CN107235998B - The preparation method of amino silane - Google Patents
The preparation method of amino silane Download PDFInfo
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- CN107235998B CN107235998B CN201710471474.8A CN201710471474A CN107235998B CN 107235998 B CN107235998 B CN 107235998B CN 201710471474 A CN201710471474 A CN 201710471474A CN 107235998 B CN107235998 B CN 107235998B
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- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 239000002077 nanosphere Substances 0.000 claims abstract description 84
- 239000007788 liquid Substances 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 39
- 239000000463 material Substances 0.000 claims abstract description 37
- 229910000077 silane Inorganic materials 0.000 claims abstract description 32
- -1 cyano alkoxy silane Chemical compound 0.000 claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- 238000012856 packing Methods 0.000 claims abstract description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 114
- 239000010941 cobalt Substances 0.000 claims description 94
- 229910017052 cobalt Inorganic materials 0.000 claims description 94
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 94
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 89
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 81
- 239000008367 deionised water Substances 0.000 claims description 76
- 229910021641 deionized water Inorganic materials 0.000 claims description 76
- 235000019441 ethanol Nutrition 0.000 claims description 46
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 41
- 239000001257 hydrogen Substances 0.000 claims description 41
- 229910052739 hydrogen Inorganic materials 0.000 claims description 41
- 239000007787 solid Substances 0.000 claims description 40
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 33
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 28
- 238000005984 hydrogenation reaction Methods 0.000 claims description 26
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 18
- 239000000908 ammonium hydroxide Substances 0.000 claims description 18
- 239000000377 silicon dioxide Substances 0.000 claims description 16
- 229910052681 coesite Inorganic materials 0.000 claims description 15
- 229910052906 cristobalite Inorganic materials 0.000 claims description 15
- 229910052682 stishovite Inorganic materials 0.000 claims description 15
- 229910052905 tridymite Inorganic materials 0.000 claims description 15
- 230000015572 biosynthetic process Effects 0.000 claims description 14
- 238000003786 synthesis reaction Methods 0.000 claims description 14
- 238000012545 processing Methods 0.000 claims description 13
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 11
- 238000005119 centrifugation Methods 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 76
- 239000007795 chemical reaction product Substances 0.000 abstract description 20
- 238000004519 manufacturing process Methods 0.000 abstract description 13
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 abstract 2
- 230000003213 activating effect Effects 0.000 abstract 1
- 239000004530 micro-emulsion Substances 0.000 description 48
- 229960004756 ethanol Drugs 0.000 description 28
- 239000000047 product Substances 0.000 description 26
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 24
- 239000006228 supernatant Substances 0.000 description 16
- 239000004793 Polystyrene Substances 0.000 description 14
- 229920002223 polystyrene Polymers 0.000 description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 230000008569 process Effects 0.000 description 12
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 10
- 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 10
- 239000006004 Quartz sand Substances 0.000 description 10
- 239000002253 acid Substances 0.000 description 10
- 230000004913 activation Effects 0.000 description 10
- 238000006555 catalytic reaction Methods 0.000 description 10
- 238000004587 chromatography analysis Methods 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- 239000012535 impurity Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 238000010606 normalization Methods 0.000 description 10
- 150000003141 primary amines Chemical class 0.000 description 10
- 239000011734 sodium Substances 0.000 description 10
- 229910052708 sodium Inorganic materials 0.000 description 10
- 238000001179 sorption measurement Methods 0.000 description 10
- 229910001220 stainless steel Inorganic materials 0.000 description 10
- 239000010935 stainless steel Substances 0.000 description 10
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 9
- GBQYMXVQHATSCC-UHFFFAOYSA-N 3-triethoxysilylpropanenitrile Chemical compound CCO[Si](OCC)(OCC)CCC#N GBQYMXVQHATSCC-UHFFFAOYSA-N 0.000 description 9
- 230000008859 change Effects 0.000 description 9
- 238000004821 distillation Methods 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 238000006277 sulfonation reaction Methods 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 229910000564 Raney nickel Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 229960000935 dehydrated alcohol Drugs 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 150000003512 tertiary amines Chemical class 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000011805 ball Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 125000002496 methyl group Chemical class [H]C([H])([H])* 0.000 description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 3
- 239000004926 polymethyl methacrylate Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- KVUMYOWDFZAGPN-UHFFFAOYSA-N 3-trimethoxysilylpropanenitrile Chemical compound CO[Si](OC)(OC)CCC#N KVUMYOWDFZAGPN-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- KSCAZPYHLGGNPZ-UHFFFAOYSA-N 3-chloropropyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CCCCl KSCAZPYHLGGNPZ-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 239000007977 PBT buffer Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229920013822 aminosilicone Polymers 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 238000005915 ammonolysis reaction Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 125000005159 cyanoalkoxy group Chemical group 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 210000004209 hair Anatomy 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011806 microball Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000011490 mineral wool Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000002990 reinforced plastic Substances 0.000 description 1
- 238000007528 sand casting Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 231100000462 teratogen Toxicity 0.000 description 1
- 239000003439 teratogenic agent Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- B01J35/51—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
Abstract
The preparation method of amino silane is related to the preparation method of amino silane.The present invention is to solve the selectivity of the conversion ratio of cyano alkoxy silane in the preparation method of existing amino silane and primary amine is lower, the problem of being unable to satisfy industrial requirement.Method: by hollow Co nanosphere Catalyst packing to the flat-temperature zone of fixed bed reactors, activating 40~120min, and then use is continuously injected into mode and material liquid is injected into fixed bed reactors, reacts 4~100h then to get amino silane.The conversion ratio of cyano alkoxy silane is 100% in this method, and the selectivity of primary amine can reach 99.65%.Reaction is the successive reaction of multiphase in the present invention, and reaction product is easily separated with catalyst；It is easy to operate, convenient for large-scale production, it can satisfy the demand of industrialized production.The present invention is used to prepare amino silane.
Description
Technical field
The present invention relates to the preparation methods of amino silane.
Background technique
High-purity amino silane defence and military, aerospace and in terms of be widely applied.It is filled out applied to mineral
The thermoplasticity such as the phenolic aldehyde, polyester, epoxy, PBT, polyamide, the carbonic ester that fill and thermosetting resin can increase substantially reinforced plastics
Dry and wet state bending strength, compression strength, physical and mechanical properties and the hygrometric state electric property such as shear strength, and improve filler poly-
Close the wetability and dispersibility in object.In resin sand casting, the adhesiveness of reinforced resin silica sand improves sand bond and moisture-resistant
Property.It in glass fiber cotton and mineral wool production, adds it in phenol-formaldehyde binders, moisture resistance can be improved and increases compression resilience.
