CN101863520A - Preparation method of microporous ultrafine high activity nickel carbonate - Google Patents
Preparation method of microporous ultrafine high activity nickel carbonate Download PDFInfo
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- CN101863520A CN101863520A CN 201010201046 CN201010201046A CN101863520A CN 101863520 A CN101863520 A CN 101863520A CN 201010201046 CN201010201046 CN 201010201046 CN 201010201046 A CN201010201046 A CN 201010201046A CN 101863520 A CN101863520 A CN 101863520A
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- carbonate
- high activity
- nickel carbonate
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- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 title claims abstract description 67
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 230000000694 effects Effects 0.000 title claims abstract description 27
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 67
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 27
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 26
- 238000001035 drying Methods 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 17
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 14
- 235000017550 sodium carbonate Nutrition 0.000 claims abstract description 14
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 24
- -1 compound nickel salt Chemical class 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000012065 filter cake Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 238000004090 dissolution Methods 0.000 claims description 7
- 238000010298 pulverizing process Methods 0.000 claims description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 150000002739 metals Chemical class 0.000 claims description 6
- 230000004044 response Effects 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000010790 dilution Methods 0.000 claims description 2
- 239000012895 dilution Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 19
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 12
- 239000000843 powder Substances 0.000 abstract description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 6
- 238000009826 distribution Methods 0.000 abstract description 6
- 150000002815 nickel Chemical class 0.000 abstract description 6
- 239000002244 precipitate Substances 0.000 abstract description 6
- 239000001569 carbon dioxide Substances 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000001556 precipitation Methods 0.000 abstract description 4
- 230000009471 action Effects 0.000 abstract description 2
- 238000005406 washing Methods 0.000 abstract description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 abstract 2
- 239000001099 ammonium carbonate Substances 0.000 abstract 2
- 239000002131 composite material Substances 0.000 abstract 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 abstract 1
- 235000012501 ammonium carbonate Nutrition 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 235000011121 sodium hydroxide Nutrition 0.000 abstract 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical group [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 16
- 239000000463 material Substances 0.000 description 13
- 229910000480 nickel oxide Inorganic materials 0.000 description 13
- 239000003054 catalyst Substances 0.000 description 12
- 230000008569 process Effects 0.000 description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000000428 dust Substances 0.000 description 4
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000007747 plating Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 230000008676 import Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 102220042174 rs141655687 Human genes 0.000 description 3
- 102220076495 rs200649587 Human genes 0.000 description 3
- 102220043159 rs587780996 Human genes 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 241000370738 Chlorion Species 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- 239000004141 Sodium laurylsulphate Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000003483 aging Methods 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910018661 Ni(OH) Inorganic materials 0.000 description 1
- 229910003310 Ni-Al Inorganic materials 0.000 description 1
- 229910021588 Nickel(II) iodide Inorganic materials 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 235000009754 Vitis X bourquina Nutrition 0.000 description 1
- 235000012333 Vitis X labruscana Nutrition 0.000 description 1
- 240000006365 Vitis vinifera Species 0.000 description 1
- 235000014787 Vitis vinifera Nutrition 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 208000018459 dissociative disease Diseases 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 description 1
- BFSQJYRFLQUZKX-UHFFFAOYSA-L nickel(ii) iodide Chemical compound I[Ni]I BFSQJYRFLQUZKX-UHFFFAOYSA-L 0.000 description 1
- DITXJPASYXFQAS-UHFFFAOYSA-N nickel;sulfamic acid Chemical compound [Ni].NS(O)(=O)=O DITXJPASYXFQAS-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
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- 238000007670 refining Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
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- 230000003068 static effect Effects 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
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Abstract
The invention discloses a preparation method of microporous ultrafine high activity nickel carbonate, comprising the following steps of adopting mixed acid solution prepared from nitric acid, sulfuric acid and hydrochloride to dissolve metal nickel to prepare composite nickel salts used as raw materials; carrying out precipitation reaction with the composite nickel salts by using mixed percipitant of sodium carbonate, ammonium carbonate or ammonium bicarbonate and sodium hydroxide in a sealed drum type reaction pot under the action of high pressure CO2; and preparing the nickel carbonate by crushing and drying precipitates by adopting an integrative machine of crushing and drying after washing the precipitates. Shown through a particle image analyzer, a full-automatic specific surface area voidage analyzer and an SEM (Scanning Electron Microscope) photograph result, the nickel carbonate has fine size, the particle size of D50 can achieve 1-5 microns, the particle size specific surface area can achieve more than 300m2/g, the content of carbon dioxide is larger than 20 percent, the nickel carbonate has multiple and small micropores, the powder nickel carbonate with the nickel content of 49-51 percent has narrow and uniform particle size distribution, wherein the particle size of D10 is 0.93 microns, the particle size of D50 is 1.81 microns and the particle size of D90 is 2.82 microns, and the dispersion of the powder nickel carbonate is favorable.
