CN103588210A - Preparation method of nano silicon dioxide - Google Patents
Preparation method of nano silicon dioxide Download PDFInfo
- Publication number
- CN103588210A CN103588210A CN201310360638.1A CN201310360638A CN103588210A CN 103588210 A CN103588210 A CN 103588210A CN 201310360638 A CN201310360638 A CN 201310360638A CN 103588210 A CN103588210 A CN 103588210A
- Authority
- CN
- China
- Prior art keywords
- solution
- combination
- silicate
- water
- active agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000005543 nano-size silicon particle Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title abstract description 17
- 235000012239 silicon dioxide Nutrition 0.000 title abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000001354 calcination Methods 0.000 claims abstract description 21
- 238000005406 washing Methods 0.000 claims abstract description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004094 surface-active agent Substances 0.000 claims abstract description 8
- 239000012065 filter cake Substances 0.000 claims abstract description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 24
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 24
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 20
- 239000013543 active substance Substances 0.000 claims description 16
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 14
- 235000019353 potassium silicate Nutrition 0.000 claims description 14
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 14
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 12
- 150000001298 alcohols Chemical class 0.000 claims description 12
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 11
- -1 amine salt Chemical class 0.000 claims description 11
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims description 8
- 229910052792 caesium Inorganic materials 0.000 claims description 8
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 7
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 7
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 7
- 239000002210 silicon-based material Substances 0.000 claims description 7
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 7
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 6
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 6
- 241000282326 Felis catus Species 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 239000004115 Sodium Silicate Substances 0.000 claims description 6
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 6
- 235000019270 ammonium chloride Nutrition 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 4
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 4
- 239000003945 anionic surfactant Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229910021331 inorganic silicon compound Inorganic materials 0.000 claims description 4
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical group [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052912 lithium silicate Inorganic materials 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 4
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 3
- 239000004111 Potassium silicate Substances 0.000 claims description 3
- 229910052913 potassium silicate Inorganic materials 0.000 claims description 3
- 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 3
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 3
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 241000047703 Nonion Species 0.000 claims description 2
- MRLMRYUHKQKFGX-UHFFFAOYSA-N O.[Rb] Chemical compound O.[Rb] MRLMRYUHKQKFGX-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 2
- FZRNJOXQNWVMIH-UHFFFAOYSA-N lithium;hydrate Chemical compound [Li].O FZRNJOXQNWVMIH-UHFFFAOYSA-N 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 claims description 2
- LTUDISCZKZHRMJ-UHFFFAOYSA-N potassium;hydrate Chemical compound O.[K] LTUDISCZKZHRMJ-UHFFFAOYSA-N 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- 229910052701 rubidium Inorganic materials 0.000 claims description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 150000003871 sulfonates Chemical class 0.000 claims description 2
- XQMTUIZTZJXUFM-UHFFFAOYSA-N tetraethoxy silicate Chemical group CCOO[Si](OOCC)(OOCC)OOCC XQMTUIZTZJXUFM-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 abstract description 13
- 239000002245 particle Substances 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 6
- 239000002535 acidifier Substances 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 150000003377 silicon compounds Chemical class 0.000 abstract 1
- 238000003828 vacuum filtration Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 90
- 239000007864 aqueous solution Substances 0.000 description 20
- 239000000843 powder Substances 0.000 description 13
- 239000002994 raw material Substances 0.000 description 13
- 229910004298 SiO 2 Inorganic materials 0.000 description 12
- 229960000935 dehydrated alcohol Drugs 0.000 description 10
- 239000012043 crude product Substances 0.000 description 9
- 229960004756 ethanol Drugs 0.000 description 7
- 239000003921 oil Substances 0.000 description 6
- 239000012321 sodium triacetoxyborohydride Substances 0.000 description 6
- 239000008118 PEG 6000 Substances 0.000 description 5
- 229920002584 Polyethylene Glycol 6000 Polymers 0.000 description 5
- 238000007605 air drying Methods 0.000 description 5
- 238000010533 azeotropic distillation Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000012716 precipitator Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 229960001866 silicon dioxide Drugs 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 239000012808 vapor phase Substances 0.000 description 4
- 241000370738 Chlorion Species 0.000 description 3
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 description 3
- 238000009527 percussion Methods 0.000 description 3
- 229920002523 polyethylene Glycol 1000 Polymers 0.000 description 3
- XTUSEBKMEQERQV-UHFFFAOYSA-N propan-2-ol;hydrate Chemical compound O.CC(C)O XTUSEBKMEQERQV-UHFFFAOYSA-N 0.000 description 3
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 description 2
- 229920002593 Polyethylene Glycol 800 Polymers 0.000 description 2
- 229920002594 Polyethylene Glycol 8000 Polymers 0.000 description 2
- AWSZRNUJNSWBRK-UHFFFAOYSA-N [Li].[Si](O)(O)(O)O Chemical compound [Li].[Si](O)(O)(O)O AWSZRNUJNSWBRK-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000004530 micro-emulsion Substances 0.000 description 2
- 238000000593 microemulsion method Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 235000019351 sodium silicates Nutrition 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000004064 cosurfactant Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
Images
Landscapes
- Silicon Compounds (AREA)
Abstract
The invention provides a preparation method of nano silicon dioxide, which comprises the following steps: adding a solution A (or solution B) into an impinging stream reactor, regulating the pH value to 4-10 with a solution B (or solution A), and then performing vacuum filtration; and washing the filter cake with a washing solution C, drying, and calcining to obtain the nano silicon dioxide, wherein A is a solution containing a silicon compound, surfactant, alcohol and water; B is a solution containing acidifier, alcohol and water; and C is a solution containing alcohol or acetone or a combination thereof, surfactant and water. According to the invention, the method is simple in process and convenient to realize industrial production; and meanwhile, the obtained nano silicon dioxide particles are uniform, small in particle size and favorable in dispersity.
