with an organic phase of 25% by adopting sodium hydroxide, and the saponification rate is 80%;
s4, extracting the nickel-cobalt-containing liquid by adopting a C272 extractant to obtain nickel-containing liquid and raffinate B, adding sulfuric acid with the concentration of 40g/L into the raffinate B to obtain nickel-washing liquid, adding hydrochloric acid with the concentration of 83g/L into the nickel-washing liquid to perform three times of back extraction to obtain cobalt chloride solution and back extraction liquid C, adding deionized water and sodium hydroxide into the back extraction liquid C to obtain treated liquid, and introducing the treated liquid into the starting point of the step S4 and the C272 extractant to extract the nickel-cobalt-containing liquid;
the volume ratio of the nickel-cobalt-containing liquid to the C272 extractant is 1:2.5; the volume ratio of the raffinate B to the sulfuric acid is 1:1.5; the volume ratio of the nickel washing liquid to the hydrochloric acid is 1:2.5; the volume ratio of the stripping solution C to deionized water to sodium hydroxide is 1:1.5:3.
And S5, evaporating, crystallizing and centrifuging the cobalt chloride solution obtained in the steps S3 and S4 to obtain a cobalt chloride product.
The cobalt chloride prepared by the method contains 29% of cobalt through detection.
Example 2
A method for producing cobalt chloride by using low-grade cobalt slag specifically comprises the following steps:
s1, saponifying a P-204 extractant into sodium salt with a saponification rate of 93% by adopting sodium hydroxide to obtain saponified P-204;
sequentially crushing and screening cobalt slag with the cobalt content of 0.2% to obtain oversize materials and undersize materials, carrying out re-crushing and screening treatment on the oversize materials, carrying out magnetic separation on the undersize materials to obtain magnetic materials and pretreated cobalt materials, and sending the magnetic materials into a recovery plant for further resource utilization;
s2, adding deionized water into the pretreated cobalt material, uniformly mixing to obtain a mixture, adding concentrated sulfuric acid with the mass fraction of 80% and sodium sulfite into the mixture, controlling the temperature to be 80 ℃ for reaction for 2.5 hours to obtain a mixed solution A, adding sodium chlorate and sodium sulfite into the mixed solution A, controlling the temperature to be 98 ℃ for reaction for 2 hours, simultaneously adding sodium carbonate to control the pH value to be 1.8, filtering to obtain filter residues and a mixed solution B, and carrying out pyrometallurgy on the filter residues;
the mass ratio of the pretreated cobalt material to the deionized water to the concentrated sulfuric acid to the sodium sulfite is 100:300:1.8:1;
the mass ratio of the mixed solution A to the sodium chlorate to the sodium sulfite is 300:1.2:0.5;
the concentrated sulfuric acid and the sodium sulfite are added into the mixture in an alkali liquor spray washing tower, and alkali liquor in the alkali liquor spray washing tower is calcium hydroxide solution with the concentration of 3.5 mol/L.
S3, extracting the mixed liquor B by using saponified P-204 to obtain nickel-containing cobalt liquor and raffinate A, adding hydrochloric acid into the raffinate A to reflux and wash cobalt to obtain cobalt-washing liquor, adding hydrochloric acid into the cobalt-washing liquor to perform primary stripping to obtain copper-containing liquor and strip liquor A, adding hydrochloric acid into the strip liquor A to perform secondary stripping to obtain iron-containing liquor and strip liquor B, performing countercurrent extraction on the strip liquor B and saponified liquor to obtain cobalt chloride solution and extract, and recycling the extract in step S1 and the P-204 extractant for saponification;
the volume ratio of the mixed solution B to the saponified P-204 is 1:2.5; the volume ratio of the raffinate A to the hydrochloric acid is 1:2; the volume ratio of the cobalt washing liquid to the hydrochloric acid is 1:1.5; the volume ratio of the back extraction liquid A to the hydrochloric acid is 1:1;
the saponified solution is a saponified solution obtained by saponifying a P-204 sulfonated kerosene solution with an organic phase of 25% by adopting sodium hydroxide, and the saponification rate is 90%;
s4, extracting the nickel-cobalt-containing liquid by adopting a C272 extractant to obtain nickel-containing liquid and raffinate B, adding sulfuric acid with the concentration of 43g/L into the raffinate B to obtain nickel-washing liquid, adding hydrochloric acid with the concentration of 80g/L into the nickel-washing liquid to perform three times of back extraction to obtain cobalt chloride solution and back extraction liquid C, adding deionized water and sodium hydroxide into the back extraction liquid C to obtain treated liquid, and introducing the treated liquid into the starting point of the step S4 and the C272 extractant to extract the nickel-cobalt-containing liquid;
the volume ratio of the nickel-cobalt-containing liquid to the C272 extractant is 1:2; the volume ratio of the raffinate B to the sulfuric acid is 1:1.8; the volume ratio of the nickel washing liquid to the hydrochloric acid is 1:2; the volume ratio of the stripping solution C to deionized water to sodium hydroxide is 1:1:2.5.
