CN107739059A - A kind of method that nonferrous heavy metal material prepares battery level sulphate - Google Patents
A kind of method that nonferrous heavy metal material prepares battery level sulphate Download PDFInfo
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- CN107739059A CN107739059A CN201710774018.0A CN201710774018A CN107739059A CN 107739059 A CN107739059 A CN 107739059A CN 201710774018 A CN201710774018 A CN 201710774018A CN 107739059 A CN107739059 A CN 107739059A
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- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 58
- 239000007769 metal material Substances 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 38
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 title claims abstract description 30
- 229910021653 sulphate ion Inorganic materials 0.000 title claims abstract description 25
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000001704 evaporation Methods 0.000 claims abstract description 30
- 239000000047 product Substances 0.000 claims abstract description 26
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000002386 leaching Methods 0.000 claims abstract description 19
- 239000007800 oxidant agent Substances 0.000 claims abstract description 19
- 230000003647 oxidation Effects 0.000 claims abstract description 19
- 230000001590 oxidative effect Effects 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 14
- 239000010941 cobalt Substances 0.000 claims abstract description 14
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 14
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052802 copper Inorganic materials 0.000 claims abstract description 12
- 239000010949 copper Substances 0.000 claims abstract description 12
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 12
- 239000011701 zinc Substances 0.000 claims abstract description 12
- 239000011133 lead Substances 0.000 claims abstract description 11
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011135 tin Substances 0.000 claims abstract description 8
- 229910052718 tin Inorganic materials 0.000 claims abstract description 8
- 150000004965 peroxy acids Chemical class 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 230000008020 evaporation Effects 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 22
- 238000000926 separation method Methods 0.000 claims description 22
- 239000007787 solid Substances 0.000 claims description 22
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 20
- 239000000706 filtrate Substances 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 230000035484 reaction time Effects 0.000 claims description 12
- 239000013078 crystal Substances 0.000 claims description 10
- 239000012535 impurity Substances 0.000 claims description 10
- 239000002562 thickening agent Substances 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 8
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 claims description 7
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 claims description 7
- 239000012141 concentrate Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052744 lithium Inorganic materials 0.000 abstract description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract description 3
- 229910052708 sodium Inorganic materials 0.000 abstract description 3
- 239000011734 sodium Substances 0.000 abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 2
- 238000011090 industrial biotechnology method and process Methods 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 11
- 230000008569 process Effects 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical group [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 3
- 229940053662 nickel sulfate Drugs 0.000 description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 3
- 238000006396 nitration reaction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 2
- 229940044175 cobalt sulfate Drugs 0.000 description 2
- UGWKCNDTYUOTQZ-UHFFFAOYSA-N copper;sulfuric acid Chemical compound [Cu].OS(O)(=O)=O UGWKCNDTYUOTQZ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000013601 eggs Nutrition 0.000 description 2
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 2
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- WQSRXNAKUYIVET-UHFFFAOYSA-N sulfuric acid;zinc Chemical compound [Zn].OS(O)(=O)=O WQSRXNAKUYIVET-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical group [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- HIRWGWMTAVZIPF-UHFFFAOYSA-N nickel;sulfuric acid Chemical compound [Ni].OS(O)(=O)=O HIRWGWMTAVZIPF-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000001180 sulfating effect Effects 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical group [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/10—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G19/00—Compounds of tin
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G21/00—Compounds of lead
- C01G21/20—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/10—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/10—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/06—Sulfates
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a kind of method that nonferrous heavy metal material prepares battery level sulphate, mainly include the following steps that：The dissolving of high temperature peracid plus water heat exchange, Oxidation Leaching, evaporating, concentrating and crystallizing, washing drying.The product that the present invention obtains is mainly LITHIUM BATTERY sulfate product, and sodium, nitrogen content are low, and crystallite size distribution is more than 2.0 microns.This method is by adding water heat exchange is rapid to reduce reaction temperature, suitable temperature is provided for the oxidation reaction of heat release, accelerate the reaction rate of oxidant dissolving metalliferous material, this not only shortens the production cycle of industrial technique at present, the utilization rate of metalliferous material can be greatly improved, and reduces processing cost and there is the characteristics of efficient stable.The method that the nonferrous heavy metal material of the present invention prepares battery level sulphate has vast potential for future development, and is applied to following nonferrous heavy metal material：Copper, nickel, cobalt, zinc, lead and tin.
