CN112573592A - Preparation method of high-purity nickel protoxide - Google Patents
Preparation method of high-purity nickel protoxide Download PDFInfo
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- CN112573592A CN112573592A CN202110131371.3A CN202110131371A CN112573592A CN 112573592 A CN112573592 A CN 112573592A CN 202110131371 A CN202110131371 A CN 202110131371A CN 112573592 A CN112573592 A CN 112573592A
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- nickel
- purity
- protoxide
- spray pyrolysis
- nickel protoxide
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 123
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000005118 spray pyrolysis Methods 0.000 claims abstract description 31
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 20
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 15
- 239000010941 cobalt Substances 0.000 claims abstract description 15
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 15
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052742 iron Inorganic materials 0.000 claims abstract description 13
- 239000000460 chlorine Substances 0.000 claims abstract description 11
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000000197 pyrolysis Methods 0.000 claims description 19
- 238000005507 spraying Methods 0.000 claims description 17
- 150000002815 nickel Chemical class 0.000 claims description 14
- 239000012535 impurity Substances 0.000 claims description 13
- 239000012266 salt solution Substances 0.000 claims description 13
- 239000012298 atmosphere Substances 0.000 claims description 12
- 238000006298 dechlorination reaction Methods 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- 239000007921 spray Substances 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 8
- 238000000605 extraction Methods 0.000 claims description 7
- 239000000654 additive Substances 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 6
- 230000008020 evaporation Effects 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 5
- QUXFOKCUIZCKGS-UHFFFAOYSA-N bis(2,4,4-trimethylpentyl)phosphinic acid Chemical compound CC(C)(C)CC(C)CP(O)(=O)CC(C)CC(C)(C)C QUXFOKCUIZCKGS-UHFFFAOYSA-N 0.000 claims description 5
- 238000000746 purification Methods 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 238000003837 high-temperature calcination Methods 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 229920002401 polyacrylamide Polymers 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- BSWXAWQTMPECAK-UHFFFAOYSA-N 6,6-diethyloctyl dihydrogen phosphate Chemical compound CCC(CC)(CC)CCCCCOP(O)(O)=O BSWXAWQTMPECAK-UHFFFAOYSA-N 0.000 claims description 2
- 229920002907 Guar gum Polymers 0.000 claims description 2
- 239000003929 acidic solution Substances 0.000 claims description 2
- 239000000665 guar gum Substances 0.000 claims description 2
- 229960002154 guar gum Drugs 0.000 claims description 2
- 235000010417 guar gum Nutrition 0.000 claims description 2
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 2
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 2
- 229940083575 sodium dodecyl sulfate Drugs 0.000 claims 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims 1
- 239000002351 wastewater Substances 0.000 abstract description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 3
- 239000011575 calcium Substances 0.000 abstract description 3
- 229910052791 calcium Inorganic materials 0.000 abstract description 3
- 230000000382 dechlorinating effect Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 7
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 6
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 229940078494 nickel acetate Drugs 0.000 description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 238000000349 field-emission scanning electron micrograph Methods 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000000696 magnetic material Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910018605 Ni—Zn Inorganic materials 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- RGZVRADFLSQOLD-UHFFFAOYSA-N bis(2,4,4-trimethylpentyl) hydrogen phosphate Chemical compound CC(C)(C)CC(C)COP(O)(=O)OCC(C)CC(C)(C)C RGZVRADFLSQOLD-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 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
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- VQBIMXHWYSRDLF-UHFFFAOYSA-M sodium;azane;hydrogen carbonate Chemical compound [NH4+].[Na+].[O-]C([O-])=O VQBIMXHWYSRDLF-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- NIAGBSSWEZDNMT-UHFFFAOYSA-M tetraoxidosulfate(.1-) Chemical compound [O]S([O-])(=O)=O NIAGBSSWEZDNMT-UHFFFAOYSA-M 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/04—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to a preparation method of high-purity nickel protoxide, which comprises the steps of dechlorinating nickel oxide obtained by spray pyrolysis, and further calcining at high temperature to obtain nickel protoxide powder with higher purity, wherein the nickel protoxide powder does not generate wastewater, has stable process and high product purity, and is prepared by the following steps: more than or equal to 77 percent of nickel, less than or equal to 0.004 percent of cobalt, less than or equal to 0.004 percent of iron, less than or equal to 0.004 percent of calcium and less than or equal to 0.01 percent of chlorine.