Description
Technical field
The present invention relates to a kind of preparation method of silicon-dioxide, be specifically related to a kind of preparation method of nano silicon.
Background technology
Nano silicon is a kind of lightweight, unbodied white powder, and nontoxic, tasteless, physicochemical property are stablized, and surface exists the hydroxyl of different states, through transmission electron microscope (TEM) test, can see that nano silicon presents cotton-shaped or reticulated structure.Nano silicon because of its particle diameter very little, specific surface area is large, surface adsorption power is strong, surface can be large, the aspects such as chemical purity is high, dispersing property good, thermal resistance, resistance have special performance, with its superior stability, reinforcement, thickening property, thixotropy and the feature such as good optical property and mechanical property, be widely used in rubber, electronic package material, coating, pigment, catalytic carrier, medicine and cosmetic field, there is the effect of not replacing.
The method of preparing nano silicon mainly contains following several: (1) vapor phase process: silicon-containing compound vapor phase hydrolysis at 1000-1400 ℃ makes nano silicon; (2) precipitator method: silicate and souring agent Direct precipitation are prepared nano silicon; (3) sol-gel method: this method is generally be hydrolyzed formation colloidal sol with silicon ester under catalyst action, then through polymeric gel, desiccant gel, burns organism and can obtain nano silicon; (4) microemulsion method: this method is to form the micro emulsion bubble of stable water-in-oil or oil-in-water-type with tensio-active agent, cosurfactant and water or oil, make the hydrolysis in micro emulsion bubble of silicon ester or silicate, then through centrifugation, washing, distillation, dryly can obtain nano silicon.
But above-mentioned several method is existent defect all: nano silicon purity prepared by (1) vapor phase process is high, particle diameter is very little, but its equipment requirements is high, technical sophistication and energy consumption large; (2) although precipitator method technique is simple, less investment but that the silicon-dioxide particle diameter prepared is bigger than normal, pattern is inhomogeneous, dispersiveness does not have vapor phase process is good, apply limited; (3) high, the easy contaminate environment of sol-gel method preparation cost; (4) organism of microemulsion method is processed loaded down with trivial details and is easily polluted, and is unfavorable for industrialization.
Summary of the invention
The mass percent of the mentioned solution of the present invention, all adopts mass volume ratio, and in the A solution referring at every 100ml as " mass percent that the add-on of tensio-active agent accounts for solution A is 0.1% ", the add-on of tensio-active agent is 0.1g.
The object of the invention is to overcome the existing precipitator method and prepare that silicon-dioxide particle diameter is bigger than normal, pattern is inhomogeneous, dispersed not good shortcoming, provide a kind of and use that impact flow reactor prepares that particle diameter is little, appearance evenly, the method for the nano silicon of good dispersity.For solving the shortcoming existing in existing nano silicon technology of preparing, the inventor is on the basis of the precipitator method, utilize impact flow reactor that strong microcosmic mixing effect and the feature of high speed shear power can be provided, prepare that particle diameter is little, the nano silicon of good dispersity.Up to the present, percussion flow has been applied to many fields, and proved that percussion flow has between strengthening phase the effect of transmitting, improving transmission coefficient, can greatly promote to mix, especially microcosmic mixes, and in nucleus developmental process, can provide high and degree of supersaturation is uniformly grown up nucleus uniformly, if add certain tensio-active agent, the particle dispersion generating is good, and in order to prepare by the precipitator method, particle diameter is little, the nano silicon of good dispersity has been obtained breakthrough condition for this.Object of the present invention completes by the following technical programs:
Technical scheme of the present invention provides a kind of preparation method of nano silicon: solution A (or solution B) is added in impact flow reactor, by solution B (or solution A), regulate pH value to suction filtration after 4-10, washings C washing for filter cake, be dried, calcination obtains nano silicon.Wherein, A is the solution of silicon-containing compound, tensio-active agent, alcohols and water; B is the solution containing souring agent, alcohols and water; C is the solution containing alcohols or acetone or its combination, tensio-active agent and water.
In some embodiments of the present invention, the silicon-containing compound concentration in solution A is 0.1-3.0,0.1-0.12,0.12-1.52,1.52-3.0mol/L, the add-on of alcohols and the volume ratio of water are 1:1-30,1:1-4,1:4-25,1:25-30, the mass percent that the add-on of tensio-active agent accounts for solution A is 0.1%-15%, 0.1%-0.5%, 0.5%-8%, 8%-15%.
In some embodiments of the present invention, the souring agent concentration in solution B is 0.4-3.5,0.4-0.5,0.5-2.87,2.87-3.5mol/L.
In some embodiments of the present invention, the alcohols in washings C or acetone or its combination are 1:2-30 with the volume ratio of water, 1:2-10, and 1:10-25,1:25-30, the mass percent of tensio-active agent is 0.1%-15%, 0.1%-0.4%, 0.4%-8%, 8%-15%.
Silicon-containing compound is selected from silicoorganic compound or inorganic silicon compound or its combination in some embodiments of the present invention.
In other embodiments of the present invention, silicoorganic compound are selected from tetraethoxy or methyl silicate or its combination, and inorganic silicon compound is selected from alkalimetal silicate, hydrated alkali metal silicate or its combination.