S5, evaporating, crystallizing and centrifuging the cobalt chloride solution obtained in the steps S3 and S4 to obtain a cobalt chloride product;
the cobalt chloride prepared by the method contains 29% of cobalt through detection.
Example 3
A method for producing cobalt chloride by using low-grade cobalt slag specifically comprises the following steps:
s1, saponifying a P-204 extractant into sodium salt with a saponification rate of 91% by adopting sodium hydroxide to obtain saponified P-204;
sequentially crushing and screening cobalt slag with the cobalt content of 0.4% to obtain oversize materials and undersize materials, carrying out re-crushing and screening treatment on the oversize materials, carrying out magnetic separation on the undersize materials to obtain magnetic materials and pretreated cobalt materials, and sending the magnetic materials into a recovery plant for further resource utilization;
s2, adding deionized water into the pretreated cobalt material, uniformly mixing to obtain a mixture, adding concentrated sulfuric acid with the mass fraction of 80% and sodium sulfite into the mixture, controlling the temperature to be 85 ℃ for reaction for 2 hours to obtain a mixed solution A, adding sodium chlorate and sodium sulfite into the mixed solution A, controlling the temperature to be 95 ℃ for reaction for 2.7 hours, simultaneously adding sodium carbonate to control the pH value to be 2.0, filtering to obtain filter residues and a mixed solution B, and carrying out pyrometallurgy on the filter residues;
the mass ratio of the pretreated cobalt material to the deionized water to the concentrated sulfuric acid to the sodium sulfite is 100:200:1.6:1.6;
the mass ratio of the mixed solution A to the sodium chlorate to the sodium sulfite is 250:0.9:1.2;
the adding of the concentrated sulfuric acid and the sodium sulfite into the mixture is performed in an alkali liquor spray washing tower, and alkali liquor in the alkali liquor spray washing tower is sodium hydroxide solution with the concentration of 5 mol/L.
S3, extracting the mixed liquor B by using saponified P-204 to obtain nickel-containing cobalt liquor and raffinate A, adding hydrochloric acid into the raffinate A to reflux and wash cobalt to obtain cobalt-washing liquor, adding hydrochloric acid into the cobalt-washing liquor to perform primary stripping to obtain copper-containing liquor and strip liquor A, adding hydrochloric acid into the strip liquor A to perform secondary stripping to obtain iron-containing liquor and strip liquor B, performing countercurrent extraction on the strip liquor B and saponified liquor to obtain cobalt chloride solution and extract, and recycling the extract in step S1 and the P-204 extractant for saponification;
the volume ratio of the mixed solution B to the saponified P-204 is 1:2.5; the volume ratio of the raffinate A to the hydrochloric acid is 1:1; the volume ratio of the cobalt washing liquid to the hydrochloric acid is 1.3; the volume ratio of the back extraction liquid A to the hydrochloric acid is 1:1.5;
the saponified solution is a saponified solution obtained by saponifying a P-204 sulfonated kerosene solution with an organic phase of 25% by adopting sodium hydroxide, and the saponification rate is 85%;
s4, extracting the nickel-cobalt-containing liquid by adopting a C272 extractant to obtain nickel-containing liquid and raffinate B, adding sulfuric acid with the concentration of 45g/L into the raffinate B to obtain nickel-washing liquid, adding hydrochloric acid with the concentration of 85g/L into the nickel-washing liquid to perform three times of back extraction to obtain cobalt chloride solution and back extraction liquid C, adding deionized water and sodium hydroxide into the back extraction liquid C to obtain treated liquid, and introducing the treated liquid into the starting point of the step S4 and the C272 extractant to extract the nickel-cobalt-containing liquid;
the volume ratio of the nickel-cobalt-containing liquid to the C272 extractant is 1:2.5; the volume ratio of the raffinate B to the sulfuric acid is 1:2; the volume ratio of the nickel washing liquid to the hydrochloric acid is 1:1.5; the volume ratio of the stripping solution C to deionized water to sodium hydroxide is 1:2:2.
And S5, evaporating, crystallizing and centrifuging the cobalt chloride solution obtained in the steps S3 and S4 to obtain a cobalt chloride product.
The cobalt chloride prepared by the method contains 30% of cobalt through detection.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is merely illustrative and explanatory of the invention, as various modifications and additions may be made to the particular embodiments described, or in a similar manner, by those skilled in the art, without departing from the scope of the invention or exceeding the scope of the invention as defined in the claims.