Description
Technical Field
The invention belongs to the field of powder materials, and particularly relates to a preparation method of high-purity nickel protoxide.
Background
Nickel protoxide (NiO) appearance: light green or dark green powdery solid, character: the specific gravity of the product is 6.6-6.8; the loose packed density is 0.5-1.5; the tap density is 1.5-2.0; the Fisher size is 2-5; insoluble in water, and soluble in sulfuric acid, hydrochloric acid, nitric acid, and ammonia water. The application is as follows: the nickel protoxide powder material is widely applied to the fields of battery materials, catalyst materials, magnetic materials, electronic materials, ceramics, glass and the like. The adhesive and colorant used as enamel in ceramic industry is the raw material used as pigment in ceramic industry. Used as raw material of Ni-Zn ferrite in the production of magnetic materials, as colorant of brown glass and glass bulb of kinescope in glass industry, and as material for making nickel salt, nickel catalyst and secondary battery.
The common preparation method of nickel protoxide is to adopt a solution precipitation and calcination method, namely soluble nickel metal salt (such as chloride and sulfate) is used as a raw material, then precipitator (such as carbonate and sodium hydroxide) is added to obtain nickel-containing precipitate, and the precipitate is calcined to obtain nickel protoxide.
Most factories use nickel sulfate as raw material, sodium carbonate and ammonium bicarbonate as precipitant and complexing agent, and adopt complex precipitation method to prepare nickel carbonate, and nickel protoxide is obtained through filtering, washing, drying and calcining.
The nickel protoxide prepared by the method has the problems of uneven granularity, agglomeration, relatively high impurity content (for example, serious sulfate radical and sodium ion coating), unstable batch and the like. And the synthesized tail solution contains a large amount of ammonium radicals, chloride radicals, sulfate radicals and the like. Meanwhile, in order to remove impurities in the precipitate, a large amount of washing water is consumed, a large amount of wastewater is generated, and the environment is polluted.
In addition, some manufacturers in China have adopted spray pyrolysis technology to produce nickel protoxide powder, and the method is to use the prepared metal nickel chloride solution as a precursor, send the precursor into a centrifugal mechanical nozzle under the conveying of a high-pressure pump, form jet flow, and enter a high-temperature atmosphere to carry out spray pyrolysis to produce the nickel protoxide powder. The method adopts a mechanical centrifugal nozzle, and uses a pump to pressurize to form jet flow, and the jet flow enters a high-temperature atmosphere to carry out spray pyrolysis to produce the nickel protoxide.
Because the thermal decomposition temperature of nickel chloride is high, the chlorine radical in the nickel oxide obtained by spray pyrolysis is often more than 1000ppm, air pollution can be caused when the nickel protoxide is prepared by subsequent high-temperature calcination, equipment is seriously corroded, and the battery gas generation is more serious when the nickel protoxide is used as a battery material due to the residual chlorine radical.
The nickelous oxide produced by the domestic existing spray pyrolysis technology has low purity and poor particle dispersibility, and the fineness of the nickelous oxide cannot meet the requirements of high-end manufacturing industry.