In other embodiments of the present invention, alkalimetal silicate is selected from lithium silicate, water glass, potassium silicate, rubidium silicate, cesium silicate or its combination; Hydrated alkali metal silicate is selected from silicate hydrate lithium, hydrated sodium silicate, silicate hydrate potassium, silicate hydrate rubidium, silicate hydrate caesium or its combination.
Tensio-active agent of the present invention is selected from cats product, anion surfactant, nonionogenic tenside or its combination in some embodiments of the present invention.
In other embodiments of the present invention, cats product is selected from amine salt class, quaternary ammonium salts, heterocyclic cats product or its combination; Anion surfactant is selected from alkyl carboxylic acid salt, Sulfonates, alkylsurfuric acid salt, phosphate ester salt analog anion surfactants or its combination; Nonionic surface active agent is selected from polyoxyethylene-type, polyvalent alcohol type, alkylol amide type, non-ion fluorin carbon surface active agent or its combination.
In some embodiments of the present invention, tensio-active agent is selected from the polyoxyethylene glycol that molecular-weight average is 400-10000 (hereinafter referred is PEG), cetyl trimethylammonium bromide (hereinafter referred is CTAB), Cetyltrimethylammonium bromide (hereinafter referred is STAB), Sodium hexametaphosphate 99, sodium laurylsulfonate or sodium lauryl sulphate or its combination.
In some embodiments of the present invention, alcohols is selected from C
1-C
4monobasic or dibasic alcohol, comprise methyl alcohol, ethanol, ethylene glycol, n-propyl alcohol, Virahol, propylene glycol, propyl carbinol, sec-butyl alcohol, isopropylcarbinol, the trimethyl carbinol, butyleneglycol or its combination.
In some embodiments of the present invention, souring agent is selected from sulfuric acid, hydrochloric acid, nitric acid, ammonium chloride, ammonium nitrate, bicarbonate of ammonia, volatile salt, ammonium sulfate or its combination.
In some embodiments of the present invention, the rotating speed of impact flow reactor is 200-10000 rev/min, and temperature of reaction is 5-90 ℃.
In other embodiments of the present invention, the rotating speed of impact flow reactor is 200-6000 rev/min, and temperature of reaction is 5-80 ℃.
In some embodiments of the present invention, drying conditions is selected from: 1) vacuum-drying, and drying temperature is 40-200 ℃, be 1-36 hour time of drying; 2) lyophilize, freezing temp-40 ℃, be 8-36 hour time of drying; 3) forced air drying, drying temperature 40-200 ℃, be 1-36 hour time of drying; 4) azeotropic distillation drying, spraying are dried or fluidised bed drying.
In some embodiments of the present invention, calcination condition is: the retort furnace of air atmosphere or oxygen atmosphere, and calcining temperature is 250-900 ℃, calcination time is 0.5-7 hour.
The method that technique scheme provides according to the present invention, wherein the feeding method of solution A and solution B is that solution A is added in solution B or solution B is added in solution A, comprises rapid loading, an one-time continuous and feeds in raw material or batch charging.
The method that above-mentioned embodiment provides according to the present invention, the median size of the resulting nano silicon of the present invention is 5-100nm.
The present invention's advantage is compared with prior art to utilize percussion flow to promote greatly reactant microcosmic mixing effect, silicon-dioxide nucleus is grown under high and uniform degree of supersaturation condition, not only technological operation simple, shortened the reaction times, and the silicon-dioxide grain median size obtaining is at 5-100nm, pattern is even, good dispersity, has good industrial prospect and application prospect.
Accompanying drawing explanation
Fig. 1 is that the present invention prepares nano silicon process flow diagram.
Fig. 2 is that the embodiment of the present invention 4 makes nano silicon transmission electron microscope photo.
Embodiment
The following stated be the preferred embodiment of the present invention, the present invention protects is not limited to following preferred implementation.It should be pointed out that on the basis of conceiving in these innovation and creation for a person skilled in the art, some distortion and the improvement made, all belong to protection scope of the present invention.
The preparation method of a kind of nano silicon provided by the invention, flow process as shown in Figure 1.
Embodiment 1
Weigh 44.98g lithium silicate (0.5mol), with methanol aqueous solution (methyl alcohol and water volume ratio the are 1:10) dissolving of 0.7%PEG-600, be settled to 2.5L, join to such an extent that contain the A solution that silicic acid lithium concentration is 0.2mol/L; The methanol aqueous solution of 0.3%PEG-600 (methyl alcohol and water volume ratio are 1:8) 776mL and 240mL concentrated hydrochloric acid mix, and the massfraction of joining is hydrochloricly 10%(2.87mol/L) B solution; Get 2.3L A solution in impact flow reactor, 400 revs/min of rotating speeds, under normal temperature, drip B solution, when arriving 5.0, the pH of reaction soln value stops feeding in raw material, reaction solution decompress filter, each is 1:12 with the methanol aqueous solution C(methyl alcohol of 0.5%PEG-600 and the volume ratio of water) 900ml washs several, until detect without chlorion, under 40 ℃ of conditions of crude product, forced air drying is 30 hours, afterwards in the retort furnace of air atmosphere 300 ℃ calcining 3 hours, obtain the SiO 2 powder that median size is 70nm.