Description
Technical field
The present invention relates to battery material technical field, particularly a kind of nonferrous heavy metal material prepares battery level sulphate
Method.
Background technology
Nonferrous heavy metal is more than 4.5g/cm including non-ferrous metal Midst density3Non-ferrous metal, as copper, nickel, cobalt, lead, zinc,
Tin, antimony, mercury etc..And common are color heavy metal mainly has copper, nickel, cobalt, zinc and lead.At present, it is continuous with New Energy Industry
Heating, the attention rate on nickel, cobalt, lead improve constantly, will focus on introduce nickel cobalt metal below.
Nonferrous heavy metal sulfate is widely used in the industrial circles such as chemical industry, light industry, machinery, oil, battery, in recent years
Come, with the fast development of new material, New Energy Industry, battery material and its manufacturing technology are constantly updated and replaced, battery industry
Tremendous development is obtained.The new-energy automobile volume of production and marketing especially promoted by country drives, huge to have stimulated to electrokinetic cell and phase
Close the demand of material, and electrokinetic cell is at present mainly based on ternary material battery, nickel cobalt metal be even more wherein content highest, make
With the element of maximum.Therefore the higher electrolytic nickel of home costs, the manufacturing enterprise of cobalt make the transition one after another produces nickel sulfate, cobaltous sulfate production
Product.
China produces technical grade sulfuric acid nickel at present, there is Jinchuan in the producer of cobaltous sulfate, Ji En, golden jade-like stone and some with byproduct
The medium-sized and small enterprises of sale.The producer that battery level sulphate can wherein be produced is then very few, technical grade sulfuric acid salt and battery
The difference of level sulphate is impurity content difference and pattern particle requirement, and the raw material of industrialization production battery level sulphate is not
Together, its technique also differs widely.
Current most common raw material is exactly nonferrous heavy metal material, main to be dissolved using three kinds of methods：1st, the direct acid-hatching of young eggs；
2nd, electrolysis；3rd, molten method is heated.
The direct acid-hatching of young eggs can obtain technical grade sulfuric acid salt, but because sulfuric acid or nitration mixture are reacted to certain journey with metalliferous material
After degree, acidity reduce can influence its reaction rate, though therefore the process processing cost it is relatively low and simple and convenient；But it is former
Expect that impurity requires higher, reaction time is longer.The production efficiency of electrolysis is higher, metalliferous material utilization rate is also higher, but work
Higher equipment investment and requirement are needed in industry.Molten method is heated mainly by high-temperature process, or by sulfating roasting,
Nonferrous heavy metal is converted into sulfate, then by being dissolved in water, obtain impure sulfate liquor, pyrogenic process must produce greatly
Waste gas is measured, and energy consumption is higher.Therefore LITHIUM BATTERY sulfate product is prepared, then existing method must be upgraded and be dropped
Low process costs.
Chinese invention patent CN101863520（A kind of preparation method of microporous ultrafine high activity nickel carbonate）Middle use is mixed
The method processing metallic nickel that acid directly leaches, then prepares nickelous carbonate by Compressed CO_2 and precipitating reagent.Nitration mixture is used in this method
Metallic nickel is dissolved, the complex salt for generating nickel can be caused, be not suitable for during preparing battery grade cobalt sulfate, this can not only be added
Impurity, and the anion of nitration mixture is mingled with the quality that can have a strong impact on product.
Existing technology, should mainly using the process production battery level sulphate of the direct acidleach of nonferrous heavy metal material
Do not add other chemical reagent in technique productions course of dissolution, the surface reaction rate of sulfuric acid and dissolving with hydrochloric acid nonferrous heavy metal compared with
Slowly, therefore industrially using nitric acid or perchloric acid as mixing addition acid, and hydrogen-oxygen can be added when controlling terminal acidity
Change sodium solution regulation, metals content impurity can not be guaranteed.The process can cause following shortcoming：1st, the production cycle compared with
Length, production efficiency are relatively low.2nd, the sodium of technical grade sulfuric acid product salt, nitrogen content are higher.3rd, for the purity of nonferrous heavy metal raw material
It is it is required that higher.4th, the utilization rate of nonferrous heavy metal is not universal high.And electrolysis dissolving nonferrous heavy metal material prepares LITHIUM BATTERY sulphur
The technique of hydrochlorate product then needs higher equipment investment and operation difficulty higher.
