CN1305617C - Production method of dentritic morphology nickel powder - Google Patents
Production method of dentritic morphology nickel powder Download PDFInfo
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- CN1305617C CN1305617C CNB2005100073164A CN200510007316A CN1305617C CN 1305617 C CN1305617 C CN 1305617C CN B2005100073164 A CNB2005100073164 A CN B2005100073164A CN 200510007316 A CN200510007316 A CN 200510007316A CN 1305617 C CN1305617 C CN 1305617C
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 238000004519 manufacturing process Methods 0.000 title claims description 22
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 42
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 claims abstract description 25
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 21
- 238000000605 extraction Methods 0.000 claims abstract description 16
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 14
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims abstract description 13
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 11
- 150000002500 ions Chemical class 0.000 claims abstract description 9
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000654 additive Substances 0.000 claims abstract description 7
- 230000000996 additive effect Effects 0.000 claims abstract description 7
- 238000003828 vacuum filtration Methods 0.000 claims abstract description 5
- 229910001453 nickel ion Inorganic materials 0.000 claims description 19
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 10
- 229910021529 ammonia Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000005416 organic matter Substances 0.000 claims description 9
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 239000010941 cobalt Substances 0.000 claims description 7
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000006228 supernatant Substances 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- CEYULKASIQJZGP-UHFFFAOYSA-L disodium;2-(carboxymethyl)-2-hydroxybutanedioate Chemical compound [Na+].[Na+].[O-]C(=O)CC(O)(C(=O)O)CC([O-])=O CEYULKASIQJZGP-UHFFFAOYSA-L 0.000 claims description 5
- 238000001179 sorption measurement Methods 0.000 claims description 5
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 3
- 238000012546 transfer Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 22
- 238000002360 preparation method Methods 0.000 abstract description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 11
- 239000013078 crystal Substances 0.000 abstract description 7
- 238000001914 filtration Methods 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 6
- 239000007789 gas Substances 0.000 abstract description 4
- 238000005868 electrolysis reaction Methods 0.000 abstract description 2
- 238000005272 metallurgy Methods 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000843 powder Substances 0.000 abstract description 2
- 230000008021 deposition Effects 0.000 abstract 4
- NBFQLHGCEMEQFN-UHFFFAOYSA-N N.[Ni] Chemical compound N.[Ni] NBFQLHGCEMEQFN-UHFFFAOYSA-N 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 229910001873 dinitrogen Inorganic materials 0.000 abstract 1
- 239000012535 impurity Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 50
- 239000003054 catalyst Substances 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000001764 infiltration Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910000480 nickel oxide Inorganic materials 0.000 description 4
- 241001062472 Stokellia anisodon Species 0.000 description 3
- 239000000696 magnetic material Substances 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 238000001033 granulometry Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000006210 lotion Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 1
- 230000004308 accommodation Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- -1 electrode Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000010407 vacuum cleaning Methods 0.000 description 1
Classifications
-
- 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 present invention relates to a method for preparing dentritic crystal shape nickel powder, particularly to a method for preparing dentritic crystal shape nickel powder, which relates to a method for preparing metal powder by using a wet metallurgy method. The present invention is characterized in that the preparation steps comprise the extraction of a nickel solution, the preparation of a nickel-ammonia complex solution, nickel oxalate deposition, filtration, wash, drying, reduction and crush. A dentritic crystal shape nickel powder product can be obtained. The present invention has the method that a nickel sulphate solution is converted into a nickel chloride solution or a nickel nitrate solution by complete extraction. During the extraction, the solution is simultaneously purified in depth to reduce the contents of various impurity ions. Then, under the function of additive agents, various technical parameters are strictly controlled. An oxalic acid solution is used for deposition, and dentritic crystal shape or crystal needle shape nickel oxalate deposition can be formed. After vacuum filtration, wash and drying, the nickel oxalate deposition is reduced by the mixing gases of a hydrogen gas and a nitrogen gas in a shaft furnace device to prepare dentritic crystal shape nickel powder. The present invention has the advantages of wide source of preparation raw material and wide application range, and the cost of the present invention is lower than that of electrolysis.
Description
Technical field
A kind of production method of dentritic morphology nickel powder, relate to a kind of method of utilizing Wet-process metallurgy method to produce metal dust, particularly adopt nickel, copper, cobalt to smelt the solution containing nickel in the production process, transform nickel chloride (nickel nitrate) by extraction process, be prepared into oxalic acid nickel salt again, carry out the production method of dentritic morphology nickel powder with special appearance.