Embodiment 2
Weigh respectively 224.91g lithium silicate (2.5mol) and 320g ammonium nitrate (4mol), with the aqueous ethanolic solution (ethanol and water volume ratio are 1:8) of the Sodium hexametaphosphate 99 of 2%PEG-800 and 1%, dissolve, be settled to respectively 2.5L, join respectively to such an extent that contain the A solution that silicic acid lithium concentration is 1.0mol/L and contain the B solution that ammonium nitrate concn is 1.6mol/L; Get 2.3L B solution in impact flow reactor, 900 revs/min of rotating speeds, be preheated to 30 ℃ and drip A solution, when arriving 9, the pH of reaction soln value stops feeding in raw material, reaction solution decompress filter, each is 1:15 with aqueous ethanolic solution C(ethanol and the water volume ratio of 3%PEG-800) 1000ml washs 4 times, under 60 ℃ of conditions of crude product, forced air drying is 7 hours, use again Virahol azeotropic distillation drying, under 100 ℃ of conditions of gained solid, forced air drying is 5 hours, afterwards in the retort furnace of oxygen atmosphere 400 ℃ calcining 3 hours, obtain the SiO 2 powder that median size is 55nm.
Embodiment 3
Weigh 152.56g water glass (1.25mol), with aqueous glycol solution (ethylene glycol and water volume ratio the are 1:15) dissolving of the CTAB of 5%PEG-1000 and 0.5%, be settled to 2.5L, join to such an extent that contain the A solution that sodium silicate silicate is 0.5mol/L; Aqueous glycol solution (ethylene glycol and water volume ratio are 1:15) 863mL and the 150mL concentrated nitric acid of 0.5%PEG-1000 and 0.5% CTAB mix, and joining containing nitric acid massfraction is 13%(3.6mol/L) B solution; Get 2.4L A solution in impact flow reactor, 850 revs/min of rotating speeds, under normal temperature, drip B solution, when arriving 4.6, the pH of reaction soln value stops feeding in raw material, reaction solution decompress filter is 1:15 with aqueous glycol solution C(ethylene glycol and the water volume ratio of 0.5%PEG-1000 and 0.5%CTAB at every turn) 1200ml washing 5 times, under 80 ℃ of conditions of crude product, vacuum-drying is 17 hours, afterwards in the retort furnace of air atmosphere 550 ℃ calcining 2 hours, obtain the SiO 2 powder that median size is 50nm.
Embodiment 4
Weigh respectively the ammonium chloride (3mol) of 355.25g nine hydrated sodium silicates (1.25mol) and 160.47g, with the dehydrated alcohol aqueous solution (dehydrated alcohol and water volume ratio are 1:10) of 1.2%PEG-6000, dissolve, be settled to respectively 2.5L, join respectively to obtain the A that is 0.5mol/L containing the concentration of nine water water glass and the containing ammonium chloride concentration B solution that is 1.2mol/L, get 2.3L B solution in impact flow reactor, 950 revs/min of rotating speeds, while being preheated to 50 ℃, start to drip A solution, when arriving 8, the pH of reaction soln value stops feeding in raw material, reaction solution decompress filter, each is 1:10 with dehydrated alcohol aqueous solution C(dehydrated alcohol and the water volume ratio of 1.2%PEG-6000) 1300ml washs several, until detect without chlorion, under 70 ℃ of conditions of crude product, vacuum drying oven is 20 hours, afterwards in the retort furnace of air atmosphere 400 ℃ calcining 6 hours, obtain the SiO 2 powder that median size is 25nm, its transmission electron microscope photo is shown in Fig. 2.
Embodiment 5
Weigh 497.35g nine hydrated sodium silicates (1.75mol), with the n-propyl alcohol aqueous solution (n-propyl alcohol and water volume ratio the are 1:10) dissolving of 0.5%STAB, be settled to 2.5L, join to such an extent that contain the A solution that the concentration of nine water water glass is 0.7mol/L; Weigh 316g bicarbonate of ammonia (4mol), with the n-propyl alcohol aqueous solution (n-propyl alcohol and water volume ratio the are 1:5) dissolving of 0.5%STAB, be settled to 2.5L, join to such an extent that contain the B solution that the concentration of bicarbonate of ammonia is 1.6mol/L; Get 2.3L B solution in impact flow reactor, 900 revs/min of rotating speeds, be preheated to 25 ℃ and drip A solution, when arriving 8.5, the pH of reaction soln value stops feeding in raw material, reaction solution decompress filter is 1:15 with n-propyl alcohol aqueous solution C(n-propyl alcohol and the water volume ratio of 0.5%STAB at every turn) 1000ml washing 5 times, crude product propyl carbinol azeotropic distillation drying, afterwards in the retort furnace of air atmosphere 600 ℃ calcining 4 hours, obtain the SiO 2 powder that median size is 45nm.
Embodiment 6
The water glass 725g(3.14mol water glass that to weigh modulus be 3.2), with the dehydrated alcohol aqueous solution (dehydrated alcohol and water volume ratio the are 1:25) dissolving of 4%PEG-10000, be settled to 2.5L, join to such an extent that contain the A solution that sodium silicate silicate is 1.25mol/L; The dehydrated alcohol aqueous solution of 4%PEG-10000 (dehydrated alcohol and water volume ratio are 1:15) 889mL and the 128mL vitriol oil mix, and join to such an extent that vitriolated massfraction is 20%(2.4mol/L) B solution; Get 2.3L A solution in impact flow reactor, after insulation to 5 ℃, drip B solution, 800 revs/min of rotating speeds, when arriving 4, the pH of reaction soln value stops feeding in raw material, reaction solution decompress filter, each is 1:25 with dehydrated alcohol aqueous solution C(dehydrated alcohol and the water volume ratio of 0.4%PEG-10000) 600ml washs several, until detect sulfate radical-free ion, under 80 ℃ of conditions of crude product, air dry oven is 20 hours, afterwards in the retort furnace of air atmosphere 500 ℃ calcining 4 hours, obtain the SiO 2 powder that median size is 85nm.