Description
Background technology
The research and the applicating history of nickel catalyst are long, and just making acetaldehyde reduction with nickel catalyzator as far back as Saba-tier in 1903 is methyl alcohol.The nineteen thirty Exxon NiO/Al of company
2O
3Steam transforms preparing synthetic gas.The nickel carbonyl catalyst of Reppe method acetylene system acetaldehyde in 1931 is developed success.1934, Fischer and Trop-sch built up first hand Al in German Rule chemical company
2O
3Carry the factory of NiO oxo process system oil.At present, Ni can be used for alkene, aromatic hydrocarbons, aniline, phenol, nitrous acid ester, naphthalene, alcohol, aldehyde, CO and CO
2(Fischer-Tropsch) hydrogenation.NiO can be used for the oxidation of dehydrating alkanes and hydrocarbon.
Nickel catalyzator is low because of its price, process controllability is strong, and is active higher in hydrogenation reaction, thereby has a wide range of applications.As nickel catalyst active substance component, nickel is present in the catalyzer with two kinds of forms: a kind of is that metallic nickel (elemental nickel) form exists, as skeletal nickel catalyst (methanation catalyst), nickel-alumina catalyst (phenol and benzene hydrogenating catalyst), Raney's nickel catalyst etc.; Another kind is that oxide compound (nickel oxide) form exists, as supporter nickel catalyst (methanation catalyst), one (two) section conversion catalyst of Sweet natural gas, Z
301Type catalyzer (No. one, training of qi steam reforming catalysts triumph) etc.
Along with the develop rapidly of catalysis technique, nickel catalyst is faced with three big fundamental issues promptly to be improved activity, improves environment and reduce production costs and need to break through.Exploitation high reactivity, low cost, low pollution, novel hydrogenation catalyst have great importance.
Adopt Raney-Ni as catalyzer now in the industrial production mostly.Raney-Ni is the nickel catalyzator that utilizes the scorification preparation, and its preparation process mainly comprises the refining of Ni-AI alloy and two parts of leaching of Ni-Al alloy, and the catalyzer that minority is used for successive reaction also passes through molding procedure.Its major defect be reaction preference low, than being easier to inactivation, poor heat resistance, limited throughput and life of catalyst.
Three kinds of methods of the normal employing of nickel catalyst industrially preparing process: (1) precipitator method; (2) pickling process; (3) hybrid system;
(4) the molten method of hot melt.Wherein the most frequently used method is: (1) nickelous nitrate wiring solution-forming is immersed in the carrier, and roasting becomes nickel oxide; The nitrate roasting produces the oxynitride with yellow cigarette, contaminate environment; The nickelous carbonate activity of making is not high, granularity is bigger, influences the performance of nickel catalyst.(2) nickel nitrate solution and yellow soda ash or volatile salt precipitation is made nickelous carbonate, and roasting becomes nickel oxide.And obtain nickel powder, thereby preparation nickel catalyst by hydrogen reduction.
Nickelous carbonate is mainly used in (1) activity of such catalysts material; (2) presoma of nickel oxide and nickel powder; (3) raw material of other inorganic nickel (nickelous bromide, nickelous iodide etc.); (4) raw material of organic nickel salt (nickel sulfamic acid, boron acidylate nickel, nickel acetate, grape acid nickel); (5) nickel, the removal of impurity and accent PH are mended in chemically coating nickel by magnesium-alloy and plating.The quality of the quality decision nickel catalyst of nickelous carbonate.