The content of the invention
The main purpose of the present invention is the provision of a kind of method that nonferrous heavy metal material prepares battery level sulphate,
With the characteristics of technological operation is simple, circulation production and cost is cheap.
The present invention can be achieved through the following technical solutions：
The invention discloses a kind of method that nonferrous heavy metal material prepares battery level sulphate, comprise the following steps：
Step 1, the dissolving of high temperature peracid：Weigh nonferrous heavy metal material and be put into reactor, be passed through steam heating and keeping temperature, add
Enter the sulfuric acid solution of high concentration, the reaction time is 4-8 hours；
Step 2 plus water heat exchange：Pure water is added, dilute solution to designated volume, the temperature of regulation Oxidation Leaching reaction, specifies body
The mass concentration of long-pending Numerical Control nonferrous heavy metal is 80-120g/L；
Step 3, Oxidation Leaching：Be continuously added into oxidant in a kettle, when reach home pH value after stop add oxidant, institute
It is 3.0-6.0 to state endpoint pH；
Step 4, separation of solid and liquid, filter residue direct circulation return to reactor, and filtrate enters thickener；
Step 5, evaporating, concentrating and crystallizing：Heating evaporation concentrates, and cooling separates out separation of solid and liquid after nickel sulfate hexahydrate crystal, and filtrate returns to concentration
Groove；
Step 6, washing and drying：Washed with 95% ethanol and obtain battery after 90-110 °C of drying in vacuum drying oven
Level sulphate product.
Further, the metallic element of the nonferrous heavy metal material is copper, nickel, cobalt, zinc, lead and tin, described coloured heavy
Metalliferous material is shaped as block or powdery, and major metal content >=99.8%, impurity content in the nonferrous heavy metal material≤
0.2%。
Further, in step 1, the keeping temperature is 95-100 DEG C, H in the high concentrated acid solution+Concentration is 6-
10mol/L, wherein metalliferous material and H2SO4Total moles ratio be 1.0-1.3:1.
Further, described oxidant is hydrogen peroxide or drift ice.
Further, the evaporation and concentration temperature is 95-98 DEG C, and chilling temperature is 35-40 DEG C, and striking point is solution ripple
U.S. degree reaches 45-55 DEG C.
The method that nonferrous heavy metal material of the present invention prepares battery level sulphate has following beneficial technique effect：
Compared with existing process technology, the present invention has that process cycle is shorter, reaction efficiency is higher, saves at time and reduction
The advantages of managing cost, the recyclable return first step of filter residue is leached, and evaporate mother liquor and be also recycled to evaporating, concentrating and crystallizing section, it is real
Pollution-free, recycling economy theory is showed, and there is more preferable adaptability and stability.And compared with electrolysis, the present invention
Processing cost it is relatively low, the input of equipment and require also can be lower.Therefore, Oxidation Leaching method of the invention provides a kind of letter
Single feasible nonferrous heavy metal material prepares the process of battery level sulphate.
Embodiment
In order that those skilled in the art will better understand the technical solution of the present invention, with reference to embodiment and to this
Invention product is described in further detail.
Embodiment 1
The invention discloses a kind of method that nonferrous heavy metal material prepares battery level sulphate, comprise the following steps：
Step 1, the dissolving of high temperature peracid：Weigh nonferrous heavy metal material and be put into reactor, be passed through steam heating and keeping temperature, add
Enter the sulfuric acid solution of high concentration, the reaction time is 5 hours；
Step 2 plus water heat exchange：Pure water is added, dilute solution to designated volume, the temperature of regulation Oxidation Leaching reaction, specifies body
The mass concentration of long-pending Numerical Control nonferrous heavy metal is 90g/L；
Step 3, Oxidation Leaching：Be continuously added into oxidant in a kettle, when reach home pH value after stop add oxidant, institute
Endpoint pH is stated as 5；
Step 4, separation of solid and liquid, filter residue direct circulation return to reactor, and filtrate enters thickener；
Step 5, evaporating, concentrating and crystallizing：Heating evaporation concentrates, and cooling separates out separation of solid and liquid after nickel sulfate hexahydrate crystal, and filtrate returns to concentration
Groove；
Step 6, washing and drying：Washed with 95% ethanol and obtain battery after 90-110 °C of drying in vacuum drying oven
Level sulphate product.