Embodiment 7
Weigh respectively 721g modulus and be 2.6 sodium potash water glass (water glass that is equivalent to 3mol) and the ammonium sulfate (5mol) of 660g, with the n-propyl alcohol aqueous solution (n-propyl alcohol and water volume ratio are 1:20) containing 8% sodium laurylsulfonate, dissolve, be settled to respectively 2.5L, join to such an extent that be equivalent to the B solution that the concentration of A solution that the concentration of water glass is 1.2mol/L and liquid containing ammonium sulfate is 2mol/L, wherein B solution adds the 10mL vitriol oil simultaneously; Get 2.3L B solution in impact flow reactor, 1000 revs/min of rotating speeds, while being preheated to 75 ℃, start to drip A solution, when arriving 8.0, the pH of reaction soln stops feeding in raw material, reaction solution decompress filter, each is 1:20 with n-propyl alcohol aqueous solution C(n-propyl alcohol and water volume ratio containing 8% sodium laurylsulfonate) 800ml washs several, until detect sulfate radical-free ion, under 100 ℃ of conditions of crude product, vacuum-drying is 5 hours, afterwards in the retort furnace of oxygen atmosphere 500 ℃ calcining 2 hours, obtain the SiO 2 powder that median size is 47nm.
Embodiment 8
Weigh the industrial sodium-potassium silicate (the low mould of 1:1) (water glass that is equivalent to 3.8mol) that 950g modulus is 2.6, with the isopropanol water solution (Virahol and water volume ratio are 1:30) of the sodium lauryl sulphate containing 3%PEG-6000 and 5%, dissolve, be settled to 2.5L, join to such an extent that be equivalent to the A solution that the concentration of water glass is 1.5mol/L; With isopropanol water solution (Virahol is 1:30 with the water volume ratio) 966mL containing 3%PEG-6000 and 5% sodium lauryl sulphate, mix with the 29mL vitriol oil, join to such an extent that vitriolated massfraction is 5%(0.5mol/L) B solution; Get 2.3L A solution in impact flow reactor, 1000 revs/min of rotating speeds, while being preheated to 40 ℃, start to drip B solution, when arriving 6, the pH of reaction soln stops feeding in raw material, reaction solution decompress filter, each isopropanol water solution C(Virahol and water volume ratio by the sodium lauryl sulphate containing 3%PEG-6000 and 5% is 1:30) 800ml washing, until detect sulfate radical-free ion, crude product Virahol azeotropic distillation drying, afterwards in the retort furnace of oxygen atmosphere 450 ℃ calcining 6 hours, obtain the SiO 2 powder that median size is 80nm.
Embodiment 9
Weigh 102.57g cesium silicate (0.3mol), with aqueous solution of propylene glycol (propylene glycol and water volume ratio the are 1:14) dissolving of 2%PEG-2000, be settled to 1L, join to such an extent that contain the A solution that the concentration of cesium silicate is 0.3mol/L; Weigh 160.47g ammonium chloride (3mol), with the aqueous solution of propylene glycol (propylene glycol and water volume ratio are 1:10) of 10%PEG-2000, dissolve and be settled to 2.5L, join to obtain the concentration of the containing ammonium chloride B solution that is 1.2mol/L; Get 2.3L B solution in impact flow reactor, after being preheated to 30 ℃, drip A solution, 500 revs/min of rotating speeds, when arriving 7.5, the pH of reaction soln value stops feeding in raw material, reaction solution decompress filter, each is 1:20 with aqueous solution of propylene glycol C(propylene glycol and the water volume ratio of 2%PEG-2000) 600ml washing, until detect without chlorion, under ℃ condition of crude product-40, lyophilize is 24 hours, afterwards in the retort furnace of air atmosphere 600 ℃ calcining 3 hours, obtain the SiO 2 powder that median size is 90nm.
Embodiment 10
Weigh 427.36g cesium silicate (1.25mol), with aqueous ethanolic solution (ethanol and water volume ratio the are 1:10) dissolving of 0.5%CTAB, be settled to 2.5L, join to such an extent that contain the A solution that the concentration of cesium silicate is 0.5mol/L; With aqueous ethanolic solution (ethanol is 1:10 with the water volume ratio) 966mL of 1.5%CTAB, mix with the 29mL vitriol oil, join to such an extent that vitriolated massfraction is 5%(0.5mol/L) B solution; Get 2.3L A solution in impact flow reactor, insulation drips B solution after 10 ℃, and 600 revs/min of rotating speeds stop feeding in raw material when the pH of reaction soln value arrives 4.5, react 8 minutes; Reaction solution decompress filter, each is 1:10 with aqueous ethanolic solution C(ethanol and the water volume ratio of 0.5%CTAB) 800ml washs several, until detect sulfate radical-free ion, it is dry that crude product and aqueous ethanolic solution (ethanol and water volume ratio are 1:10) are deployed into after the suspension that solid-to-liquid ratio is 1:9 under 200 ℃ of conditions spraying, afterwards in the retort furnace of air atmosphere 500 ℃ calcining 1.5 hours, obtain the SiO 2 powder that median size is 80nm.