Aminopropyl triethoxysilane can be used for polyurethane, epoxy, nitrile, modified phenolic adhesive and close as excellent adhesive accelerant
Closure material, improve the dispersibility of pigment and improve to glass, aluminium, ferrous metal adhesiveness, be also applied for polyurethane, epoxy and third
Olefin(e) acid latex paint.In recent years since polymer coupling, powder and modification of fiberfill surface, coating, dyestuff and adhesive etc. are led
Domain demand growth is powerful, and it is that silane field is only second to that the direct pull demand of amino silane, average annual rate of rise, which are more than 20%,
The second largest kind of sulfuric silane, therefore, the market prospects of amino silane are unlimited.
The amino silane of domestic enterprise's production at present still uses ammonolysis process, and this method carries out ammonia with chloropropyl triethoxysilane
Solution reaction is characterized, and this method is haveed the shortcomings that many inevitable.First, in the synthesis process can due to poor selectivity,
And the by-products such as more secondary amine and tertiary amine are generated, to reduce yield, improve manufacturing cost.Second, in process of production
The release of the dangerous wastes such as ammonia emission and by-product ammonium chloride is had, the basic principle of Green Chemistry is not met, has to ecological environment
Huge adverse effect.Third, being not only increased since reaction pressure excessively high (70-120 atmospheric pressure) is stringent to equipment requirement
Production cost, and production process security risk is larger.Under this background environment, the exploitation of amino silane novel process and industry
It is particularly important to change research limit, is the important directions of current silane field industrialization development.It adopts new technology the amino silicone of production
Alkane not only has the advantage of purity is high (chloride ion content is lower than 1ppm), and technique is environmentally protective, at low cost.Meanwhile in mesh
It marks in product synthesis process, the more other high added value products of coproduction, atom utilization is high, and economic value is significant.
And industrially prepared in the method for amino silane using cyano alkoxy silane hydrogenation reaction at present, catalyst is main
For Raney's nickel, production process is intermittent reaction, is needed before reaction with the water in corresponding alcohol displacement Raney's nickel, due to Raney's nickel
Settling property is poor, so that part Raney's nickel catalyst is flowed out with displacement liquid, while also increasing separation and recovery of catalyst
Difficulty improves production cost, and is difficult to carry out mass production.Raney's nickel is flammable harmful substance, by international cancer
Disease research institution is considered carcinogenic substance and teratogen, can burn rapidly once exposed in air, thus other combustibility of igniting
Substance leads to fire.Therefore, developmental research safety and stability, the raw catelyst being easily isolated are of great significance.
The conversion ratio of amino silane is 97.4% in the preparation method of existing amino silane and the selectivity of primary amine is
95.8%, although the selectivity of conversion ratio and primary amine in existing method is higher, as country is to chemical industry environmental protection
Problem is increasingly paid attention to, especially further stringent to the processing of ammonia nitrogen compound, secondary amine, tertiary amine and the ammonium chloride that out-of-date methods generate
By-product needs to put into a large amount of processing cost and improves production cost, and chlorine in the amino silane product produced of out-of-date methods
Ion and amine ion concentration are excessively high；Still it is unable to satisfy the demand of industry.
Summary of the invention
The present invention is to solve the conversion ratio of cyano alkoxy silane in the preparation method of existing amino silane and primary amine
The problem of selectivity is lower, is unable to satisfy industrial requirement, provides the preparation method of amino silane.
The preparation method of amino silane of the present invention, comprising the following steps:
One, the preparation of hollow Co nanosphere is with process sulfonation processing with the polymethylacrylic acid extended transversely through
The polystyrene hollow microballoon that methyl esters-polymethylacrylic acid channel diameter is 70~125nm is templated synthesis, specific to prepare
Method are as follows:
1. in mass ratio it is 9:(13.9~21.7 by cobalt source, ammonium hydroxide, secondary deionized water and polystyrene hollow microballoon):
312:(1.6~3.3) weigh；Wherein cobalt source is Co (CH3COO)2·4H2O or CoSO4·7H2The concentration of O, the ammonium hydroxide is
10mol/L；
2. first by process sulfonation processing with the polymethyl methacrylate extended transversely through-polymethylacrylic acid channel
Diameter be 70nm polystyrene hollow microballoon and ammonium hydroxide mixing, and at room temperature stirring 12~for 24 hours, two are added later
Secondary deionized water is diluted, and obtains colloidal sol；
3. cobalt source, which is dissolved in secondary deionized water, obtains the cobalt source solution of 1~3mol/L, then by the cobalt source of 1~3mol/L
Solution is added dropwise in sol solutions in 2~3h, is ultrasonically treated 30~60min；It is then centrifuged for, by centrifuged solid in nothing
It is washed 3~5 times in water-ethanol, obtained solid, which is transferred in n,N-Dimethylformamide (DMF), after centrifugation removes template polystyrene,
It is centrifuged again, it is micro- to get Co nanometers of double-layer hollow that solid is transferred in Muffle furnace 450~600 DEG C of 3~5h of roasting under air atmosphere
Ball；
Wherein step 1. the weighed secondary deionized water of institute for step 2. in prepare colloidal sol and step 3. in configure cobalt
Source solution.
Two, prepare material liquid: will to cyano alkoxy silane with solvent according to mass ratio 1:(0~0.5) be uniformly mixed, obtain
To material liquid；
Three, hydrogenation reaction: by the perseverance of the hollow Co nanosphere Catalyst packing of step 1 preparation to fixed bed reactors
In warm area, 40~120min is activated under conditions of temperature is 150~400 DEG C, hydrogen flow rate is 50~100mL/min, then
Material liquid prepared by step 2 is injected into fixed bed reactors using the mode that is continuously injected into, is then 100~200 in temperature
DEG C, pressure be 3~7MPa, mass space velocity is 0.5~3.0h-1, hydrogen flow rate be 5~30mL/min under conditions of reaction 4~
100h is to get amino silane.
Wherein described in step 1 by sulfonation processing with the polymethyl methacrylate-polymethyl extended transversely through
The preparation method of the polystyrene hollow microballoon in sour channel is in article " Synthesis of Spheres with
Complex Structures Using Hollow Latex Cages as Templates " (M Yang, Advanced
Functional Materials, 2010,15 (9): 1523-1528) in disclose.
Further, 2. the speed of stirring described in step is 600~1400r/min in step 1.
Further, solvent described in step 2 be benzene,toluene,xylene, n-hexane, tetrahydrofuran, acetone, methanol,
Ethyl alcohol or isopropanol.