Background technology
Fast development along with each big industries such as hyundai electronics, magnetic material, electrocondution slurry, catalyst, parts, high-capacity battery, organic synthesis, space flight devices, requirement to powder-product is more and more higher, be not only the relative purifying of chemical analysis, the certain physical characteristics of powder-product is had higher requirement.For example with the extra-fine nickel powder of nickel oxalate preparation because the surface-active height, electric conductivity and thermal conductivity are good and be widely used in aspects such as chemical catalyst, carbide alloy bonding agent, electrocondution slurry and secondary battery electrode material.With the active superfine nickel oxide powder of nickel oxalate preparation because of having multiple crystal habit and different shape characteristics, thereby under different condition, show different physical and chemical performances, have wide market application prospect at aspects such as battery electrode, catalyst, semiconductor, magnetic material, glass and enamel, and become the new focus of nano materials research gradually.
Nickel oxalate is exactly a kind of well behaved Preparation of Catalyst raw material on organic catalysis originally in addition, especially along with the development of modern Synthetic Organic Chemistry technology, the no longer single use nickel of catalyst, cobalt and rare precious metal, seek the composite catalyst of many matrixes mostly, to improve the usefulness and the specificity of catalyst, as raw material, the needs of composite catalyst preparation have just in time been satisfied with nickel oxalate.According to another bibliographical information, nano-nickel oxide is a kind of up-and-coming material, and it is widely used in aspects such as catalyst, electrode, gas sensor and magnetic material, and nano-nickel oxide has same Co simultaneously
3O
4, RuO
2XH
2The specific capacity of O same electrical chemical capacitor, and its price is more than Co
3O
4, RuO
2XH
2O is cheap, thereby has caused a lot of people's attention, and the means of preparation nano-nickel oxide commonly used also have two kinds, i.e. solid phase method and liquid phase method.Liquid phase method is because technology is simple, and equipment cost is lower and be easy to advantage such as control and be widely studied.
In the production method of existing nickel powder, owing to the restriction of reasons such as raw material that adopts and technical process, preparation cost height.At present, be in the smelting enterprise of product particularly with copper, nickel, cobalt metal, in the extraction and electrolytic process of metal, can produce the nickel bearing raw material and the solution of a large amount of dilutions, the metal yield of production process is produced harmful effect, normally, return production procedure the handling of this part solution, to improve the metal yield, cause production procedure length, complex procedures, production cost height.
Summary of the invention
Purpose of the present invention is exactly the deficiency that exists at above-mentioned prior art, provide a kind of nickel, copper, cobalt of effectively utilizing to smelt the nickel sulfate solution that produces in the production process, be converted into nickel oxalate by technologies such as extractions with special appearance, to reach the pattern of control nickel powder, and then make nickel powder have the production method of the dentritic morphology nickel powder of specified physicochemical characteristics.
The objective of the invention is to be achieved through the following technical solutions.
A kind of production method of dentritic morphology nickel powder is characterized in that preparation process is nickel, copper, cobalt to be smelted the nickel sulfate solution that produces in the production process adopt P
204Come together entirely, carry out back extraction with hydrochloric acid HCl again and transfer nickel chloride solution to, remove organic matter through active carbon adsorption again; Be diluted to pure water that nickel ion content is 35g/l～50g/l in the solution, feed liquefied ammonia regulator solution PH to 8～8.8, make nickel ion form the nickel ammino and close ion; Again solution is heated to 60 ℃～70 ℃, in solution, add additive PVP or natrium citricum by 0.5%～0.6% of nickeliferous ion weight, stirring and dropping are 1.3～1.5 times oxalic acid solution of nickel solution volume, all the time control pH value in the entire reaction course 8～8.8, leave standstill to the supernatant nickel ion content after dripping less than 0.5g/l; The nickel oxalate suspension is carried out vacuum filtration, and to neutrality, drying is 8～10 hours under 100 ℃～110 ℃ temperature with pure water washing nickel oxalate; The good nickel oxalate of drying is put in the well formula reduction furnace, fed hydrogen and be warming up to 350 ℃～400 ℃, reductase 12 was cooled to room temperature after 5～35 minutes, obtained the nickel powder product of dendritic crystalline behind airflow crash.