Embodiment 11
Weigh respectively tetraethoxy (1.12mol) and the 320g ammonium nitrate (4mol) of 250mL, with the sec-butyl alcohol aqueous solution (sec-butyl alcohol and water volume ratio are 1:4) containing 0.5%STAB and 2%PEG-4000, dissolve, be settled to respectively 2.5L, join respectively to obtain the A that is 0.45mol/L containing the concentration of tetraethoxy and the B solution that is 1.6mol/L containing the concentration of ammonium nitrate; Get 2.3L A solution in impact flow reactor, 960 revs/min of rotating speeds, after being preheated to 82 ℃, drip B solution, when arriving 8.5, the pH of reaction soln value stops feeding in raw material, reaction solution decompress filter, each is 1:10 with sec-butyl alcohol aqueous solution C(sec-butyl alcohol and water volume ratio containing 0.5%STAB and 2%PEG-4000) 600ml washs 4 times, wet cake sec-butyl alcohol azeotropic distillation drying, forced air drying 6 hours under 105 ℃ of conditions afterwards, products therefrom in the retort furnace of oxygen atmosphere 550 ℃ calcining 3 hours, obtain the SiO 2 powder that median size is 45nm.
Embodiment 12
Weigh respectively the methyl silicate (2.01mol) of 300mL and the bicarbonate of ammonia (5mol) of 395g, with the butyleneglycol aqueous solution (butyleneglycol and water volume ratio are 1:10) containing 7%PEG-8000 and 3% sodium lauryl sulphate, dissolve, be settled to respectively 2.5L, join respectively to obtain the A solution that is 0.8mol/L containing the concentration of methyl silicate and the B solution that is 2mol/L containing the concentration of bicarbonate of ammonia; Get 2.3L A solution in impact flow reactor, 1000 revs/min of rotating speeds, while being preheated to 40 ℃, start to drip B solution, when arriving 9, the pH of reaction soln value stops feeding in raw material, reaction solution decompress filter, each is 1:15 with butyleneglycol aqueous solution C(butyleneglycol and water volume ratio containing 7%PEG-8000 and 3% sodium lauryl sulphate) 800ml washs 5 times, under ℃ condition of crude product-40, lyophilize is 27 hours, afterwards in the retort furnace of oxygen atmosphere 600 ℃ calcining 5 hours, obtain the SiO 2 powder that median size is 40nm.
Claims (16)
1. the preparation method of a nano silicon, it is characterized in that: solution A (or solution B) is added in impact flow reactor, by solution B (or solution A), regulate pH value to suction filtration after 4-10, washings C washing for filter cake, be dried, calcination obtains nano silicon; Wherein, A is the solution of silicon-containing compound, tensio-active agent, alcohols and water, and B is the solution containing souring agent, alcohols and water, and C is the solution containing alcohols or acetone or its combination, tensio-active agent and water.
2. method according to claim 1, it is characterized in that, in described solution A, silicon-containing compound concentration is 0.1-3.0mol/L, the add-on of alcohols and the volume ratio of water are 1:1-30, and the mass percent that the add-on of tensio-active agent accounts for solution A is 0.1%-15%.
3. method according to claim 1 and 2, is characterized in that, described silicon-containing compound is selected from silicoorganic compound or inorganic silicon compound or its combination.
4. method according to claim 3, is characterized in that, described silicoorganic compound are selected from tetraethoxy or methyl silicate or its combination; Inorganic silicon compound is selected from alkalimetal silicate or hydrated alkali metal silicate or its combination.
5. method according to claim 4, is characterized in that, described alkalimetal silicate is selected from lithium silicate, water glass, potassium silicate, rubidium silicate, cesium silicate or its combination.
6. method according to claim 4, is characterized in that, described hydrated alkali metal silicate is selected from silicate hydrate lithium, hydrated sodium silicate, silicate hydrate potassium, silicate hydrate rubidium, silicate hydrate caesium or its combination.
7. method according to claim 1, is characterized in that, in described solution B, souring agent concentration is 0.4-3.5mol/L.
8. method according to claim 1, is characterized in that, in described washings C, alcohols or acetone or its combination are 1:2-30 with the volume ratio of water, and the mass percent of tensio-active agent is 0.1%-15%.
9. according to the method described in claim 1 or 2 or 8, it is characterized in that, described tensio-active agent is selected from cats product, anion surfactant, nonionogenic tenside or its combination.
10. method according to claim 9, is characterized in that, described cats product is selected from amine salt class, quaternary ammonium salts or heterocyclic cats product or its combination; Anion surfactant is selected from alkyl carboxylic acid salt, Sulfonates, alkylsurfuric acid salt, phosphate ester salt analog anion surfactants or its combination; Nonionic surface active agent is selected from polyoxyethylene-type, polyvalent alcohol type, alkylol amide type, non-ion fluorin carbon surface active agent or its combination.
11. according to the method described in claim 1 or 2 or 8, it is characterized in that, described tensio-active agent is selected from polyoxyethylene glycol, cetyl trimethylammonium bromide, Cetyltrimethylammonium bromide, Sodium hexametaphosphate 99, sodium laurylsulfonate, sodium lauryl sulphate or its combination that molecular-weight average is 400-10000.
12. according to the method described in claim 1 or 2 or 8, it is characterized in that, described alcohols is selected from methyl alcohol, ethanol, ethylene glycol, n-propyl alcohol, Virahol, propylene glycol, propyl carbinol, sec-butyl alcohol, isopropylcarbinol, the trimethyl carbinol, butyleneglycol or its combination.
13. according to the method described in claim 1 or 7, it is characterized in that, described souring agent is selected from sulfuric acid, hydrochloric acid, nitric acid, ammonium chloride, ammonium nitrate, bicarbonate of ammonia, volatile salt, ammonium sulfate or its combination.