This method preparation is double-layer hollow Co nanosphere, and double-layer hollow Co nanosphere has bigger specific surface area
It can reach 1285m with the specific surface area of more meso-hole structures, double-layer hollow Co nanosphere2/ g, high specific surface area can
To provide more hydrogenation activity sites, when in the hydrogenation activity site of mesoporous inner wall hydrogenation reaction occurs for cyano alkoxy silane
When be preferentially produced the lesser primary amine of steric hindrance, secondary ammonium and tertiary amine due to cannot be timely from mesoporous after the larger generation of steric hindrance
In spread out, it is suppressed that reaction continues, improve principal product primary amine selectivity.The selectivity of primary amine can reach
99.65%.The conversion ratio of cyano alkoxy silane is 100%.
The preparation method of amino silane of the present invention, comprising the following steps:
One, the preparation of hollow Co nanosphere, is with SiO2Microballoon is templated synthesis, specific steps are as follows:
1. by ammonium hydroxide, cobalt source, secondary deionized water and SiO2Microballoon is 5:(3.9~7.2 in mass ratio): 750:(8.9~
13.3) it weighs, wherein the cobalt source is Co (CH3COO)2·4H2O or CoSO4·7H2O, the SiO2The diameter of microballoon be 10~
40nm, the concentration of the ammonium hydroxide are 0.05mol/L；
2. first by SiO2Microballoon and secondary deionized water are mixed and made into sol solutions, and cobalt source is dissolved in secondary deionized water and is obtained
To the cobalt source solution of 0.3~0.6mol/L, then the cobalt source solution of 0.3~0.6mol/L is added in sol solutions, at ultrasound
10~30min is managed, is then added dropwise to ammonium hydroxide in sol solutions in 2~3h, is ultrasonically treated 30~60min again；
3. being then centrifuged for, centrifuged solid is successively washed 3~5 times in secondary deionized water and ethyl alcohol, from
Solid is transferred to 550~700 DEG C of 3~5h of roasting in Muffle furnace after the heart, by the solid after roasting 5~10mol/L hydroxide
In sodium solution at 90~110 DEG C processing 12~for 24 hours, be centrifugated again after secondary deionized water dilutes, by solid repeat wash
After washing-being centrifuged three times, solid is transferred in baking oven and is dried to get hollow Co nanosphere；
Wherein step 1. the weighed secondary deionized water of institute for step 2. in prepare sol solutions and configuration cobalt source solution.
Two, prepare material liquid: will to cyano alkoxy silane with alcohol according to mass ratio 1:(0~0.5) be uniformly mixed, obtain
Material liquid；
Three, hydrogenation reaction: by the perseverance of the hollow Co nanosphere Catalyst packing of step 1 preparation to fixed bed reactors
In warm area, 40~120min is activated under conditions of temperature is 150~400 DEG C, hydrogen flow rate is 50~100mL/min, then
Material liquid prepared by step 2 is injected into fixed bed reactors using the mode that is continuously injected into, is then 100~200 in temperature
DEG C, pressure be 3~7MPa, mass space velocity is 0.5~3.0h-1, hydrogen flow rate be 5~30mL/min under conditions of reaction 4~
100h is to get an amino silane.
Further, temperature 3. dry described in step in step 1 is 110 DEG C, and the dry time is 12h.
Further, alcohol described in step 2 is methanol or ethyl alcohol.
This method is with SiO2Microballoon is template, can choose the size of template, and then it is micro- to control hollow Co nanometers obtained
The partial size of ball, the method for the present invention can be with the SiO of 10nm partial size2Microballoon prepares the hollow Co nanosphere of only 20nm partial size,
It is that partial size is the smallest in all methods, i.e., specific surface area is maximum, can reach 1352m2/g。
The preparation method of amino silane of the present invention, comprising the following steps:
One, the preparation of hollow Co nanosphere, is synthesized by template of F127, specific steps are as follows:
1. by sodium hydroxide, cobalt source, hexamethylene, secondary deionized water and F127 template be in mass ratio 3:(5.4~
15.9) it: 2.4:1425:(28.4~46.2) weighs；Wherein the cobalt source is Co (CH3COO)2·4H2O or CoSO4·7H2O；
It is put into insulating box 2. first mixing hexamethylene, F127 template and secondary deionized water, keeps 1 at room temperature
Microemulsion is made in~3h, and cobalt source is dissolved in secondary deionized water and obtains the cobalt source solution of 0.5~1mol/L, then by 0.5~
The cobalt source solution of 1mol/L is added in microemulsion, is then ultrasonically treated 10~30min；
3. sodium hydroxide, which is dissolved in secondary deionized water, obtains 0.03~0.05mol/L sodium hydroxide solution, then will
0.03~0.05mol/L sodium hydroxide solution is added dropwise in microemulsion in 30~60min, is ultrasonically treated 10~30min again,
It is then centrifuged for taking supernatant, 25 DEG C of supernatant is evaporated under reduced pressure, is centrifugated again after dehydrated alcohol dilutes, solid is transferred to
It dries in baking oven to get hollow Co nanosphere；
Wherein step 1. the weighed secondary deionized water of institute for step 2. in prepare microemulsion, configuration cobalt source solution and
3. step configures sodium hydroxide solution.
Two, prepare material liquid: will to cyano alkoxy silane with alcohol according to mass ratio 1:(0~0.5) be uniformly mixed, obtain
Material liquid；
Three, hydrogenation reaction: by the perseverance of the hollow Co nanosphere Catalyst packing of step 1 preparation to fixed bed reactors
In warm area, 40~120min is activated under conditions of temperature is 150~400 DEG C, hydrogen flow rate is 50~100mL/min, then
Material liquid prepared by step 2 is injected into fixed bed reactors using the mode that is continuously injected into, is then 100~200 in temperature
DEG C, pressure be 3~7MPa, mass space velocity is 0.5~3.0h-1, hydrogen flow rate be 5~30mL/min under conditions of reaction 4~
100h is to get an amino silane.
Further, the time dry in the 3. step of step 1 is 110 DEG C, drying temperature 12h.
Further, alcohol described in step 2 is methanol or ethyl alcohol.