In the present embodiment, the metallic element of the nonferrous heavy metal material is copper, nickel, cobalt, zinc, lead and tin, described to have
Color heavy metal material shapes are block or powdery, major metal content >=99.8%, impurity content in the nonferrous heavy metal material
≤0.2%.In step 1, the keeping temperature is 99 DEG C, H in the high concentrated acid solution+Concentration is 9mol/L, wherein metal object
Material and H2SO4Total moles ratio be 1.1:1.The oxidant is hydrogen peroxide or drift ice.The evaporation and concentration temperature is 96 DEG C, cold
But temperature is 38 DEG C, and striking point is that solution Baume degrees reaches 48 DEG C.
Embodiment 2
The invention discloses a kind of method that nonferrous heavy metal material prepares battery level sulphate, comprise the following steps：
Step 1, the dissolving of high temperature peracid：Weigh nonferrous heavy metal material and be put into reactor, be passed through steam heating and keeping temperature, add
Enter the sulfuric acid solution of high concentration, the reaction time is 8 hours；
Step 2 plus water heat exchange：Pure water is added, dilute solution to designated volume, the temperature of regulation Oxidation Leaching reaction, specifies body
The mass concentration of long-pending Numerical Control nonferrous heavy metal is 100g/L；
Step 3, Oxidation Leaching：Be continuously added into oxidant in a kettle, when reach home pH value after stop add oxidant, institute
Endpoint pH is stated as 3.0；
Step 4, separation of solid and liquid, filter residue direct circulation return to reactor, and filtrate enters thickener；
Step 5, evaporating, concentrating and crystallizing：Heating evaporation concentrates, and cooling separates out separation of solid and liquid after nickel sulfate hexahydrate crystal, and filtrate returns to concentration
Groove；
Step 6, washing and drying：Washed with 95% ethanol and obtain LITHIUM BATTERY sulphur after 110 °C of drying in vacuum drying oven
Hydrochlorate product.
In the present embodiment, the metallic element of the nonferrous heavy metal material is copper, nickel, cobalt, zinc, lead and tin, described to have
Color heavy metal material shapes are block or powdery, major metal content >=99.8%, impurity content in the nonferrous heavy metal material
≤0.2%.In step 1, the keeping temperature is 98 DEG C, H in the high concentrated acid solution+Concentration is 6mol/L, wherein metal object
Material and H2SO4Total moles ratio be 1.3:1.The oxidant is hydrogen peroxide or drift ice.The evaporation and concentration temperature is 96 DEG C, cold
But temperature is 35 DEG C, and striking point is that solution Baume degrees reaches 55 DEG C.
Embodiment 3
The invention discloses a kind of method that nonferrous heavy metal material prepares battery level sulphate, comprise the following steps：
Step 1, the dissolving of high temperature peracid：Weigh nonferrous heavy metal material and be put into reactor, be passed through steam heating and keeping temperature, add
Enter the sulfuric acid solution of high concentration, the reaction time is 6 hours；
Step 2 plus water heat exchange：Pure water is added, dilute solution to designated volume, the temperature of regulation Oxidation Leaching reaction, specifies body
The mass concentration of long-pending Numerical Control nonferrous heavy metal is 80g/L；
Step 3, Oxidation Leaching：Be continuously added into oxidant in a kettle, when reach home pH value after stop add oxidant, institute
Endpoint pH is stated as 6.0；
Step 4, separation of solid and liquid, filter residue direct circulation return to reactor, and filtrate enters thickener；
Step 5, evaporating, concentrating and crystallizing：Heating evaporation concentrates, and cooling separates out separation of solid and liquid after nickel sulfate hexahydrate crystal, and filtrate returns to concentration
Groove；
Step 6, washing and drying：Washed with 95% ethanol and obtain LITHIUM BATTERY sulphur after 100 °C of drying in vacuum drying oven
Hydrochlorate product.