Method of the present invention, utilize nickel, copper, cobalt to smelt the nickel sulfate solution that produces in the production process, be converted into the oxalic acid nickel salt through technologies such as extractions, the production method for preparing dentritic morphology nickel powder by the pattern of control nickel oxalate, the production process such as transition, purification, precipitation, filtration, washing, drying, reduction that relates to nickel oxalate solution, more particularly transfer nickel chloride solution to through full extraction with nickel sulfate solution, in this process, simultaneously solution is carried out deep purifying, reduce the content of various foreign ions; Under the effect of additive, the various technological parameters of strict control precipitate with oxalic acid solution then, form the nickel oxalate precipitation of dendritic crystalline or crystallization needle-like pattern, after vacuum filtration, washing, drying, in the shaft furnace device, use hydrogen reducing, prepare dentritic morphology nickel powder.Its raw material sources is wide, technology accommodation is big, and cost is lower than electrolysis.
Description of drawings
Accompanying drawing is the process flow diagram of method of the present invention.
The specific embodiment
Below in conjunction with example method of the present invention is further described.
A kind of production method of dentritic morphology nickel powder, it prepares successively that process is:
A. the nickel sulfate solution extraction is changed into nickel chloride solution
Adopt the removing calcium and magnesium feed liquid of nickelous sulfate production system, take P
204Full collection technology, with the HCl back extraction of 3～3.5N acidity, back extraction nickel chloride solution nickel ion concentration is 60～80g/l; Content of organics is higher in the solution after the back extraction, must carry out organic matter removal, and solution is through active carbon adsorption, can remove the organic matter more than 90% wherein basically;
B. prepare the nickel ammino and close solution
Through the solution behind the organic matter removal, get in the reactor with pump, being diluted to nickel ion concentration with the counter-infiltration pure water is 35g/l～50g/l, about logical liquefied ammonia regulator solution PH to 8, makes nickel ion form the nickel ammino and closes ion;
C. precipitate
The preparation oxalic acid solution is got in the head tank after filtering, and is stand-by.Solution in the reactor is heated to 60～70 ℃, press the additive (PVP or natrium citricum etc.) of nickel ion amount adding 0.5%～0.6% in the solution, under the demonstration of PH on-line testing instrument, stir and slowly drip oxalic acid solution, all the time control pH value in the entire reaction course about 8～8.8, drip until oxalic acid solution with 1.3～1.5 times of nickel solutions, continue to stir 30min then, get the supernatant test after leaving standstill, promptly react completely less than 0.5g/l as nickel ion content in the supernatant, otherwise also need to add oxalic acid solution, what this condition control was produced down is the nickel oxalate of dendritic crystalline or crystallization aciculiform shape.
D. filter, wash, drying
The nickel oxalate suspension that reacts completely is put in the vacuum cleaning groove, uses vacuum filtration, the mother liquor after filtering is got in the mother liquor holding vessel, use the counter-infiltration pure water that is heated to 60 ℃～80 ℃ to wash then and be neutral to wash water; Adopt on a small quantity during washing as far as possible, repeatedly wash.Wash qualified nickel oxalate and be contained in the stainless steel pallet, put into (temperature is at 100～110 ℃) in the drying kiln, dried by the fire continuously 8～10 hours.
E. reduction
The nickel oxalate that drying is good is put in the well formula reduction furnace, earlier logical hydrogen heats up again, until 350～400 ℃, reductase 12～2.5h has a power failure, and under the situation that continues logical hydrogen and nitrogen, is quickly cooled to room temperature, take out the nickel powder that has reduced, behind airflow crash, batch mixing, packing are the nickel powder product of dendritic crystalline.
Embodiment 1
Adopt the removing calcium and magnesium feed liquid of nickelous sulfate production system; Take P
204Full collection technology, with hydrochloric acid (HCl) back extraction of 3.5N acidity, the strip liquor nickel ion concentration is: 70～80g/l.The solution of preparing nickel chloride is through active carbon adsorption, and the organic matter rate of removing is 90%.Through the solution behind the organic matter removal, get in the reactor with pump, being diluted to nickel ion concentration with the counter-infiltration pure water is 35g/l, logical liquefied ammonia regulator solution PH to 8 makes nickel ion form the nickel ammino and closes ion; The oxalic acid solution of the about 100g/l of preparation is got in the head tank after filtering, and is stand-by.