The preparation method of amino silane of the present invention, comprising the following steps:
One, the preparation of hollow Co nanosphere, is synthesized by template of P123, specific steps are as follows:
1. by sodium hydroxide, cobalt source, hexamethylene, secondary deionized water and P123 template be in mass ratio 3:(4.8~
18.2) it: 2.4:1425:(31.9~53.7) weighs；Wherein cobalt source is Co (CH3COO)2·4H2O or CoSO4·7H2O；
It is put into insulating box 2. first mixing hexamethylene, P123 template and secondary deionized water, keeps 1 at room temperature
Microemulsion is made in~3h, and cobalt source is dissolved in secondary deionized water and obtains the cobalt source solution of 0.5~1mol/L, then by 0.5~
The cobalt source solution of 1mol/L is added in microemulsion, is then ultrasonically treated 10~30min；
3. sodium hydroxide, which is dissolved in secondary deionized water, obtains 0.03~0.05mol/L sodium hydroxide solution, then will
0.03~0.05mol/L sodium hydroxide solution is added dropwise in microemulsion in 30~60min, is ultrasonically treated 10~30min again,
It is then centrifuged for taking supernatant, 25 DEG C of supernatant is evaporated under reduced pressure, is centrifugated again after dehydrated alcohol dilutes, solid is transferred to
It dries in baking oven to get hollow Co nanosphere；
Wherein step 1. the weighed secondary deionized water of institute for step 2. in prepare microemulsion, configuration cobalt source solution and
3. step configures sodium hydroxide solution.
Two, prepare material liquid: will to cyano alkoxy silane with alcohol according to mass ratio 1:(0~0.5) be uniformly mixed, obtain
Material liquid；
Three, hydrogenation reaction: by the perseverance of the hollow Co nanosphere Catalyst packing of step 1 preparation to fixed bed reactors
In warm area, 40~120min is activated under conditions of temperature is 150~400 DEG C, hydrogen flow rate is 50~100mL/min, then
Material liquid prepared by step 1 is injected into fixed bed reactors using the mode that is continuously injected into, is then 100~200 in temperature
DEG C, pressure be 3~7MPa, mass space velocity is 0.5~3.0h-1, hydrogen flow rate be 5~30mL/min under conditions of reaction 4~
100h is to get an amino silane.
Further, the time dry in the 3. step of step 1 is 110 DEG C, drying temperature 12h.
Further, alcohol described in step 2 is methanol or ethyl alcohol.
Beneficial effects of the present invention:
For the present invention using hollow Co nanosphere as catalyst, which has high-ratio surface, high table
Face activity, high Surface Permeability and good hydrogen storage ability, to have good catalytic hydrogenation property；To cyano alkoxy
The hydrogenation reaction of silane and hydrogen has higher catalytic activity, the selectivity of primary amine and higher carbon accumulation resisting ability.
The present invention is used as catalyst using double-layer hollow Co nanosphere, with bigger specific surface area and more mesoporous
Structure, high specific surface area can provide more hydrogenation activity sites, when cyano alkoxy silane adds hydrogen in mesoporous inner wall
Active site occurs to be preferentially produced the lesser primary amine of steric hindrance, secondary ammonium and tertiary amine due to the larger life of steric hindrance when hydrogenation reaction
It cannot timely be spread out from mesoporous after, it is suppressed that reaction continues, and improves the selectivity of principal product primary amine.
The conversion ratio of cyano alkoxy silane is 100% in the present invention, and the selectivity of primary amine can reach 99.65%.This hair
In bright, raw material is mixed by reactant cyano alkoxy silane and corresponding alcohol, reacts the successive reaction for multiphase, instead
Answer product easily separated with catalyst；It is easy to operate, convenient for large-scale production, it can satisfy the demand of industrialized production.
Detailed description of the invention
Fig. 1 is SiO of the embodiment 2 with diameter for 10nm2Microballoon is the scanning electricity of the hollow Co nanosphere of templated synthesis
Mirror figure；
Fig. 2 is the enlarged drawing of Fig. 1；
Fig. 3 is SiO of the embodiment 2 with diameter for 10nm2Microballoon is the transmission electricity of the hollow Co nanosphere of templated synthesis
Mirror figure.
Specific embodiment
The technical solution of the present invention is not limited to the following list, further includes between each specific embodiment
Any combination.
Specific embodiment 1: the preparation method of present embodiment amino silane, comprising the following steps:
One, the preparation of hollow Co nanosphere is with process sulfonation processing with the polymethylacrylic acid extended transversely through
The polystyrene hollow microballoon that methyl esters-polymethylacrylic acid channel diameter is 70~125nm is templated synthesis, specific to prepare
Method are as follows:
1. in mass ratio it is 9:(13.9~21.7 by cobalt source, ammonium hydroxide, secondary deionized water and polystyrene hollow microballoon):
312:(1.6~3.3) weigh；Wherein cobalt source is Co (CH3COO)2·4H2O or CoSO4·7H2The concentration of O, the ammonium hydroxide is
10mol/L；
2. first by process sulfonation processing with the polymethyl methacrylate extended transversely through-polymethylacrylic acid channel
Diameter be 70nm polystyrene hollow microballoon and ammonium hydroxide mixing, and at room temperature stirring 12~for 24 hours, two are added later
Secondary deionized water is diluted, and obtains colloidal sol；
3. cobalt source, which is dissolved in secondary deionized water, obtains the cobalt source solution of 1~3mol/L, then by the cobalt source of 1~3mol/L
Solution is added dropwise in sol solutions in 2~3h, is ultrasonically treated 30~60min；It is then centrifuged for, by centrifuged solid in nothing
It is washed 3~5 times in water-ethanol, obtained solid, which is transferred in n,N-Dimethylformamide (DMF), after centrifugation removes template polystyrene,
It is centrifuged again, it is micro- to get Co nanometers of double-layer hollow that solid is transferred in Muffle furnace 450~600 DEG C of 3~5h of roasting under air atmosphere
Ball；
Wherein step 1. the weighed secondary deionized water of institute for step 2. in prepare colloidal sol and step 3. in configure cobalt
Source solution；
Two, prepare material liquid: will to cyano alkoxy silane with solvent according to mass ratio 1:(0~0.5) be uniformly mixed, obtain
To material liquid；
Three, hydrogenation reaction: by the perseverance of the hollow Co nanosphere Catalyst packing of step 1 preparation to fixed bed reactors
In warm area, 40~120min is activated under conditions of temperature is 150~400 DEG C, hydrogen flow rate is 50~100mL/min, then
Material liquid prepared by step 2 is injected into fixed bed reactors using the mode that is continuously injected into, is then 100~200 in temperature
DEG C, pressure be 3~7MPa, mass space velocity is 0.5~3.0h-1, hydrogen flow rate be 5~30mL/min under conditions of reaction 4~
100h is to get amino silane.
Specific embodiment 2: the present embodiment is different from the first embodiment in that: in step 1 2. described in step
The speed of stirring is 600~1400r/min.It is other same as the specific embodiment one.