Nickelous carbonate has three kinds of forms to exist: positive nickelous carbonate, basic nickel carbonate and acid nickelous carbonate.Common preparation method is that carbonate and nickel salt reaction are synthetic.The solubility product Ksp=6.6x10 of nickelous carbonate
-9, dissociation reaction: CO takes place in carbonate in water
3 2-+ H
2O → HCO
3 -+ OH
-, in solution, have CO
3 2-, HCO
3 -, OH
-, the solubility product Ksp=6.6x10 of nickelous carbonate
-9, precipitate completely PH at 8-9, and nickel hydroxide precipitate PH is at 7-9.So, in nickelous carbonate precipitates completely process, nickel hydroxide precipitate is arranged unavoidably.Therefore, pure nickelous carbonate and acid nickelous carbonate is difficult to prepare in the reality.It is the complex body (xNiCO of a kind of nickelous carbonate, nickel hydroxide and water
3.yNi (OH)
2.zH
2O).To prepare bibliographical information rarely seen about pure nickelous carbonate and acid nickelous carbonate.Normalized address should be " combined type nickelous carbonate " or " basic nickel carbonate ".
Existing report combined type nickelous carbonate structural formula has:
2NiCO
3.3Ni(OH)
2.4H
2O
NiCO
3.2Ni(OH)
2.4H
2O
NiCO
3.Ni(OH)
2.4H
2O
It is actually the complex body of nickelous carbonate and nickel hydroxide.Carbon Dioxide nickel (alkali formula) is green flour powder thing, and is water insoluble, is soluble in acid.Nickelous carbonate (alkali formula) product micropore seldom, carbon dioxide content about 10-15%, D
50Granularity is greater than more than the 10 μ m.
Nickel oxide is a kind of powdery product, belongs to NaCL type cubic system.Its oxygen level is indefinite, can change within the specific limits, and its lattice parameter also changes according to oxygen level, because this inherent lattice imperfection makes it to become a kind of good P-type semiconductor material.The color of nickel oxide changes along with oxygen level, and according to the order that oxygen level reduces, the color of powder is grey black, greyish-green and the green that arrive.With the rising of calcination temperature, the nickel oxide powder of being produced is active to be reduced, and catalytic activity and solubleness also descend, and density and resistance then can increase.
As a kind of functional material, nickel oxide mainly is used as the basic material of materials such as process gas transmitter, magneticsubstance, battery electrode, catalyzer, glass and enamel coloring agent, alloy material.
Along with the development of these industries, more and more higher requirement has been proposed for the performance of nickel oxide powder.Mainly be that the many physics in the novel material preparation process is also relevant with the size of powder stock with chemical phenomenon owing to the influence that is subjected to grain-size in the performance that is many novel materials of feedstock production to a great extent with it.Use ultra-fine nickel oxide powder to make raw material, its huge particle surface tends to bring some special variation for whole technological process, as when preparing sensitive ceramic element, electrode, the motivating force that the small-size effect of particle and interfacial effect have changed sintering process greatly is a surface energy, the diffusion path of material can shorten, contact interface increases, thereby has quickened diffusion and chemical reaction process, and the ceramic product Effect on Performance that sintering is obtained is remarkable.Applied research that oneself has report shows, behind the nickel oxide powder super-refinement, has improved some physical and chemical index of material product significantly, for the application extension of nickel oxide powder more wide field.
Utilize precipitin reaction, the control grain is brilliant to be generated, prepare fine size, narrowly distributing and evenly, the superior nickel oxide presoma of big, the multi-cellular structure of good dispersity, specific surface area (every gram square metre), surface property or claim the intermediate activity nickelous carbonate, being good, the novel effective catalyst nickel oxide of the production traits and the basis of other nickel catalyst, also is the emphasis of current research.
" research of metallic impurity in the active carbonate of nickel absorption nickel-plating liquid " (electroplating September calendar year 2001 and the 21st the 5th phase of volume of environmental protection) disclosed active carbonate of nickel and can adsorb metallic impurity in the nickel-plating liquid, has the characteristics of method of chemical treatment and surface chemistry absorption method concurrently.Removal of impurities mechanism is the CO that metallic impurity ion and nickelous carbonate dissociate out
3 2-Be combined into the precipitation conversion reaction of carbonate.Active carbonate of nickel system with industrial single nickel salt and yellow soda ash be by weight 1: 1～1.5 under rare (0.5%), cold (30～35 ℃) condition violent stirring slowly act on and forming, react finish after, static 0.5h.Incline and charge into cold water washing behind the supernatant liquid for several times.To the pH value at 7～8 o'clock, can use.As use filter to filter, must be with the filter cake cleaned with the careful furnishing mashed prod of a small amount of nickel-plating liquid.Just can use.