How to find a proper preparation method and a modification technology thereof to ensure that the prepared nickel protoxide meets the requirements of uniform granularity, good dispersibility, high purity and stable batch is the key point of current research.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method of high-purity nickel protoxide, which comprises the following steps of dechlorinating nickel oxide obtained by spray pyrolysis, and further calcining at high temperature to obtain nickel protoxide powder with higher purity, wherein no wastewater is generated, the process is stable, the product purity is high, and the preparation method comprises the following steps: more than or equal to 77 percent of nickel, less than or equal to 0.004 percent of cobalt, less than or equal to 0.004 percent of iron, less than or equal to 0.004 percent of calcium and less than or equal to 0.01 percent of chlorine.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a preparation method of high-purity nickel protoxide is realized by the following steps:
step 1, selecting nickel soluble salt as a raw material, and adding pure water to prepare a nickel salt solution with the concentration of 1.7-2.5 mol/L;
step 2, purifying the nickel salt solution obtained in the step 1;
step 3, adding the nickel salt solution into a spray pyrolysis device;
step 4, starting the spray pyrolysis device to prepare nickel oxide;
step 5, feeding the nickel oxide prepared in the step 4 into a dechlorination device;
and 6, calcining the dechlorinated nickel oxide in the step 5 at high temperature to obtain high-purity nickel protoxide powder.
In the preparation method of the high-purity nickel protoxide, in the step 1, the nickel soluble salt is one or more of nitrate, acetate and chloride.
In the step 2 of the preparation method of the high-purity nickel protoxide, cobalt is removed by adopting an extraction process in the purification treatment, the cobalt is removed to be below 0.005g/L, the pH is adjusted to be 4.0-4.6, iron impurities are removed, and a nickel salt solution with the iron content of below 0.005g/L is obtained after filtration.
When the extraction process is adopted for removing cobalt, the extracting agent is one or two of P507 and Cyanex272, wherein the chemical formula of P507 is 2-ethylhexyl phosphate mono-2-ethylhexyl ester, and the chemical formula of Cyanex272 is di (2, 4, 4-trimethylpentyl) phosphate.
In the preparation method of the high-purity nickel protoxide, in the step 4, the spray pressure of a spray pyrolysis device is set to be 0.2-1.0 MPa, the pyrolysis temperature is 600-950 ℃, and the pyrolysis atmosphere is air or oxygen atmosphere.
In the step 5, the dechlorination device adopts water spray evaporation to remove chlorine, the nickel oxide obtained by spray pyrolysis at the temperature of 600-950 ℃ is mixed with pure water sprayed from the spraying device, and the chlorine, nitrate and acetate impurities in the nickel oxide particles are taken away by the quick evaporation of the pure water.
In the preparation method of the high-purity nickel protoxide, in the step 6, the high-temperature calcination temperature is 700-1200 ℃, and nickel oxide is completely converted into nickel protoxide at the temperature.
In the preparation method of the high-purity nickel protoxide, in the step 4, the tail gas generated by spray pyrolysis is leached to prepare the acidic solution.
In the step 3, when the nickel salt solution is added into the spray pyrolysis device, a proper amount of additive is added, wherein the additive is one or more of polyethylene glycol, polyacrylamide, guar gum, triethylhexylphosphoric acid, sodium dodecyl sulfate and sodium hexametaphosphate, the viscosity and the surface tension of the spray solution can be further adjusted, and the spray pyrolysis reaction is favorably carried out.
In the preparation method of the high-purity nickel protoxide, the additive accounts for 0.2-2.0% of the total mass of the solution.
The invention has the beneficial effects that: a preparation method of high-purity nickel protoxide, on one hand, solve the multiple problems such as uneven granularity of products prepared by present solution precipitation + calcining method, reunion, high impurity content, batch instability, etc., and avoid the production of waste water, compared with liquid phase precipitation method, the spray pyrolysis method has the advantages of short preparation time, large yield, low cost, no pollution, adjustable particle size, narrow particle size distribution, easy doping, easy control of element distribution uniformity, etc.; on the other hand, the problem that the purity of the nickel protoxide prepared by the existing spray pyrolysis technology is not high is solved, the nickel oxide obtained by spray pyrolysis is dechlorinated and then is further calcined at high temperature, the nickel protoxide powder with higher purity is obtained, no wastewater is generated, the process is stable, the product purity is high, and the preparation method comprises the following steps: the high-purity nickel protoxide product with nickel content more than or equal to 77 percent, cobalt content less than or equal to 0.004 percent, iron content less than or equal to 0.004 percent, calcium content less than or equal to 0.004 percent and chlorine content less than or equal to 0.01 percent is added into the spray pyrolysis device, and the viscosity and surface tension of the spray solution can be further adjusted, thereby being beneficial to the implementation of the spray pyrolysis reaction. The method is simple to operate, can be widely applied to the production process of metal oxide powder, and is particularly suitable for the production process of high-purity nickel protoxide powder materials.