Specific embodiment 3: the present embodiment is different from the first and the second embodiment in that: it is molten described in step 2
Agent is benzene,toluene,xylene, n-hexane, tetrahydrofuran, acetone, methanol, ethyl alcohol or isopropanol.Other and specific embodiment
One or two is identical.
Specific embodiment 4: the preparation method of present embodiment amino silane, comprising the following steps:
One, the preparation of hollow Co nanosphere, is with SiO2Microballoon is templated synthesis, specific steps are as follows:
1. by ammonium hydroxide, cobalt source, secondary deionized water and SiO2Microballoon is 5:(3.9~7.2 in mass ratio): 750:(8.9~
13.3) it weighs, wherein the cobalt source is Co (CH3COO)2·4H2O or CoSO4·7H2O, the SiO2The diameter of microballoon be 10~
40nm, the concentration of the ammonium hydroxide are 0.05mol/L；
2. first by SiO2Microballoon and secondary deionized water are mixed and made into sol solutions, and cobalt source is dissolved in secondary deionized water and is obtained
To the cobalt source solution of 0.3~0.6mol/L, then the cobalt source solution of 0.3~0.6mol/L is added in sol solutions, at ultrasound
10~30min is managed, is then added dropwise to ammonium hydroxide in sol solutions in 2~3h, is ultrasonically treated 30~60min again；
3. being then centrifuged for, centrifuged solid is successively washed 3~5 times in secondary deionized water and ethyl alcohol, from
Solid is transferred to 550~700 DEG C of 3~5h of roasting in Muffle furnace after the heart, by the solid after roasting 5~10mol/L hydroxide
In sodium solution at 90~110 DEG C processing 12~for 24 hours, be centrifugated again after secondary deionized water dilutes, by solid repeat wash
After washing-being centrifuged three times, solid is transferred in baking oven and is dried to get hollow Co nanosphere；
Wherein step 1. the weighed secondary deionized water of institute for step 2. in prepare sol solutions and configuration cobalt source solution.
Two, prepare material liquid: will to cyano alkoxy silane with alcohol according to mass ratio 1:(0~0.5) be uniformly mixed, obtain
Material liquid；
Three, hydrogenation reaction: by the perseverance of the hollow Co nanosphere Catalyst packing of step 1 preparation to fixed bed reactors
In warm area, 40~120min is activated under conditions of temperature is 150~400 DEG C, hydrogen flow rate is 50~100mL/min, then
Material liquid prepared by step 2 is injected into fixed bed reactors using the mode that is continuously injected into, is then 100~200 in temperature
DEG C, pressure be 3~7MPa, mass space velocity is 0.5~3.0h-1, hydrogen flow rate be 5~30mL/min under conditions of reaction 4~
100h is to get an amino silane.
Specific embodiment 5: present embodiment is unlike specific embodiment four: in step 1 3. described in step
Dry temperature is 110 DEG C, and the dry time is 12h.It is other identical as specific embodiment four.
Specific embodiment 6: present embodiment is unlike specific embodiment four or five: alcohol described in step 2 is
Methanol or ethyl alcohol.It is other identical as specific embodiment four or five.
Specific embodiment 7: the preparation method of present embodiment amino silane, comprising the following steps:
One, the preparation of hollow Co nanosphere, is synthesized by template of F127, specific steps are as follows:
1. by sodium hydroxide, cobalt source, hexamethylene, secondary deionized water and F127 template be in mass ratio 3:(5.4~
15.9) it: 2.4:1425:(28.4~46.2) weighs；Wherein the cobalt source is Co (CH3COO)2·4H2O or CoSO4·7H2O；
It is put into insulating box 2. first mixing hexamethylene, F127 template and secondary deionized water, keeps 1 at room temperature
Microemulsion is made in~3h, and cobalt source is dissolved in secondary deionized water and obtains the cobalt source solution of 0.5~1mol/L, then by 0.5~
The cobalt source solution of 1mol/L is added in microemulsion, is then ultrasonically treated 10~30min；
3. sodium hydroxide, which is dissolved in secondary deionized water, obtains 0.03~0.05mol/L sodium hydroxide solution, then will
0.03~0.05mol/L sodium hydroxide solution is added dropwise in microemulsion in 30~60min, is ultrasonically treated 10~30min again,
It is then centrifuged for taking supernatant, 25 DEG C of supernatant is evaporated under reduced pressure, is centrifugated again after dehydrated alcohol dilutes, solid is transferred to
It dries in baking oven to get hollow Co nanosphere；
Wherein step 1. the weighed secondary deionized water of institute for step 2. in prepare microemulsion, configuration cobalt source solution and
3. step configures sodium hydroxide solution.
Two, prepare material liquid: will to cyano alkoxy silane with alcohol according to mass ratio 1:(0~0.5) be uniformly mixed, obtain
Material liquid；
Three, hydrogenation reaction: by the perseverance of the hollow Co nanosphere Catalyst packing of step 1 preparation to fixed bed reactors
In warm area, 40~120min is activated under conditions of temperature is 150~400 DEG C, hydrogen flow rate is 50~100mL/min, then
Material liquid prepared by step 2 is injected into fixed bed reactors using the mode that is continuously injected into, is then 100~200 in temperature
DEG C, pressure be 3~7MPa, mass space velocity is 0.5~3.0h-1, hydrogen flow rate be 5~30mL/min under conditions of reaction 4~
100h is to get an amino silane.
Specific embodiment 8: present embodiment is unlike specific embodiment seven: being done in the 3. step of step 1
The dry time is 110 DEG C, drying temperature 12h.It is other identical as specific embodiment seven.
Specific embodiment 9: present embodiment is unlike specific embodiment seven or eight: alcohol described in step 2 is
Methanol or ethyl alcohol.It is other identical as specific embodiment seven or eight.
Specific embodiment 10: the preparation method of present embodiment amino silane, comprising the following steps:
One, the preparation of hollow Co nanosphere, is synthesized by template of P123, specific steps are as follows:
1. by sodium hydroxide, cobalt source, hexamethylene, secondary deionized water and P123 template be in mass ratio 3:(4.8~
18.2) it: 2.4:1425:(31.9~53.7) weighs；Wherein cobalt source is Co (CH3COO)2·4H2O or CoSO4·7H2O；
It is put into insulating box 2. first mixing hexamethylene, P123 template and secondary deionized water, keeps 1 at room temperature
Microemulsion is made in~3h, and cobalt source is dissolved in secondary deionized water and obtains the cobalt source solution of 0.5~1mol/L, then by 0.5~
The cobalt source solution of 1mol/L is added in microemulsion, is then ultrasonically treated 10~30min；
3. sodium hydroxide, which is dissolved in secondary deionized water, obtains 0.03~0.05mol/L sodium hydroxide solution, then will
0.03~0.05mol/L sodium hydroxide solution is added dropwise in microemulsion in 30~60min, is ultrasonically treated 10~30min again,
It is then centrifuged for taking supernatant, 25 DEG C of supernatant is evaporated under reduced pressure, is centrifugated again after dehydrated alcohol dilutes, solid is transferred to
It dries in baking oven to get hollow Co nanosphere；
Wherein step 1. the weighed secondary deionized water of institute for step 2. in prepare microemulsion, configuration cobalt source solution and
3. step configures sodium hydroxide solution.