Chinese patent CN200710050492.5 discloses a kind of method for preparing high specific surface area meso-porous nickelous oxide, is that nickel source, yellow soda ash are that precipitation agent, sodium lauryl sulphate are template with the nickelous chloride; Add an amount of sodium lauryl sulphate and make structure directing agent in nickel salt solution, carry out precipitin reaction with sodium carbonate solution then, the throw out filter cake adds 90 ℃ of baking oven ageings of ammoniacal liquor and spends the night, and ageing washs after finishing, grind and obtain presoma (basic nickel carbonate).Presoma is calcined under certain condition, is cooled off, and promptly gets meso-porous nickelous oxide.
Summary of the invention
The purpose of this invention is to provide a kind of preparation method of microporous ultrafine high activity combined type nickelous carbonate, this method comprises:
1) with the mixed acid solution of nitric acid, sulfuric acid and hydrochloric acid preparation, dissolution of metals nickel prepares compound nickel salt;
2) in compound nickel salt and mixed precipitant weight part 1: the 1.1-1.3 ratio, dilution is the compound nickel salt aqueous solution of 4-12% and the 8-17% mixed precipitant aqueous solution respectively, and stream pumps in the airtight retort pressurization feeding CO
2, at 0.5～1 normal atmosphere of pressure, under 40～45 ℃ of conditions of temperature, stir, carry out precipitin reaction; Described mixed precipitant is yellow soda ash, volatile salt or bicarbonate of ammonia and sodium hydroxide;
3) filter, filter cake washs with pure water; Dry under 125～135 ℃ of conditions of temperature, pulverizing is carried out simultaneously, gets microporous ultrafine high activity combined type nickelous carbonate;
Described mixed acid solution is in pure nitric acid, sulfuric acid and hydrochloric acid weight part: 4～8: 2～6: the preparation of 1～3 ratio;
Described mixed precipitant is in yellow soda ash, volatile salt or bicarbonate of ammonia and sodium hydroxide weight part: 5.0～8.5: 1.0～4.5: the preparation of 0.1～0.05 ratio;
Described confined reaction jar is garden shape, is provided with puddle support and zirconia ball or agate ball in the retort, and puddle support is fixed on the tank skin, adopts the drum-type alr mode of rotational response jar to stir;
Described filtration is the filtration unit that the cover by retort is provided with, CO in retort
2Under the pressure effect, the back direct filtration reacts completely;
Described drying, pulverizing are carried out simultaneously, are to adopt the pure all-in-one drying of xeraphium, pulverizing.
The preparation method of a kind of microporous ultrafine high activity nickel carbonate of the present invention, adopt the mixed acid solution dissolution of metals nickel of nitric acid, sulfuric acid and hydrochloric acid preparation, the compound nickel salt of preparation is made raw material, mixed precipitant with yellow soda ash, volatile salt or bicarbonate of ammonia and sodium hydroxide, in the drum-type retort of sealing, high pressure CO
2Effect is carried out precipitin reaction down, the preparation nickelous carbonate; Nitric acid has strong oxidizing property, dissolution rate is fast, chlorion in the hydrochloric acid helps infiltration, there are nitrate ion, chlorion to exist more tiny in the system than the nickelous carbonate particle that generates in the independent sulfate radical system, size range is narrower, sedimentary filter cake washs well, and the nickelous carbonate salt impurity content of preparation is low; Volatile salt or bicarbonate of ammonia in the mixed precipitant, form nickel amine complex in the reaction process, controlled speed of response, add carbon dioxide under condition of high voltage, adopt the drum-type retort, gas-liquid under high pressure mixes in the reaction process, helps the formation of microvoid structure, good dispersity, the CARBONATE COMPONENT of compound nickelous carbonate increases relatively, oxyhydroxide reduces relatively, and the yellow soda ash in the mixed precipitant makes precipitin reaction complete, the nickel content height in the nickelous carbonate, filtrate does not need recycling, adopt and pulverize dry all-in-one pulverizing drying, dispersed better, particle is more even.