Drawings
FIG. 1 is a 4000-fold FESEM image of high purity nickel protoxide prepared in example 1;
FIG. 2 is a 4000-fold FESEM image of high purity nickel protoxide prepared in example 2;
fig. 3 is a 4000-fold FESEM image of high purity nickel protoxide prepared in example 3.
Detailed Description
The following examples are presented to enable those skilled in the art to more fully understand the present invention and are not intended to limit the invention in any way.
Example 1
A preparation method of high-purity nickel protoxide is realized by the following steps:
step 1, selecting nickel nitrate as a raw material, and adding pure water to prepare a 1.7-2.5 mol/L nickel nitrate solution;
step 2, purifying the nickel nitrate solution obtained in the step 1, wherein P507 is adopted as an extractant for extraction and cobalt removal in the purification treatment, the cobalt is removed to be below 0.005g/L, the pH value is adjusted to be 4.0, iron impurities are removed, and a nickel salt solution with the iron content lower than 0.005g/L is obtained after filtration;
step 3, adding the nickel nitrate solution into a spray pyrolysis device, and then adding polyethylene glycol accounting for 0.2% of the total mass of the solution;
step 4, setting the spraying pressure of the spraying pyrolysis device to be 0.2MPa, setting the pyrolysis temperature to be 600 ℃, setting the pyrolysis atmosphere to be air atmosphere, starting the spraying pyrolysis device to prepare nickel oxide, and leaching tail gas generated by spraying pyrolysis to prepare an acid solution;
step 5, feeding the nickel oxide prepared in the step 4 into a dechlorination device; the dechlorination device adopts water spray evaporation to remove chlorine, nickel oxide obtained by spray pyrolysis at the temperature of 600 ℃ is mixed with pure water sprayed from the spraying device, the pure water is quickly evaporated to take away nitrate impurities in nickel oxide particles, and generated tail gas is recovered;
and 6, calcining the dechlorinated nickel oxide obtained in the step 5 at a high temperature of 700 ℃ to obtain high-purity nickel protoxide powder.
Example 2
A preparation method of high-purity nickel protoxide is realized by the following steps:
step 1, selecting nickel chloride as a raw material, and adding pure water to prepare a 2.5mol/L nickel chloride solution;
step 2, purifying the nickel chloride solution obtained in the step 1, wherein the cobalt is removed by extraction by using Cyanex272 as an extractant in the purification treatment, the cobalt is removed to be below 0.005g/L, the pH is adjusted to be 4.6, iron impurities are removed, and a nickel salt solution with the iron content of less than 0.005g/L is obtained after filtration;
step 3, adding the nickel chloride solution into a spray pyrolysis device, and then adding polyacrylamide accounting for 2.0% of the total mass of the solution;
step 4, setting the spraying pressure of the spraying pyrolysis device to be 1.0MPa, setting the pyrolysis temperature to be 950 ℃, setting the pyrolysis atmosphere to be an oxygen atmosphere, starting the spraying pyrolysis device to prepare nickel oxide, and leaching tail gas generated by spraying pyrolysis to prepare an acid solution;
step 5, feeding the nickel oxide prepared in the step 4 into a dechlorination device; the dechlorination device adopts water spray evaporation to remove chlorine, nickel oxide obtained by spray pyrolysis at the temperature of 950 ℃ is mixed with pure water sprayed from the spraying device, the pure water is quickly evaporated to take away chlorine impurities in nickel oxide particles, and generated tail gas is recovered;
and 6, calcining the dechlorinated nickel oxide obtained in the step 5 at 1200 ℃ to obtain high-purity nickel protoxide powder.