Two, prepare material liquid: will to cyano alkoxy silane with alcohol according to mass ratio 1:(0~0.5) be uniformly mixed, obtain
Material liquid；
Three, hydrogenation reaction: by the perseverance of the hollow Co nanosphere Catalyst packing of step 1 preparation to fixed bed reactors
In warm area, 40~120min is activated under conditions of temperature is 150~400 DEG C, hydrogen flow rate is 50~100mL/min, then
Material liquid prepared by step 1 is injected into fixed bed reactors using the mode that is continuously injected into, is then 100~200 in temperature
DEG C, pressure be 3~7MPa, mass space velocity is 0.5~3.0h-1, hydrogen flow rate be 5~30mL/min under conditions of reaction 4~
100h is to get an amino silane.
Specific embodiment 11: present embodiment is unlike specific embodiment ten: in the 3. step of step 1
The dry time is 110 DEG C, drying temperature 12h.It is other identical as specific embodiment ten.
Specific embodiment 12: present embodiment is unlike specific embodiment ten or 11: described in step 2
Alcohol is methanol or ethyl alcohol.It is other identical as specific embodiment ten or 11.
Elaborate below to the embodiment of the present invention, following embodiment under the premise of the technical scheme of the present invention into
Row is implemented, and gives detailed embodiment and specific operating process, but protection scope of the present invention is not limited to following realities
Apply example.
Embodiment 1:
The hydrogenation reaction of the hollow Co nanosphere catalysis cyano alkoxy silane of the present embodiment prepares the side of amino silane
Method carries out according to the following steps:
One, take 1.06g with process sulfonation processing with the polymethyl methacrylate-polymethylacrylic acid extended transversely through
The polystyrene hollow microballoon that the diameter in channel is 70nm is the double-layer hollow Co nanosphere of templated synthesis, and it is micro- to be packed into fixed bed
The flat-temperature zone of the stainless steel reaction pipe of type reaction unit, both ends are equipped with inertia quartz sand.Temperature is 200 DEG C, hydrogen flow rate is
2h is activated under conditions of 70ml/min, removes the water and impurity of adsorption, active sites are exposed；Two, by step 1
Hollow Co nanosphere after obtained activation, reaction temperature is 130 DEG C, reaction pressure 4MPa, reaction mass air speed are
1.0h-1, under conditions of hydrogen flow rate is 10ml/min, by the quality to cyanoethyl triethoxysilane and ethyl alcohol according to 1:0.5
Material liquid is made than being uniformly mixed, the catalyst bed of fixed bed reactors is continuously injected by Micro-metering Pumps, is reacted, is obtained
Amino silane；Three, the time that product is dripped in outflow first is calculated as t=0, and acquires the product once flowed out every 1h.
Double-layer hollow Co nanosphere described in the present embodiment is with process sulfonation processing with the poly- first extended transversely through
The polystyrene hollow microballoon that base methyl acrylate-polymethylacrylic acid channel diameter is 70nm is templated synthesis, specifically
Step are as follows: by cobalt source, ammonium hydroxide, secondary deionized water and polystyrene hollow microballoon be in mass ratio that 9:17:312:2 weighs (its
The middle weighed secondary deionized water of institute is used to prepare colloidal sol and configuration cobalt source solution), first by having by sulfonation processing
The polymethyl methacrylate extended transversely through-polymethylacrylic acid channel diameter be 70nm polystyrene hollow microballoon and
The ammonium hydroxide of 10mol/L is sufficiently mixed in proportion, and at room temperature stir 12h after, be added the amount of calculating it is secondary go from
Sub- water is diluted, and is then added dropwise to the cobalt source solution of 1mol/L in sol solutions in 2h, is ultrasonically treated 30min；Then will
Centrifuged solid washs three times in ethanol, and obtained solid, which is transferred in DMF, after centrifugation removes template polystyrene, centrifugation
Solid is transferred to the lower 500 DEG C of roasting 3h of air atmosphere in Muffle furnace up to double-layer hollow Co nanosphere afterwards；Wherein cobalt source is Co
(CH3COO)2·4H2O。
Gas chromatographic analysis is used to reaction product, calculates reaction product composition with area normalization method, it is known that cyanoethyl three
The conversion ratio of Ethoxysilane is 100%, and the selectivity of aminopropyl triethoxysilane can reach 99.65%.
Embodiment 2:
The hydrogenation reaction of the hollow Co nanosphere catalysis cyano alkoxy silane of the present embodiment prepares the side of amino silane
Method carries out according to the following steps:
One, SiO of the 1.06g with diameter for 10nm is taken2Microballoon is that the hollow Co nanosphere of templated synthesis is packed into fixed bed
The flat-temperature zone of the stainless steel reaction pipe of micro-reaction equipment, both ends are equipped with inertia quartz sand.It is 200 DEG C, hydrogen flow rate in temperature
To activate 2h under conditions of 70ml/min, the water and impurity of adsorption are removed, active sites are exposed；Two, by step
Hollow Co nanosphere after one obtained activation, reaction temperature be 130 DEG C, reaction pressure 4MPa, reaction mass air speed
For 1.0h-1, under conditions of hydrogen flow rate is 10ml/min, by the matter to cyanoethyl triethoxysilane and ethyl alcohol according to 1:0.5
Material liquid is made than being uniformly mixed in amount, and the catalyst bed of fixed bed reactors is continuously injected by Micro-metering Pumps, is reacted,
Obtain amino silane；Three, the time that product is dripped in outflow first is calculated as t=0, and acquires the product once flowed out every 1h.