The microporous ultrafine high activity combined type nickelous carbonate that utilizes the inventive method to produce shows fine size, D by Rise-3002 particle image instrument, Rise-1030 type full-automatic specific surface area voidage analyser and SEM photo result
50Granularity can reach the 1-5 micron, and the size ratio surface-area reaches more than 300 (every gram square metre), and carbon dioxide content is greater than 20%, and micropore is many, and nickel content is the powdery nickelous carbonate of 49-51% and little, and particle size distribution is narrow and even, D10=0.93 μ m; D50=1.81 μ m; D90=2.82 μ m, good dispersity.
Description of drawings
Fig. 1 is the drum-type retort synoptic diagram of preparation method's use of microporous ultrafine high activity combined type nickelous carbonate of the present invention.
Fig. 2 is the cross-sectional schematic of drum-type retort cover.
Fig. 3 is the utility model drying and crushing all-in-one assembling synoptic diagram.
Fig. 4 is the utility model drying and crushing all-in-one cyclone drying crush tower cross-sectional schematic.
Fig. 5 is the utility model drying and crushing all-in-one cyclone drying crush tower agitator vertical view.
Fig. 6 is a combined type nickelous carbonate SEM photo, and wherein: A, C are the microporous ultrafine high activity combined type nickelous carbonate combined type nickelous carbonate of the inventive method preparation; B, D are the combined type nickelous carbonate of ordinary method preparation.
Fig. 7 is combined type nickelous carbonate Rise-3002 particle image instrument analytical results figure, and wherein: A is the microporous ultrafine high activity combined type nickelous carbonate combined type nickelous carbonate of the inventive method preparation; B is the combined type nickelous carbonate of conventional preparation method's preparation.
The particle size distribution figure that Fig. 8 records for laser particle analyzer, wherein: A is an ordinary method nickelous carbonate particle size distribution figure, D10=6 μ m; D50=20 μ m; D90=40 μ m; B is the nickelous carbonate particle size distribution figure that the inventive method is produced, D10=0.93 μ m; D50=1.81 μ m; D90=2.82 μ m.
Embodiment
See also Fig. 1,2, the drum-type retort, comprise: the charging opening 8 of retort body 3, whippletree 7, bracing frame 1, cover 5, band valve, body 1 is circular, whippletree 7 is integral with retort body 3, whippletree 7 is fixed on the bracing frame 3, cover 5 is at retort body 3 one end tops, and whippletree is connected with drive unit, and fixed comb formula sledge whipping appts 4 is housed in the retort body 3, what body 3 also was provided with the band valve adds gas port 9, is provided with filtration unit in the cover; Zirconia ball 2 also is housed in the retort; Described cover 5 is provided with the band valve discharge port 51 that blowing is used, and filtration unit is to accompany filter cloth 53 in the middle of the two-layer screen cloth 52.
As Fig. 3,4, shown in 5, the drying and crushing all-in-one, it is by feeder 1, calorifier 2, cyclone drying crush tower 3, whirlwind rewinding tower 4, tower 5 gathers dust, induced draft fan 6, heat exchanger 7, tower seat 9 is formed, described cyclone drying crush tower 3, by opening for feed 315, hot blast pressure stabilizing cavity import 38, several hot blast imports 37, hot blast agitator and discharge port 312 and discharge port 313 are formed, the hot blast pressure stabilizing cavity is the chamber of dimension around the body 31 basis pontiss formation of cyclone drying crush tower 3, opening for feed 315 is located at the middle part of the body 31 of cyclone drying crush tower 3, the top of agitator, connect with feeder 1, hot blast import 38 is located on the bottom sidewall of body 31, link with calorifier 2, discharge port 312 and discharge port 313 are equipped with valve port, be located at the top of body 31, discharge port 313 is below discharging 312, they are connected with whirlwind rewinding tower 4, whirlwind rewinding tower 4, tower 5 gathers dust, induced draft fan 6 links to each other successively with heat exchanger 7, described agitator is located at the bottom of body 31, by stir shaft 35, stir shaft power wheel 353, stir axle sleeve 39, body sledge 311, stir shaft sledge 351, stirring arm 352 is formed, stirring arm 352 is a ladder type, stir shaft sledge 351 is above stirring arm 352, stirring arm 352 and stir shaft sledge 351 all are fixed on the stir shaft 35, and stir shaft sledge 351 intersects with the body sledge 311 comb formulas that are fixed on the body 31; Stir axle sleeve 39 and be provided with air-cooling device 36; Body 31 is provided with adjustable top cover 33 and annular ring washer 314, and they are adjustable up and down; But body 31 also is provided with the viewing window 34 of free switch.