In the present embodiment, the metallic element of the nonferrous heavy metal material is copper, nickel, cobalt, zinc, lead and tin, described to have
Color heavy metal material shapes are block or powdery, major metal content >=99.8%, impurity content in the nonferrous heavy metal material
≤0.2%.In step 1, the keeping temperature is 95 DEG C, H in the high concentrated acid solution+Concentration is 10mol/L, wherein metal
Material and H2SO4Total moles ratio be 1.15:1.The oxidant is hydrogen peroxide or drift ice.The evaporation and concentration temperature is 95 DEG C,
Chilling temperature is 40 DEG C, and striking point is that solution Baume degrees reaches 50 DEG C.
Embodiment 4
The invention discloses a kind of method that nonferrous heavy metal material prepares battery level sulphate, comprise the following steps：
Step 1, the dissolving of high temperature peracid：Weigh nonferrous heavy metal material and be put into reactor, be passed through steam heating and keeping temperature, add
Enter the sulfuric acid solution of high concentration, the reaction time is 4 hours；
Step 2 plus water heat exchange：Pure water is added, dilute solution to designated volume, the temperature of regulation Oxidation Leaching reaction, specifies body
The mass concentration of long-pending Numerical Control nonferrous heavy metal is 120g/L；
Step 3, Oxidation Leaching：Be continuously added into oxidant in a kettle, when reach home pH value after stop add oxidant, institute
Endpoint pH is stated as 4.5；
Step 4, separation of solid and liquid, filter residue direct circulation return to reactor, and filtrate enters thickener；
Step 5, evaporating, concentrating and crystallizing：Heating evaporation concentrates, and cooling separates out separation of solid and liquid after nickel sulfate hexahydrate crystal, and filtrate returns to concentration
Groove；
Step 6, washing and drying：Washed with 95% ethanol and obtain LITHIUM BATTERY sulphur after 90 °C of drying in vacuum drying oven
Hydrochlorate product.
In the present embodiment, the metallic element of the nonferrous heavy metal material is copper, nickel, cobalt, zinc, lead and tin, described to have
Color heavy metal material shapes are block or powdery, major metal content >=99.8%, impurity content in the nonferrous heavy metal material
≤0.2%.In step 1, the keeping temperature is 100 DEG C, H in the high concentrated acid solution+Concentration is 8mol/L, wherein metal
Material and H2SO4Total moles ratio be 1.0:1.The oxidant is hydrogen peroxide or drift ice.The evaporation and concentration temperature is 98 DEG C,
Chilling temperature is 37 DEG C, and striking point is that solution Baume degrees reaches 45 DEG C.
Application Example 1
Step 1, weigh and metallic nickel is added in beaker（Powdery）110g, add 7mol/L H+ sulfuric acid solution 450mL, electricity
Hot stove heats and maintains the temperature at 95 °C, and the reaction time is 4 hours；
Step 2, addition pure water are diluted to designated volume 900mL, and can adjust Oxidation Leaching reaction temperature is about 65 °C；
Step 3, hydrogen peroxide is continuously added into beaker, stops adding when endpoint pH reaches 4.0；
Filtrate is put into concentration beaker after step 4, separation of solid and liquid, and heating evaporation is concentrated into Baume degrees as 45 degree, is cooled to 35 °C：
Step 5, using centrifuge separation of solid and liquid after, filter residue is nickel sulfate hexahydrate crystal, is washed and in vacuum with 95% ethanol after taking-up
Drying can obtain LITHIUM BATTERY nickel sulfate product in 90 °C in baking oven.The D50 of the product is 2.0 microns, chemical composition such as table 1 below
It is shown：
The chemical component table of table 1
In the present embodiment, described metallic nickel and H2SO4Mol ratio be about 1.2, be diluted to the quality of nickel after designated volume
Concentration is about 100g/L, and the temperature of evaporation and concentration remains 93 °C, NiSO in nickel sulfate content4•H2O content meets >=98%.