Hollow Co nanosphere described in the present embodiment is the SiO with diameter for 10nm2Microballoon is templated synthesis, specifically
Step are as follows: by ammonium hydroxide, cobalt source, secondary deionized water and SiO2Microballoon (is wherein weighed by 5:4.2:750:10.6 in mass ratio
Secondary deionized water be used to prepare sol solutions and configuration cobalt source solution), first by diameter be 10nm SiO2It microballoon and goes
Ionized water is that after the ratio of 10.6:450 is sufficiently mixed sol solutions are made, the cobalt source solution of 0.6mol/L is added in mass ratio
In sol solutions, it is then ultrasonically treated 10min, is next added dropwise to 0.05mol/L ammonia spirit in sol solutions in 2h, again
It is ultrasonically treated 30min；Then centrifuged solid is successively washed in secondary deionized water and ethyl alcohol three times, after centrifugation
Solid is transferred to 600 DEG C of roasting 3h in Muffle furnace, by the solid after roasting in the sodium hydroxide solution of 10mol/L at 90 DEG C
12h is managed, is centrifugated again after secondary deionized water dilutes, after repeated washing-centrifugation three times, solid is transferred to 110 DEG C
Dry 12h is in baking oven to get hollow Co nanosphere；Wherein cobalt source is Co (CH3COO)2·4H2O.The hollow Co prepared receives
The partial size of meter Wei Qiu is only 20nm.
Gas chromatographic analysis is used to reaction product, calculates reaction product composition with area normalization method, it is known that cyanoethyl three
The conversion ratio of Ethoxysilane is 99.4%, and the selectivity of aminopropyl triethoxysilane is 98.37%.
Embodiment 3:
The hydrogenation reaction of the hollow Co nanosphere catalysis cyano alkoxy silane of the present embodiment prepares the side of amino silane
Method carries out according to the following steps:
One, 1.06g is taken to be packed into fixed-bed micro-reactor using the hollow Co nanosphere that F127 is synthesized as template
The flat-temperature zone of stainless steel reaction pipe, both ends are equipped with inertia quartz sand.In the item that temperature is 200 DEG C, hydrogen flow rate is 70ml/min
2h is activated under part, the water and impurity of adsorption is removed, active sites is exposed, hollow Co nanometers after being activated are micro-
Ball；Two, the hollow Co nanosphere after the activation for obtaining step 1, reaction temperature be 150 DEG C, reaction pressure 5MPa,
Reaction mass air speed is 1.0h-1, hydrogen flow rate be 10ml/min under conditions of, cyanoethyl triethoxysilane will be pressed with ethyl alcohol
According to 1:0.5 mass ratio be uniformly mixed material liquid is made, the catalyst bed of fixed bed reactors is continuously injected by Micro-metering Pumps
Layer, is reacted, obtains amino silane；Three, the time that product is dripped in outflow first is calculated as t=0, and acquires primary outflow every 1h
Product.
Hollow Co nanosphere is synthesized by template of F127 described in the present embodiment, specific steps are as follows: by hydrogen-oxygen
It is (wherein weighed by 3:5.4:2.4:1425:28.4 in mass ratio to change sodium, cobalt source, hexamethylene, secondary deionized water and F127
Secondary deionized water be used to prepare microemulsion, configuration cobalt source solution and configuration sodium hydroxide solution), first by hexamethylene,
F127 and deionized water are that the ratio of 2.4:28.4:1200 is sufficiently mixed to be put into insulating box and keeps 1h at 25 DEG C in mass ratio
After microemulsion is made, the cobalt source solution of 0.5mol/L is added in microemulsion, 10min is then ultrasonically treated, next will
0.05mol/L sodium hydroxide solution is added dropwise in microemulsion in 30min, is ultrasonically treated 10min again；It then will be through being centrifuged
It after the supernatant arrived depressurizes 25 DEG C of distillations, is centrifugated, solid is transferred in 110 DEG C of baking oven dry again after ethyl alcohol dilutes
12h is to get hollow Co nanosphere；Wherein cobalt source is Co (CH3COO)2·4H2O。
Gas chromatographic analysis is used to reaction product, calculates reaction product composition with area normalization method, it is known that cyanoethyl
The conversion ratio of triethoxysilane is 100%, and the selectivity of aminopropyl triethoxysilane is 97.53%.
Embodiment 4:
The hydrogenation reaction of the hollow Co nanosphere catalysis cyano alkoxy silane of the present embodiment prepares the side of amino silane
Method carries out according to the following steps:
One, 1.06g is taken to be packed into fixed-bed micro-reactor using the hollow Co nanosphere that F127 is synthesized as template
The flat-temperature zone of stainless steel reaction pipe, both ends are equipped with inertia quartz sand.In the item that temperature is 200 DEG C, hydrogen flow rate is 70ml/min
2h is activated under part, the water and impurity of adsorption is removed, active sites is exposed；Two, after the activation for obtaining step 1
Hollow Co nanosphere, reaction temperature is 150 DEG C, reaction pressure 4MPa, reaction mass air speed are 1.0h-1, hydrogen stream
Under conditions of speed is 10ml/min, system will be uniformly mixed according to the mass ratio of 1:0.5 with ethyl alcohol to cyanoethyl triethoxysilane
At material liquid, it is continuously injected into the catalyst bed of fixed bed reactors by Micro-metering Pumps, is reacted, amino silane is obtained；Three,
The time that product is dripped in outflow first is calculated as t=0, and acquires the product once flowed out every 1h.
Hollow Co nanosphere is synthesized by template of F127 described in the present embodiment, specific steps are as follows: by hydrogen-oxygen
Change sodium, cobalt source, hexamethylene, secondary deionized water and F127 (wherein to be weighed by 3:15.9:2.4:1425:46.2 in mass ratio
Secondary deionized water be used to prepare microemulsion, configuration cobalt source solution and configuration sodium hydroxide solution), first by hexamethylene,
F127 and deionized water are that the ratio of 2.4:28.4:1200 is sufficiently mixed to be put into insulating box and keeps 1h at 25 DEG C in mass ratio
After microemulsion is made, the cobalt source solution of 0.5mol/L is added in microemulsion, 10min is then ultrasonically treated, next will
0.05mol/L sodium hydroxide solution is added dropwise in microemulsion in 30min, is ultrasonically treated 10min again；It then will be through being centrifuged
It after the supernatant arrived depressurizes 25 DEG C of distillations, is centrifugated, solid is transferred in 110 DEG C of baking oven dry again after ethyl alcohol dilutes
12h is to get hollow Co nanosphere；Wherein cobalt source is Co (CH3COO)2·4H2O。
Using gas chromatographic analysis, reaction product composition is calculated with area normalization method, it is known that cyanoethyl triethoxysilane
Conversion ratio be 100%, the selectivity of aminopropyl triethoxysilane is 98.96%.