During work, humidity and granularity according to material, select discharge port 312 or discharge port 313 dischargings, if select discharge port 312 dischargings, open its valve, close the valve of discharge port 313, adjustable top cover is transferred to discharge port 312 tops, be fixed on the body 31, ring-like washer 314 is transferred to the below of discharge port 312 with bolt 32, be fixed on the body 31, feeder advances wet stock in the body 31, at the body sledge 311 of agitator, stir shaft sledge 351, the stirring of stirring arm 352, the hot blast that blows into, under the sucking action of induced draft fan 6, material and hot blast thorough mixing, spiral making progress, dry fine particle is little because of centrifugal force, is carried secretly by hot blast, and a wet coarse particles part directly falls, a part is upwards lived for 33 grades by ring-like ring washer along the tower wall, falls down continuation and pulverizes dry; See through the viewing window 34 interior material grinding situation of observing tower at any time, window 34 switch dynamics are judged positive negative pressure condition in the tower according to the observation, adjust and blow or the air inducing amount; Material after the drying and crushing by discharge port 312 enter whirlwind rewinding tower 4 successively, the tower 5 that gathers dust, rewinding, gather dust, the heat exchanger 7 of induced draft fan 6 rear ends is collected waste heats.
Referring to Fig. 1,2;
1, in pure nitric acid, sulfuric acid and hydrochloric acid weight part: 4～8: 2～6: 1～3 ratio, the mixed acid solution of preparation is used mixed acid solution dissolution of metals nickel again, prepares compound nickel salt;
2, press yellow soda ash, volatile salt or bicarbonate of ammonia and sodium hydroxide weight part: 5.0～8.5: 1.0～4.5: 0.05～0.1 mixed is even, the preparation mixed precipitant;
3, by weight than compound nickel salt: mixed precipitant=1: 1.1-1.3 ratio, with concentration is that compound nickel salt aqueous solution of 4-12% and concentration are the 8-17% mixed precipitant aqueous solution, and by the charging opening 8 of band valve, and stream pumps in the retort, close charging opening 8, feed CO by adding gas port 9 high pressure
2, open band valve discharge port 51 emptying air simultaneously after, close band valve discharge port 51, at 0.5～1 normal atmosphere of pressure, under 40～45 ℃ of conditions of temperature, electric motor driving whippletree 7 drives retort bodies 3 and rotates and stir, and carries out precipitin reaction;
3, react completely after, open band valve discharge port 51, filter; Filter cake washs with pure water; Adopt the described drying and crushing all-in-one of embodiment 2 dry down 125～135 ℃ of temperature, pulverize, the high nickelous carbonate of living of microporous ultrafine.
Referring to Fig. 1,2;
1, in pure nitric acid, sulfuric acid and hydrochloric acid weight part: 8: 2: 3 ratios, the mixed acid solution of preparation is used mixed acid solution dissolution of metals nickel again, prepares compound nickel salt;
2, press yellow soda ash, volatile salt or bicarbonate of ammonia and sodium hydroxide weight part: mixed was even in 8.5: 1.0: 0.5, the preparation mixed precipitant;
3, by weight than compound nickel salt: mixed precipitant=1: 1.2 ratio, with concentration is that compound nickel salt aqueous solution of 4-12% and concentration are the 8-17% mixed precipitant aqueous solution, and by the charging opening 8 of band valve, and stream pumps in the retort, close charging opening 8, feed CO by adding gas port 9 high pressure
2, open band valve discharge port 51 emptying air simultaneously after, close band valve discharge port 51, at 0.5～1 normal atmosphere of pressure, under 40～45 ℃ of conditions of temperature, electric motor driving whippletree 7 drives retort bodies 3 and rotates and stir, and carries out precipitin reaction;
3, react completely after, open band valve discharge port 51, filter; Filter cake washs with pure water; Adopt embodiment 2 described drying and crushing all-in-ones,, get microporous ultrafine high activity nickel carbonate in temperature 125～135 ℃ of dry down, pulverizing.