Claims (10)
1. The method for producing the cobalt chloride by utilizing the low-grade cobalt slag is characterized by comprising the following steps of:
s1, saponifying the P-204 extractant to obtain saponified P-204; pretreating cobalt slag to obtain a magnetic material and pretreated cobalt material;
s2, adding deionized water into the pretreated cobalt material, uniformly mixing to obtain a mixture, adding concentrated sulfuric acid and sodium sulfite into the mixture, performing primary temperature control reaction to obtain a mixed solution A, adding sodium chlorate and sodium sulfite into the mixed solution A, performing secondary temperature control reaction, controlling pH, filtering to obtain filter residues and a mixed solution B, and performing pyrometallurgy on the filter residues;
s3, extracting the mixed liquor B by using saponified P-204 to obtain nickel-containing cobalt liquor and raffinate A, adding hydrochloric acid into the raffinate A to reflux and wash cobalt to obtain cobalt-washing liquor, adding hydrochloric acid into the cobalt-washing liquor to perform primary stripping to obtain copper-containing liquor and strip liquor A, adding hydrochloric acid into the strip liquor A to perform secondary stripping to obtain iron-containing liquor and strip liquor B, performing countercurrent extraction on the strip liquor B and saponified liquor to obtain cobalt chloride solution and extract, and recycling the extract in step S1 and the P-204 extractant for saponification;
s4, extracting the nickel-cobalt-containing liquid by using a C272 extractant to obtain a nickel-containing liquid and a raffinate B, adding sulfuric acid-washed nickel into the raffinate B to obtain a nickel-washing liquid, adding hydrochloric acid into the nickel-washing liquid to perform three times of back extraction to obtain a cobalt chloride solution and a back extraction liquid C, adding deionized water and sodium hydroxide into the back extraction liquid C to obtain a treated liquid, and introducing the treated liquid into the starting point of the step S4 and the C272 extractant to perform extraction of the nickel-cobalt-containing liquid;
and S5, evaporating, crystallizing and centrifuging the cobalt chloride solution obtained in the steps S3 and S4 to obtain a cobalt chloride product.
2. The method for producing cobalt chloride by using low-grade cobalt slag according to claim 1, wherein the content of cobalt in the cobalt slag in the step S1 is not more than 0.5%.
3. The method for producing cobalt chloride by using low-grade cobalt slag according to claim 1, wherein the saponification of step S1 is specifically: and (3) saponifying the P-204 extractant into sodium salt with the saponification rate of 90-93% by adopting sodium hydroxide.
4. The method for producing cobalt chloride by using low-grade cobalt slag according to claim 1, wherein the pretreatment in step S1 specifically comprises: sequentially crushing and screening cobalt slag to obtain oversize materials and undersize materials, carrying out re-crushing and screening treatment on the oversize materials, carrying out magnetic separation on the undersize materials to obtain magnetic materials and pretreated cobalt materials, and carrying out resource utilization on the magnetic materials.
5. The method for producing cobalt chloride by utilizing low-grade cobalt slag according to claim 1, wherein the mass ratio of the pretreated cobalt material to deionized water to concentrated sulfuric acid to sodium sulfite in the step S2 is 100:200-300:1-1.8:0.5-1.6; the temperature of the primary temperature control reaction is 75-85 ℃ and the time is 2-3h; the mass fraction of the concentrated sulfuric acid is 80%.
6. The method for producing cobalt chloride by utilizing low-grade cobalt slag according to claim 1, wherein the mass ratio of the mixed liquor A, sodium chlorate and sodium sulfite in the step S2 is 250-300:0.7-1.2:0.5-1.2; the temperature of the secondary temperature control reaction is 93-98 ℃ and the time is 2-3.5h; the pH control is specifically to add sodium carbonate to control the pH value to be 1.5-2.0.
7. The method for producing cobalt chloride by using low-grade cobalt slag according to claim 1, wherein the adding of concentrated sulfuric acid and sodium sulfite to the mixture in the step S2 is performed in an alkali liquor spray scrubber, and the alkali liquor in the alkali liquor spray scrubber comprises any one of sodium hydroxide with a concentration of 2-5mol/L and calcium hydroxide with a concentration of 2-5.5 mol/L.
8. The method for producing cobalt chloride by utilizing low-grade cobalt slag according to claim 1, wherein in the step S3, the concentration of hydrochloric acid added in the reflux cobalt washing, the primary back extraction and the secondary back extraction is 10mol/L, and the volume ratio of raffinate A to hydrochloric acid is 1:1-2; the volume ratio of the cobalt washing liquid to the hydrochloric acid is 1:1-1.5; the volume ratio of the back extraction liquid A to the hydrochloric acid is 1:1-2; the saponified solution is a saponified solution obtained by saponifying a P-204 sulfonated kerosene solution with an organic phase of 25% by adopting sodium hydroxide, and the saponification rate is 80-90%.
9. The method for producing cobalt chloride by using low-grade cobalt slag according to claim 1, wherein the volume ratio of the raffinate B to the sulfuric acid in the step S4 is 1:1.5-2; the volume ratio of the nickel washing liquid to the hydrochloric acid is 1:1.5-2.5; the volume ratio of the stripping solution C to the deionized water to the sodium hydroxide is 1:1-2:2-3.
10. The method for producing cobalt chloride by utilizing low-grade cobalt slag according to claim 9, wherein the concentration of sulfuric acid is 40-45g/L; the concentration of the hydrochloric acid is 80-85g/L.
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