14. methods according to claim 1, is characterized in that, the rotating speed of impact flow reactor is 200-10000 rev/min, and temperature of reaction is 5-90 ℃.
15. methods according to claim 1, is characterized in that, the rotating speed of impact flow reactor is 200-6000 rev/min, and temperature of reaction is 5-80 ℃.
16. methods according to claim 1 and 2, is characterized in that, the condition of described calcining is: the retort furnace of air atmosphere or oxygen atmosphere, and calcining temperature is 250-900 ℃, calcination time is 0.5-7 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310360638.1A CN103588210B (en) | 2012-08-17 | 2013-08-16 | A kind of preparation method of nano silicon |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210293773 | 2012-08-17 | ||
| CN201210293773.4 | 2012-08-17 | ||
| CN2012102937734 | 2012-08-17 | ||
| CN201310360638.1A CN103588210B (en) | 2012-08-17 | 2013-08-16 | A kind of preparation method of nano silicon |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103588210A true CN103588210A (en) | 2014-02-19 |
| CN103588210B CN103588210B (en) | 2016-12-28 |
Family
ID=50078577
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310360638.1A Active CN103588210B (en) | 2012-08-17 | 2013-08-16 | A kind of preparation method of nano silicon |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103588210B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104891506A (en) * | 2015-06-05 | 2015-09-09 | 确成硅化学股份有限公司 | Manufacturing method of low-BET high-dispersivity silica white |
| CN106499145A (en) * | 2016-09-13 | 2017-03-15 | 内蒙古博大新型墙体材料研究所 | A kind of complex heat-preservation fire resisting energy-saving decorated sheet and preparation method thereof |
| CN108017061A (en) * | 2017-12-06 | 2018-05-11 | 上海应用技术大学 | One kind prepares large-specific surface area nano SiO using waterglass2Method |
| CN108862290A (en) * | 2018-08-17 | 2018-11-23 | 佛山朝鸿新材料科技有限公司 | A kind of preparation method of rubber composite material special-purpose nanometer silica |
| CN109911907A (en) * | 2017-12-13 | 2019-06-21 | 天津龙华诚信粉体技术有限公司 | A kind of preparation method and product of ultra-fine high oil absorption value food grade silicon dioxide |
| WO2020155603A1 (en) * | 2019-01-29 | 2020-08-06 | 原初科技（北京）有限公司 | Ammonia preparation device and preparation method |
| CN111807375A (en) * | 2020-07-04 | 2020-10-23 | 山东联科科技股份有限公司 | Preparation of nano silicon dioxide by impact flow |
| CN113350205A (en) * | 2021-06-21 | 2021-09-07 | 广州市飞雪材料科技有限公司 | High-loading high-cleaning friction type silicon dioxide for dentifrice and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101172608A (en) * | 2006-10-31 | 2008-05-07 | 中南大学 | Method of producing high-specific area nano-silicon dioxide |
| CN102092721A (en) * | 2010-11-24 | 2011-06-15 | 陈君华 | Method for preparing nanoscale white carbon black through sulfuric acid precipitation method |
-
2013
- 2013-08-16 CN CN201310360638.1A patent/CN103588210B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101172608A (en) * | 2006-10-31 | 2008-05-07 | 中南大学 | Method of producing high-specific area nano-silicon dioxide |
| CN102092721A (en) * | 2010-11-24 | 2011-06-15 | 陈君华 | Method for preparing nanoscale white carbon black through sulfuric acid precipitation method |
Non-Patent Citations (3)
| Title |
|---|
| 伍沅等: "撞击流反应制取"超细"白炭黑", 《化工学报》 * |
| 周玉新等: "撞击流反应－沉淀法制备超细白炭黑", 《化学工程与装备》 * |
| 甘露: "稻壳制备白炭黑及纳米级白炭黑的研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104891506A (en) * | 2015-06-05 | 2015-09-09 | 确成硅化学股份有限公司 | Manufacturing method of low-BET high-dispersivity silica white |
| CN106499145A (en) * | 2016-09-13 | 2017-03-15 | 内蒙古博大新型墙体材料研究所 | A kind of complex heat-preservation fire resisting energy-saving decorated sheet and preparation method thereof |
| CN108017061A (en) * | 2017-12-06 | 2018-05-11 | 上海应用技术大学 | One kind prepares large-specific surface area nano SiO using waterglass2Method |
| CN108017061B (en) * | 2017-12-06 | 2020-12-08 | 上海应用技术大学 | Method for preparing large-specific-surface-area nano SiO by using water glass2Method (2) |
| CN109911907A (en) * | 2017-12-13 | 2019-06-21 | 天津龙华诚信粉体技术有限公司 | A kind of preparation method and product of ultra-fine high oil absorption value food grade silicon dioxide |
| CN108862290A (en) * | 2018-08-17 | 2018-11-23 | 佛山朝鸿新材料科技有限公司 | A kind of preparation method of rubber composite material special-purpose nanometer silica |
| WO2020155603A1 (en) * | 2019-01-29 | 2020-08-06 | 原初科技（北京）有限公司 | Ammonia preparation device and preparation method |
| CN111807375A (en) * | 2020-07-04 | 2020-10-23 | 山东联科科技股份有限公司 | Preparation of nano silicon dioxide by impact flow |
| CN111807375B (en) * | 2020-07-04 | 2022-02-22 | 山东联科科技股份有限公司 | Preparation of nano silicon dioxide by impact flow |
| CN113350205A (en) * | 2021-06-21 | 2021-09-07 | 广州市飞雪材料科技有限公司 | High-loading high-cleaning friction type silicon dioxide for dentifrice and preparation method thereof |
| CN113350205B (en) * | 2021-06-21 | 2022-02-22 | 广州市飞雪材料科技有限公司 | High-loading high-cleaning friction type silicon dioxide for dentifrice and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103588210B (en) | 2016-12-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103588210A (en) | Preparation method of nano silicon dioxide | |