Referring to Fig. 1,2;
1, in pure nitric acid, sulfuric acid and hydrochloric acid weight part: 4: 3: 3 ratios, the mixed acid solution of preparation is used mixed acid solution dissolution of metals nickel again, prepares compound nickel salt;
2, press yellow soda ash, volatile salt or bicarbonate of ammonia and sodium hydroxide weight part: mixed was even in 5.0: 4.5: 0.1, the preparation mixed precipitant;
3, by weight than compound nickel salt: mixed precipitant=1: 1.3 ratio, with concentration is that compound nickel salt aqueous solution of 4-12% and concentration are the 8-17% mixed precipitant aqueous solution, and by the charging opening 8 of band valve, and stream pumps in the retort, close charging opening 8, feed CO by adding gas port 9 high pressure
2, open band valve discharge port 51 emptying air simultaneously after, close band valve discharge port 51, at 0.5～1 normal atmosphere of pressure, under 40～45 ℃ of conditions of temperature, electric motor driving whippletree 7 drives retort bodies 3 and rotates and stir, and carries out precipitin reaction;
3, react completely after, open band valve discharge port 51, filter; Filter cake washs with pure water; Adopt the described drying and crushing all-in-one of embodiment 2 dry down 125～135 ℃ of temperature, pulverize, the high nickelous carbonate of living of microporous ultrafine.
The nickelous carbonate test result that the present invention makes:
1, the SEM photo shows the nickelous carbonate that present method makes, and, micropore littler than the nickelous carbonate granularity of ordinary method system manys (see figure 6);
2, Rise-3002 particle image instrument photo shows that the nickelous carbonate granularity that this law preparation method makes is significantly less than conventional preparation method, and the relatively more even (see figure 7) of size-grade distribution.
3, Rise-1030 type full-automatic specific surface area voidage analyser and the results are shown in (table 1).
The full-automatic specific surface area voidage of table 1 nickelous carbonate Rise-1030 type analyser test result
Index the inventive method conventional method
Specific surface area (every gram square metre): 313.2946087 194.0647666
Single-point specific surface area (every gram square metre): 250.4616358 188.0532854
Micro pore volume (every gram milliliter): 7.196732929 20.08063633
Micropore area (every gram square metre): 5.10583E-05 0.007458787
Bjh adsorption hole area (every gram square metre): 219.3920494 170.1713878
Bjh desorption hole area (every gram square metre): 228.7160948 153.1424578
Bjh adsorption hole volume (every gram milliliter): 0.342106526 0.313490355
Bjh desorption pore volume (every gram milliliter): 0.313886314 0.277574649
Bjh adsorbs mean diameter (A): 62.37355029 73.68814667
Bjh desorption mean diameter (A): 54.89536086 72.50103012
During relative pressure 0.973 less than the total pore volume of 870.31A: 0.398920006 0.330950034
Claims (6)
1. the preparation method of microporous ultrafine high activity nickel carbonate, this method comprises:
1) with the mixed acid solution of nitric acid, sulfuric acid and hydrochloric acid preparation, dissolution of metals nickel prepares compound nickel salt;
2) in compound nickel salt and mixed precipitant weight part 1: the 1.1-1.3 ratio, dilution is the compound nickel salt aqueous solution of 4-12% and the 8-17% mixed precipitant aqueous solution respectively, and stream pumps in the airtight retort pressurization feeding CO
2, at 0.5～1 normal atmosphere of pressure, under 40～45 ℃ of conditions of temperature, stir, carry out precipitin reaction; Described mixed precipitant is yellow soda ash, volatile salt or bicarbonate of ammonia and sodium hydroxide;
3) filter, filter cake washs with pure water; Dry under 125～135 ℃ of conditions of temperature, pulverizing is carried out simultaneously, gets microporous ultrafine high activity combined type nickelous carbonate.
2. the preparation method of microporous ultrafine high activity nickel carbonate according to claim 1 is characterized in that: the described mixed acid solution of step 1) is in pure nitric acid, sulfuric acid and hydrochloric acid weight part: 4～8: 2～6: the preparation of 1～3 ratio.
3. the preparation method of microporous ultrafine high activity nickel carbonate according to claim 2 is characterized in that: step 2) described mixed precipitant is in yellow soda ash, volatile salt or bicarbonate of ammonia and sodium hydroxide weight part: 5.0～8.5: 1.0～4.5: the preparation of 0.1～0.05 ratio.