Example 3
A preparation method of high-purity nickel protoxide is realized by the following steps:
step 1, selecting nickel acetate soluble salt as a raw material, and adding pure water to prepare a 2.0mol/L nickel acetate solution;
step 2, purifying the nickel acetate solution obtained in the step 1, wherein the cobalt is removed by extraction by using Cyanex272 as an extractant in the purification treatment, the cobalt is removed to be below 0.005g/L, the pH is adjusted to be 4.3, iron impurities are removed, and a nickel salt solution with the iron content of less than 0.005g/L is obtained after filtration;
step 3, adding the nickel acetate solution into a spray pyrolysis device, and then adding sodium dodecyl sulfate accounting for 1.0 percent of the total mass of the solution;
step 4, setting the spraying pressure of the spraying pyrolysis device to be 0.6MPa, setting the pyrolysis temperature to be 780 ℃, setting the pyrolysis atmosphere to be air atmosphere, starting the spraying pyrolysis device to prepare nickel oxide, and leaching tail gas generated by spraying pyrolysis to prepare an acid solution;
step 5, feeding the nickel oxide prepared in the step 4 into a dechlorination device; the dechlorination device adopts water spray evaporation to remove chlorine, nickel oxide obtained by spray pyrolysis at the temperature of 780 ℃ is mixed with pure water sprayed from the spraying device, the pure water is quickly evaporated to take away acetate impurities in nickel oxide particles, and generated tail gas is recovered;
and 6, calcining the dechlorinated nickel oxide obtained in the step 5 at a high temperature of 1000 ℃ to obtain high-purity nickel protoxide powder.
Claims (10)
1. A preparation method of high-purity nickel protoxide is characterized by comprising the following steps:
step 1, selecting nickel soluble salt as a raw material, and adding pure water to prepare a nickel salt solution with the concentration of 1.7-2.5 mol/L;
step 2, purifying the nickel salt solution obtained in the step 1;
step 3, adding the nickel salt solution into a spray pyrolysis device;
step 4, starting the spray pyrolysis device to prepare nickel oxide;
step 5, feeding the nickel oxide prepared in the step 4 into a dechlorination device;
and 6, calcining the dechlorinated nickel oxide in the step 5 at high temperature to obtain high-purity nickel protoxide powder.
2. The method for preparing high-purity nickel protoxide according to claim 1, wherein in the step 1, the nickel soluble salt is one or more of nitrate, acetate and chloride.
3. The method for preparing high-purity nickel protoxide according to claim 1, wherein in the step 2, cobalt is removed by an extraction process in a purification treatment, the cobalt is removed to be below 0.005g/L, the pH is adjusted to be 4.0-4.6, iron impurities are removed, and a nickel salt solution with the iron content of below 0.005g/L is obtained after filtration.
4. The method for preparing high-purity nickel protoxide according to claim 3, wherein when the cobalt is removed by adopting an extraction process, the extractant is one or two of P507 and Cyanex 272.
5. The method for preparing high-purity nickel protoxide according to claim 1, wherein in the step 4, the spray pyrolysis device is set to have a spray pressure of 0.2 to 1.0MPa, a pyrolysis temperature of 600 to 950 ℃, and a pyrolysis atmosphere is an air or oxygen atmosphere.
6. The method for preparing high-purity nickel protoxide according to claim 1, wherein in the step 5, the chlorine removing device removes chlorine by water spray evaporation, the nickel oxide obtained by spray pyrolysis and having a temperature of 600-950 ℃ is mixed with pure water sprayed from the spraying device, and the pure water rapidly evaporates to remove impurities such as chloride, nitrate and acetate in the nickel oxide particles.