| EP3392198B1 (en) | Method for preparing metal oxide-silica composite aerogel | |
| CN101891206B (en) | Preparation method of SiO2/TiO2 composite microspheres | |
| CN106477587B (en) | Preparation method of silica gel for polyolefin catalyst carrier | |
| CN108854870A (en) | A kind of preparation method of high purity silicon Aluminum sol | |
| CN108083316B (en) | Preparation method of nano rare earth oxide powder | |
| CN102701221B (en) | Method for preparing nano white carbon black from coal gangue | |
| CN104439276B (en) | A kind of quick method and product preparing hollow porous silica/argentum nano composite material | |
| CN101412818B (en) | Industrialized preparation of nano-calcium carbonate for antibacterial fungistatic silicon rubber | |
| CN102367572B (en) | Sintering-free spraying method of polysilicon ingot crucible | |
| CN108516590A (en) | A kind of preparation method of the manganese dioxide@gold/silicon dioxide nano complex particles of nucleocapsid structure | |
| CN103360795A (en) | Modified production method for nano silicon dioxide for special rubber | |
| CN107011707A (en) | A kind of preparation method of the novel nano-material of antifogging self-cleaning | |
| CN103359747A (en) | Method for in situ modification of nano silica in batches | |
| CN114195158A (en) | Preparation method of high-purity monodisperse nano spherical silicon dioxide powder | |
| CN102417307A (en) | Preparation method of inorganic organic electrochromic composite film | |
| CN104211071A (en) | Synthetic method of CdS@SiO2 nano composite material | |
| CN101172610B (en) | Method of producing high-temperature silica powder | |
| CN102716701A (en) | Method for preparing nickel-doped bismuth silicon oxide microspheres by ultrasonic spray | |
| CN105236427A (en) | Nano-scale ordered mesoporous silicon dioxide spheres and preparation method of same | |
| CN109266148A (en) | A kind of energy conservation and environmental protection building coating and preparation method thereof | |
| CN103359739A (en) | Method for producing special modified nano silicon dioxide for plastics in large scale | |
| CN106861566A (en) | A kind of Zirconium oxide nano grain modifies the preparation method of Bio-sil microballoon | |
| CN113264765A (en) | HfO2-Si spray coating material and preparation method thereof | |
| CN106564905A (en) | Method for large-scale preparation of low-cost silicon dioxide composite aerogel |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: No. 368 East Sunshine Science Park 523871 Guangdong city of Dongguan province Changan Zhen Sha Zhen'an Road Applicant after: DONGGUAN HEC TECH R&D Co.,Ltd. Address before: No. 368 East Sunshine Science Park 523871 Guangdong city of Dongguan province Changan Zhen Sha Zhen'an Road Applicant before: DONGGUAN CHANG'AN DONGYANGGUANG ALUMINUM R&D Co.,Ltd. |
|
| COR | Change of bibliographic data | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20171227 Address after: 512000 Ruyuan County Development Zone, Shaoguan, Guangdong Patentee after: RUYUAN YAOZUZHIZHIXIAN DONGYANGGUANG FORMED FOIL Co.,Ltd. Address before: No. 368 East Sunshine Science Park 523871 Guangdong city of Dongguan province Changan Zhen Sha Zhen'an Road Patentee before: DONGGUAN HEC TECH R&D Co.,Ltd. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20180528 Address after: 101300 room 711, 2 building, 1 Jin Hang Zhong Road, Shunyi District, Beijing (Tianzhu comprehensive bonded zone -031) Patentee after: Beijing culture science and technology finance leasing Limited by Share Ltd. Address before: 512000 Ruyuan County Development Zone, Shaoguan, Guangdong Patentee before: RUYUAN YAOZUZHIZHIXIAN DONGYANGGUANG FORMED FOIL Co.,Ltd. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210629 Address after: 512600 Development Zone, Ruyuan County, Shaoguan City, Guangdong Province Patentee after: RUYUAN YAOZUZHIZHIXIAN DONGYANGGUANG FORMED FOIL Co.,Ltd. Address before: 101300 room 711, 2 building, 1 Jin Hang Zhong Road, Shunyi District, Beijing (Tianzhu comprehensive bonded zone -031) Patentee before: Beijing culture science and technology finance leasing Limited by Share Ltd. |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A preparation method of nano silica Effective date of registration: 20230523 Granted publication date: 20161228 Pledgee: Jiangxi Bank Co.,Ltd. Guangzhou Branch Pledgor: RUYUAN YAOZUZHIZHIXIAN DONGYANGGUANG FORMED FOIL Co.,Ltd. Registration number: Y2023980041541 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Granted publication date: 20161228 Pledgee: Jiangxi Bank Co.,Ltd. Guangzhou Branch Pledgor: RUYUAN YAOZUZHIZHIXIAN DONGYANGGUANG FORMED FOIL Co.,Ltd. Registration number: Y2023980041541 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A preparation method of nano silica Granted publication date: 20161228 Pledgee: Jiangxi Bank Co.,Ltd. Guangzhou Branch Pledgor: RUYUAN YAOZUZHIZHIXIAN DONGYANGGUANG FORMED FOIL Co.,Ltd. Registration number: Y2024980006169 |