Is nickel ion content 200 liters of the nickel chloride solutions of 35g/l, gets to 0.5m
3Reactor in, logical liquefied ammonia is regulated pH to 8.2, press the nickel ion amount and adds 0.50% PVP or natrium citricum additive, leads to that to be steam heated to solution temperature be 60 ℃, begin to drip the oxalic acid solution of 100g/l, and logical on a small quantity liquefied ammonia, keep pH to be stabilized between 8.0～8.8, until the oxalic acid of 1.30 times of nickel chloride solution volumes is added, get supernatant and measure nickel content, nickel ion content 0.49g/l stirs 20min. again, reacts completely.
Above-mentioned solid-liquid mixture, put the suction filtration cylinder into, and with 70 ℃ hot wash, washing lotion pH is at 6.1 o'clock, it is qualified to wash.Filter cake is put in the stainless steel pallet, and put on the dry shelf, close the door of dry kiln, be warming up to 100 ℃, dry 8 hours.
Above-mentioned nickel oxalate product, the charging tray in the full shaft furnace of tiling, horizontal sliding is advanced in the shaft furnace, sealed open behind the mixed gas of logical hydrogen and nitrogen, begins heating, temperature in inner bag reaches about 350 ℃, reaction 25min. takes out, and reduces the flow of hydrogen, the flow of increase nitrogen this moment, and be cooled to room temperature with water cooling rapidly, take out magazine, after the sampling, pack rapidly.
The product chemical composition, %
| Cu | Fe | Ca | C | S | Oxygen content |
| 0.013 | 0.010 | 0.022 | 0.23 | 0.0049 | 0.20 |
Granulometry: mean particle size D
50Be 2.09um, apparent density 0.35g/cm
3
Embodiment 2
Other condition is used hydrochloric acid (HCl) back extraction of 3N acidity with example 1, prepares to contain the solution process active carbon adsorption that nickel ion concentration is 70～80g/l nickel chloride, and the organic matter rate of removing is 90%.Through the solution behind the organic matter removal, get in the reactor with pump, be diluted to the counter-infiltration pure water that to contain nickel ion concentration be 50g/l, logical liquefied ammonia regulator solution PH to 8.3 makes nickel ion formation nickel ammino close ion; The oxalic acid solution of the about 100g/l of preparation is got in the head tank after filtering, and is stand-by.
Is nickel ion content 200 liters of the nickel chloride solutions of 50g/l, gets to 0.5m
3Reactor in, logical liquefied ammonia is regulated pH to 8.5, press the nickel ion amount and adds 0.6% PVP or natrium citricum additive, leads to that to be steam heated to solution temperature be 70 ℃, begin to drip the oxalic acid solution of 100g/l, and logical on a small quantity liquefied ammonia, keep pH to be stabilized between 8.0～8.8, until the oxalic acid of 1.50 times of nickel chloride solution volumes is added, get supernatant and measure nickel content, nickel ion content 0.48g/l stirs 20min. again, reacts completely.
Above-mentioned solid-liquid mixture, put the suction filtration cylinder into, and with 70 ℃ hot wash, washing lotion pH is at 6.4 o'clock, it is qualified to wash.Filter cake is put in the stainless steel pallet, and put on the dry shelf, close the door of dry kiln, be warming up to 110 ℃, dry 10 hours.
Above-mentioned nickel oxalate product, the charging tray in the full shaft furnace of tiling, horizontal sliding is advanced in the shaft furnace, sealed open behind the mixed gas of logical hydrogen and nitrogen, begins heating, temperature in inner bag reaches about 400 ℃, reaction 35min. takes out, and reduces the flow of hydrogen, the flow of increase nitrogen this moment, and be cooled to room temperature with water cooling rapidly, take out magazine, after the sampling, pack rapidly.
The product chemical composition, %
| Cu | Fe | Ca | C | S | Oxygen content |
| 0.013 | 0.010 | 0.022 | 0.23 | 0.0049 | 0.20 |
Granulometry: mean particle size D
50Be 4.82um, apparent density 0.43g/cm
3
Claims (1)
1. the production method of a dentritic morphology nickel powder is characterized in that copper, nickel, cobalt are smelted the nickel sulfate solution that produces in the production process adopts P
204Come together entirely, carry out back extraction with hydrochloric acid HCl again and transfer nickel chloride solution to, remove organic matter through active carbon adsorption again; Be diluted to pure water that nickel ion content is 35g/l～50g/l in the solution, logical liquefied ammonia regulator solution PH to 8～8.8 make nickel ion form the nickel ammino and close ion; Again solution is heated to 60 ℃～70 ℃, in solution, add additive PVP or natrium citricum by 0.5%～0.6% of nickeliferous ion weight, at 1.3～1.5 times the oxalic acid solution that stirs and drip to the volume of nickel solution, all the time control pH value in the entire reaction course 8～8.8, leave standstill after dripping to supernatant nickel ion content less than 0.5g/l; The nickel oxalate suspension is carried out vacuum filtration, and to neutrality, drying is 8～10 hours under 100 ℃～110 ℃ temperature with pure water washing nickel oxalate; The good nickel oxalate of drying is put in the well formula reduction furnace, and logical hydrogen is warming up to 350 ℃～400 ℃, is cooled to room temperature after reductase 12 5-35 minute, and airflow crash obtains the nickel powder product of dendritic crystalline.