7. The method for preparing high-purity nickel protoxide according to claim 1, wherein the high-temperature calcination temperature in the step 6 is 700 to 1200 ℃.
8. The method for preparing high-purity nickel protoxide according to claim 1, wherein in the step 4, the tail gas generated by the spray pyrolysis is leached to prepare an acidic solution.
9. The method of claim 1, wherein in step 3, when the nickel salt solution is fed into the spray pyrolysis apparatus, a proper amount of additive is added, wherein the additive is one or more selected from polyethylene glycol, polyacrylamide, guar gum, triethylhexylphosphoric acid, sodium dodecylsulfate, and sodium hexametaphosphate.
10. The method according to claim 9, wherein the additive is 0.2 to 2.0% by mass of the total solution.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113636608A (en) * | 2021-08-25 | 2021-11-12 | 金川集团股份有限公司 | Preparation method of micron-sized nickel protoxide |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102115215A (en) * | 2011-03-29 | 2011-07-06 | 兰州金川新材料科技股份有限公司 | Preparation method of nickel oxide powder |
| WO2013077296A1 (en) * | 2011-11-22 | 2013-05-30 | 住友金属鉱山株式会社 | Method for producing high-purity nickel sulfate |
| CN204543859U (en) * | 2015-01-14 | 2015-08-12 | 贾坚 | Gas purifying equipment |
| CN105349780A (en) * | 2015-11-20 | 2016-02-24 | 兰州金川新材料科技股份有限公司 | Purification method for nickel electric accumulated liquid for manufacturing high-purity nickel plate |
| CN107385210A (en) * | 2017-07-07 | 2017-11-24 | 金川集团股份有限公司 | A kind of nickel nitrate/cobalt liquor system transition and the method for nitric acid reuse |
| CN108178197A (en) * | 2017-12-14 | 2018-06-19 | 金川集团股份有限公司 | A kind of preparation method of electron level nickel protoxide |
| CN109518006A (en) * | 2018-10-30 | 2019-03-26 | 金川集团股份有限公司 | The minimizing technology of trace cobalt in a kind of nickel chloride solution |
| CN109775768A (en) * | 2019-03-20 | 2019-05-21 | 金川集团股份有限公司 | A method of producing nickel protoxide |
-
2021
- 2021-01-30 CN CN202110131371.3A patent/CN112573592A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102115215A (en) * | 2011-03-29 | 2011-07-06 | 兰州金川新材料科技股份有限公司 | Preparation method of nickel oxide powder |
| WO2013077296A1 (en) * | 2011-11-22 | 2013-05-30 | 住友金属鉱山株式会社 | Method for producing high-purity nickel sulfate |
| CN204543859U (en) * | 2015-01-14 | 2015-08-12 | 贾坚 | Gas purifying equipment |
| CN105349780A (en) * | 2015-11-20 | 2016-02-24 | 兰州金川新材料科技股份有限公司 | Purification method for nickel electric accumulated liquid for manufacturing high-purity nickel plate |
| CN107385210A (en) * | 2017-07-07 | 2017-11-24 | 金川集团股份有限公司 | A kind of nickel nitrate/cobalt liquor system transition and the method for nitric acid reuse |
| CN108178197A (en) * | 2017-12-14 | 2018-06-19 | 金川集团股份有限公司 | A kind of preparation method of electron level nickel protoxide |
| CN109518006A (en) * | 2018-10-30 | 2019-03-26 | 金川集团股份有限公司 | The minimizing technology of trace cobalt in a kind of nickel chloride solution |
| CN109775768A (en) * | 2019-03-20 | 2019-05-21 | 金川集团股份有限公司 | A method of producing nickel protoxide |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113636608A (en) * | 2021-08-25 | 2021-11-12 | 金川集团股份有限公司 | Preparation method of micron-sized nickel protoxide |
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