Application Example 2
Step 1, weigh and add metallic cobalt in a kettle（It is block）2 tons, 9mol/L H+ sulfuric acid solution 7m3 is added, is passed through
Steam heats and maintains the temperature at 93 °C, and the reaction time is 6 hours；
Step 2, addition pure water are diluted to designated volume 15m3, and regulation Oxidation Leaching reaction temperature is about 60 °C；
Step 3, drift ice is continuously added into a kettle（HClO）, stop adding when endpoint pH reaches 3.5；
Filtrate is put into thickener after step 4, separation of solid and liquid, is heated to 90 °C, and it is 48 degree to be concentrated by evaporation to Baume degrees, is cooled to
40°C：
Step 5, using centrifuge separation of solid and liquid after, filter residue is cobaltous sulfate crystal, is washed and in vacuum with 95% ethanol after taking-up
Drying can obtain battery grade cobalt sulfate product in 100 °C in baking oven.The D50 of the product is 2.5 microns, chemical composition such as following table
Shown in 2；
The chemical component table of table 2
In the present embodiment, described metallic cobalt and H2SO4Mol ratio be about 1.08, cobalt quality is dense after being diluted to designated volume
Degree is about 90g/L, and the temperature of evaporation and concentration remains 95 °C, CoSO in cobaltous sulfate product4•H2O content meets >=99%.
Application Example 3
Step 1, weigh and add metallic zinc in a kettle（Powdery）5 tons, 9mol/L H+ sulfuric acid solution 16m3 is added, is led to
Enter steam to heat and maintain the temperature at 90 °C, the reaction time is 8 hours；
Step 2, addition pure water are diluted to designated volume 40m3, and regulation Oxidation Leaching reaction temperature is about 70 °C；
Step 3, hydrogen peroxide is continuously added into a kettle, stop adding when endpoint pH reaches 4.5；
Filtrate is put into thickener after step 4, separation of solid and liquid, is heated to 98 °C, and it is 55 degree to be concentrated by evaporation to Baume degrees, is cooled to
38°C：
Step 5, using centrifuge separation of solid and liquid after, filter residue is zinc sulfate crystal, is washed and in vacuum with 95% ethanol after taking-up
Drying can obtain LITHIUM BATTERY sulfuric acid zinc product in 105 °C in baking oven.The D50 of the product is 3.0 microns, chemical composition such as following table
Shown in 3；
The chemical component table of table 3
In the present embodiment, described metallic zinc and H2SO4Mol ratio be about 1.06, zinc concentration is about after being diluted to designated volume
For 110g/L, the temperature of evaporation and concentration remains 98 °C, the ZnSO of sulfuric acid zinc product4•H2O content meets >=98%.
Application Example 4
Step 1, weigh and add metallic lead in a kettle（Powdery）4.5 tons, 6mol/L H+ sulfuric acid solution 8m3 is added, is led to
Enter steam to heat and maintain the temperature at 90 °C, the reaction time is 6 hours；
Step 2, addition pure water are diluted to designated volume 25m3, and regulation Oxidation Leaching reaction temperature is about 50 °C；
Step 3, hydrogen peroxide is continuously added into a kettle, stop adding when endpoint pH reaches 4.5；
Filtrate is put into thickener after step 4, separation of solid and liquid, is heated to 98 °C, and it is 55 degree to be concentrated by evaporation to Baume degrees, is cooled to
38°C：
Step 5, using centrifuge separation of solid and liquid after, filter residue is lead sulfate precipitation, is washed and in vacuum with 95% ethanol after taking-up
Drying can obtain LITHIUM BATTERY lead sulfate product in 105 °C in baking oven.Chemical composition is as shown in table 4 below；
The chemical component table of table 4
In the present embodiment, described metallic lead and H2SO4Mol ratio be about 1.12, lead quality is dense after being diluted to designated volume
Degree is about 150g/L, and the temperature of evaporation and concentration remains 98 °C, the PbSO of lead sulfate product4Content meets >=99.0%.