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| CNB2005100073164A CN1305617C (en) | 2005-02-06 | 2005-02-06 | Production method of dentritic morphology nickel powder |
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| CNB2005100073164A CN1305617C (en) | 2005-02-06 | 2005-02-06 | Production method of dentritic morphology nickel powder |
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| CN1305617C true CN1305617C (en) | 2007-03-21 |
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| CN102154549B (en) * | 2011-02-21 | 2012-12-19 | 宇辰新能源材料科技无锡有限公司 | Production method for high-purity hard-agglomeration-free superfine nickel oxide or cobalt and nickel or cobalt powder |
| CN102392270B (en) * | 2011-11-03 | 2013-12-11 | 上海交通大学 | Method for preparing dendritic Ni nanocrystalline |
| CN103103354B (en) * | 2011-11-13 | 2014-08-27 | 深圳市环境友好金属材料工程技术研究开发中心 | Production method for circularly recovering ultrafine nickel powder from shadow mask of discarded CRT (Cathode Ray Tube) screen |
| CN102409178A (en) * | 2011-11-28 | 2012-04-11 | 镇江中孚复合材料有限公司 | Method for recovering iron, cobalt and nickel metal products from high-temperature alloy waste material |
| CN103951555A (en) * | 2014-04-30 | 2014-07-30 | 金川集团股份有限公司 | Preparation method of dendrite-shaped nickel oxalate |
| CN104475748A (en) * | 2014-11-21 | 2015-04-01 | 广西大学 | Method for preparing ultra-fine copper powder |
| JP6202348B2 (en) * | 2015-10-26 | 2017-09-27 | 住友金属鉱山株式会社 | Method for producing high-density nickel powder |
| CN105296763B (en) * | 2015-11-27 | 2017-11-21 | 江苏理工学院 | The method of cobalt and manganese in the high manganese waste material of low cobalt is separated and recovered with ammonia ammonium carbonate |
| CN105349789B (en) * | 2015-11-27 | 2017-11-21 | 江苏理工学院 | The method of cobalt and manganese in the high manganese waste material of low cobalt is separated and recovered with ammonia sodium carbonate |
| CN106315731A (en) * | 2016-09-13 | 2017-01-11 | 苏州湛清环保科技有限公司 | Method for producing nickel oxide from nickel-plating wastewater |
| CN108994308B (en) * | 2018-08-06 | 2019-10-22 | 金川集团股份有限公司 | A kind of preparation method of low-apparent-density atomization nickel powder |
| JP6990437B2 (en) | 2019-06-14 | 2022-01-12 | 清川メッキ工業株式会社 | Dendrite nickel crystal particles and their manufacturing method |
| CN111187921B (en) * | 2020-01-18 | 2021-03-09 | 昆明理工大学 | Method and system for preparing nickel sulfate by ammonia-enhanced laterite reduction calcine slurry method desulfurization and denitrification cooperation |
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| CN1217960A (en) * | 1997-11-17 | 1999-06-02 | 北京有色金属研究总院 | Preparation of ultrafine metal powders |
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| CA2418063A1 (en) * | 2003-01-30 | 2004-07-30 | Falconbridge Limited | Production of active nickel powder and transformation thereof into nickel carbonyl |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1217960A (en) * | 1997-11-17 | 1999-06-02 | 北京有色金属研究总院 | Preparation of ultrafine metal powders |
| CN1506182A (en) * | 2002-12-06 | 2004-06-23 | 深圳市格林美高新技术有限公司 | Process of producing superfine nickel powder added into active matter for nickel power cell |
| CA2418063A1 (en) * | 2003-01-30 | 2004-07-30 | Falconbridge Limited | Production of active nickel powder and transformation thereof into nickel carbonyl |
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