4. the preparation method of microporous ultrafine high activity nickel carbonate according to claim 1, it is characterized in that: step 2) described confined reaction jar, be garden shape, be provided with puddle support and zirconia ball or agate ball in the retort, puddle support is fixed on the tank skin, adopts the drum-type alr mode of rotational response jar to stir.
5. the preparation method of microporous ultrafine high activity nickel carbonate according to claim 4 is characterized in that: the described filtration of step 3) is the filtration unit that the cover by retort is provided with, CO in retort
2Under the pressure effect, the back direct filtration reacts completely.
6. according to the preparation method of claim 1,2,3,4 or 5 described microporous ultrafine high activity nickel carbonates, it is characterized in that: the described drying of step 3), pulverizing are carried out simultaneously, are to adopt the pure all-in-one of xeraphium to carry out drying and crushing.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103084180A (en) * | 2013-02-28 | 2013-05-08 | 中国矿业大学 | Preparation method of supported ultrafine amorphous metal nickel catalyst for realizing catalytic full hydrogenation of aromatic ring |
| CN106745341A (en) * | 2017-01-07 | 2017-05-31 | 邵阳学院 | The hydrothermal synthesis method of Carbon Dioxide nickel |
| CN106898504A (en) * | 2017-05-05 | 2017-06-27 | 孝感双华应用科技开发有限公司 | A kind of preparation method of the nano composite material based on Graphene |
| CN112939099A (en) * | 2021-02-09 | 2021-06-11 | 荆门市格林美新材料有限公司 | Preparation method of basic nickel carbonate |
| CN115368154A (en) * | 2022-09-05 | 2022-11-22 | 衡阳凯新特种材料科技有限公司 | Production process and equipment of silicon nitride wave-absorbing material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001335326A (en) * | 2000-05-24 | 2001-12-04 | Sumitomo Metal Mining Co Ltd | Method for manufacturing basic nickel carbonates |
| WO2003020644A1 (en) * | 2001-09-04 | 2003-03-13 | Inco Limited | Method for reducing the crystallinity of nickel hydroxide powders |
| CN101519229A (en) * | 2009-03-19 | 2009-09-02 | 金川集团有限公司 | Method for continuously synthesizing nickel carbonate |
| CN101624215A (en) * | 2008-07-10 | 2010-01-13 | 中国石油化工股份有限公司 | Method for preparing nano nickel oxide |
-
2010
- 2010-06-17 CN CN2010102010461A patent/CN101863520B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001335326A (en) * | 2000-05-24 | 2001-12-04 | Sumitomo Metal Mining Co Ltd | Method for manufacturing basic nickel carbonates |
| WO2003020644A1 (en) * | 2001-09-04 | 2003-03-13 | Inco Limited | Method for reducing the crystallinity of nickel hydroxide powders |
| CN101624215A (en) * | 2008-07-10 | 2010-01-13 | 中国石油化工股份有限公司 | Method for preparing nano nickel oxide |
| CN101519229A (en) * | 2009-03-19 | 2009-09-02 | 金川集团有限公司 | Method for continuously synthesizing nickel carbonate |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103084180A (en) * | 2013-02-28 | 2013-05-08 | 中国矿业大学 | Preparation method of supported ultrafine amorphous metal nickel catalyst for realizing catalytic full hydrogenation of aromatic ring |
| CN106745341A (en) * | 2017-01-07 | 2017-05-31 | 邵阳学院 | The hydrothermal synthesis method of Carbon Dioxide nickel |
| CN106898504A (en) * | 2017-05-05 | 2017-06-27 | 孝感双华应用科技开发有限公司 | A kind of preparation method of the nano composite material based on Graphene |
| CN112939099A (en) * | 2021-02-09 | 2021-06-11 | 荆门市格林美新材料有限公司 | Preparation method of basic nickel carbonate |
| CN112939099B (en) * | 2021-02-09 | 2023-05-12 | 荆门市格林美新材料有限公司 | Preparation method of basic nickel carbonate |
| CN115368154A (en) * | 2022-09-05 | 2022-11-22 | 衡阳凯新特种材料科技有限公司 | Production process and equipment of silicon nitride wave-absorbing material |
| CN115368154B (en) * | 2022-09-05 | 2023-03-14 | 衡阳凯新特种材料科技有限公司 | Production process and equipment of silicon nitride wave-absorbing material |
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