Application Example 5
Step 1, weigh and add metallic copper in a kettle（It is block）4 tons, 7mol/L H+ sulfuric acid solution 9.7m3 is added, is led to
Enter steam to heat and maintain the temperature at 90 °C, the reaction time is 4 hours；
Step 2, addition pure water are diluted to designated volume 25m3, and regulation Oxidation Leaching reaction temperature is about 50 °C；
Step 3, hydrogen peroxide is continuously added into a kettle, stop adding when endpoint pH reaches 4.5；
Filtrate is put into thickener after step 4, separation of solid and liquid, is heated to 98 °C, and it is 55 degree to be concentrated by evaporation to Baume degrees, is cooled to
38°C：
Step 5, using centrifuge separation of solid and liquid after, filter residue is copper sulfate crystal, is washed and in vacuum with 95% ethanol after taking-up
Drying can obtain LITHIUM BATTERY sulfuric acid copper products in 105 °C in baking oven.The D50 of the product is 2.0 microns, chemical composition such as following table
Shown in 5；
The chemical component table of table 5
In the present embodiment, described metallic copper and H2SO4Mol ratio be about 1.25, be diluted to the quality of copper after designated volume
Concentration is about 130g/L, and the temperature of evaporation and concentration remains 98 °C, the CuSO of sulfuric acid copper products4•H2O content meets >=98.0%.
The foregoing is only a preferred embodiment of the present invention, not makees any formal limitation to the present invention；It is all
The those of ordinary skill of the industry can be shown in by specification and described above and swimmingly implement the present invention；It is but all familiar
Professional and technical personnel without departing from the scope of the present invention, makes using disclosed above technology contents
A little variation, modification and evolution equivalent variations, be the present invention equivalent embodiment；Meanwhile all realities according to the present invention
Variation, modification and evolution of any equivalent variations that matter technology is made to above example etc., still fall within the technology of the present invention
Within the protection domain of scheme.
Claims (5)
1. a kind of method that nonferrous heavy metal material prepares battery level sulphate, it is characterised in that comprise the following steps：
Step 1, the dissolving of high temperature peracid：Weigh nonferrous heavy metal material and be put into reactor, be passed through steam heating and keeping temperature, add
Enter the sulfuric acid solution of high concentration, the reaction time is 4-8 hours；
Step 2 plus water heat exchange：Pure water is added, dilute solution to designated volume, the temperature of regulation Oxidation Leaching reaction, specifies body
The mass concentration of long-pending Numerical Control nonferrous heavy metal is 80-120g/L；
Step 3, Oxidation Leaching：Be continuously added into oxidant in a kettle, when reach home pH value after stop add oxidant, institute
It is 3.0-6.0 to state endpoint pH；
Step 4, separation of solid and liquid, filter residue direct circulation return to reactor, and filtrate enters thickener；
Step 5, evaporating, concentrating and crystallizing：Heating evaporation concentrates, and cooling separates out separation of solid and liquid after nickel sulfate hexahydrate crystal, and filtrate returns to concentration
Groove；
Step 6, washing and drying：Washed with 95% ethanol and obtain battery after 90-110 °C of drying in vacuum drying oven
Level sulphate product.
2. the method that nonferrous heavy metal material according to claim 1 prepares battery level sulphate, it is characterised in that：It is described
The metallic element of nonferrous heavy metal material is copper, nickel, cobalt, zinc, lead and tin, and the nonferrous heavy metal material shapes are block or powder
Shape, major metal content >=99.8%, impurity content≤0.2% in the nonferrous heavy metal material.
3. the method that nonferrous heavy metal material according to claim 1 or 2 prepares battery level sulphate, it is characterised in that：
In step 1, the keeping temperature is 95-100 DEG C, H in the high concentrated acid solution+Concentration is 6-10mol/L, wherein metal object
Material and H2SO4Total moles ratio be 1.0-1.3:1.
4. the method that nonferrous heavy metal material according to claim 3 prepares battery level sulphate, it is characterised in that：It is described
Oxidant be hydrogen peroxide or drift ice.
5. the method that nonferrous heavy metal material according to claim 4 prepares battery level sulphate, it is characterised in that：It is described
It is 95-98 DEG C to be concentrated by evaporation temperature, and chilling temperature is 35-40 DEG C, and striking point is that solution Baume degrees reaches 45-55 DEG C.
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| WO2021105365A1 (en) * | 2019-11-27 | 2021-06-03 | Solvay Sa | A process for manufacturing nickel sulphate |
| CN113195418A (en) * | 2018-12-20 | 2021-07-30 | 住友金属矿山株式会社 | Method and apparatus for producing nickel sulfate solution |
| WO2022053448A1 (en) * | 2020-09-09 | 2022-03-17 | Northvolt Ab | Process for preparing battery grade metal sulphate solutions |
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