Embodiment 5:
The hydrogenation reaction of the hollow Co nanosphere catalysis cyano alkoxy silane of the present embodiment prepares the side of amino silane
Method carries out according to the following steps:
One, 1.06g is taken to be packed into fixed-bed micro-reactor using the hollow Co nanosphere that F127 is synthesized as template
The flat-temperature zone of stainless steel reaction pipe, both ends are equipped with inertia quartz sand.In the item that temperature is 200 DEG C, hydrogen flow rate is 70ml/min
2h is activated under part, the water and impurity of adsorption is removed, active sites is exposed；Two, after the activation for obtaining step 1
Hollow Co nanosphere, reaction temperature is 150 DEG C, reaction pressure 4MPa, reaction mass air speed are 1.5h-1, hydrogen stream
Under conditions of speed is 10ml/min, system will be uniformly mixed according to the mass ratio of 1:0.5 with ethyl alcohol to cyanoethyl triethoxysilane
At material liquid, it is continuously injected into the catalyst bed of fixed bed reactors by Micro-metering Pumps, is reacted, amino silane is obtained；Three,
The time that product is dripped in outflow first is calculated as t=0, and acquires the product once flowed out every 1h.
Hollow Co nanosphere is synthesized by template of F127 described in the present embodiment, specific steps are as follows: by hydrogen-oxygen
It is (wherein weighed by 3:7.3:2.4:1425:36.8 in mass ratio to change sodium, cobalt source, hexamethylene, secondary deionized water and F127
Secondary deionized water be used to prepare microemulsion, configuration cobalt source solution and configuration sodium hydroxide solution), first by hexamethylene,
F127 and deionized water are that the ratio of 2.4:28.4:1200 is sufficiently mixed to be put into insulating box and keeps 1h at 25 DEG C in mass ratio
After microemulsion is made, the cobalt source solution of 0.5mol/L is added in microemulsion, 10min is then ultrasonically treated, next will
0.05mol/L sodium hydroxide solution is added dropwise in microemulsion in 30min, is ultrasonically treated 10min again；It then will be through being centrifuged
It after the supernatant arrived depressurizes 25 DEG C of distillations, is centrifugated, solid is transferred in 110 DEG C of baking oven dry again after ethyl alcohol dilutes
12h is to get hollow Co nanosphere；Wherein cobalt source is CoSO4·7H2O。
Gas chromatographic analysis is used to reaction product, calculates reaction product composition with area normalization method, it is known that cyanoethyl three
The conversion ratio of Ethoxysilane is 99.12%, and the selectivity of aminopropyl triethoxysilane is 98.30%.
Embodiment 6:
The hydrogenation reaction of the hollow Co nanosphere catalysis cyano alkoxy silane of the present embodiment prepares the side of amino silane
Method carries out according to the following steps:
One, 1.06g is taken to be packed into fixed-bed micro-reactor using the hollow Co nanosphere that F127 is synthesized as template
The flat-temperature zone of stainless steel reaction pipe, both ends are equipped with inertia quartz sand.In the item that temperature is 200 DEG C, hydrogen flow rate is 70ml/min
2h is activated under part, the water and impurity of adsorption is removed, active sites is exposed；Two, after the activation for obtaining step 1
Hollow Co nanosphere, reaction temperature is 130 DEG C, reaction pressure 4MPa, reaction mass air speed are 1.0h-1, hydrogen stream
Under conditions of speed is 10ml/min, system will be uniformly mixed according to the mass ratio of 1:0.5 with ethyl alcohol to cyanoethyl triethoxysilane
At material liquid, it is continuously injected into the catalyst bed of fixed bed reactors by Micro-metering Pumps, is reacted, amino silane is obtained；Three,
The time that product is dripped in outflow first is calculated as t=0, and acquires the product once flowed out every 1h.
Hollow Co nanosphere is synthesized by template of F127 described in the present embodiment, specific steps are as follows: by hydrogen-oxygen
It is (wherein weighed by 3:8.9:2.4:1425:36.7 in mass ratio to change sodium, cobalt source, hexamethylene, secondary deionized water and F127
Secondary deionized water be used to prepare microemulsion, configuration cobalt source solution and configuration sodium hydroxide solution), first by hexamethylene,
F127 and deionized water are that the ratio of 2.4:28.4:1200 is sufficiently mixed to be put into insulating box and keeps 1h at 25 DEG C in mass ratio
After microemulsion is made, the cobalt source solution of 0.5mol/L is added in microemulsion, 10min is then ultrasonically treated, next will
0.05mol/L sodium hydroxide solution is added dropwise in microemulsion in 30min, is ultrasonically treated 10min again；It then will be through being centrifuged
It after the supernatant arrived depressurizes 25 DEG C of distillations, is centrifugated, solid is transferred in 110 DEG C of baking oven dry again after ethyl alcohol dilutes
12h is to get hollow Co nanosphere；Wherein cobalt source is Co (CH3COO)2·4H2O。
Gas chromatographic analysis is used to reaction product, calculates reaction product composition with area normalization method, it is known that cyanoethyl three
The conversion ratio of Ethoxysilane is 100%, and the selectivity of aminopropyl triethoxysilane is 99.25%.
Embodiment 7:
The hydrogenation reaction of the hollow Co nanosphere catalysis cyano alkoxy silane of the present embodiment prepares the side of amino silane
Method carries out according to the following steps:
One, 1.06g is taken to be packed into fixed-bed micro-reactor using the hollow Co nanosphere that P123 is synthesized as template
The flat-temperature zone of stainless steel reaction pipe, both ends are equipped with inertia quartz sand.In the item that temperature is 200 DEG C, hydrogen flow rate is 70ml/min
2h is activated under part, the water and impurity of adsorption is removed, active sites is exposed；Two, after the activation for obtaining step 1
Hollow Co nanosphere, reaction temperature is 130 DEG C, reaction pressure 4MPa, reaction mass air speed are 1.0h-1, hydrogen stream
Under conditions of speed is 10ml/min, it is made being uniformly mixed with ethyl alcohol according to the mass ratio of 1:0 to cyanoethyl triethoxysilane
Material liquid is continuously injected into the catalyst bed of fixed bed reactors by Micro-metering Pumps, is reacted, obtains amino silane；Three, will
The time of outflow the first drop product is calculated as t=0, and the product once flowed out is acquired every 1h.
Hollow Co nanosphere is synthesized by template of P123 described in the present embodiment, specific steps are as follows: by hydrogen-oxygen
It is (wherein weighed by 3:4.8:2.4:1425:53.7 in mass ratio to change sodium, cobalt source, hexamethylene, secondary deionized water and P123
Secondary deionized water be used to prepare microemulsion, configuration cobalt source solution and configuration sodium hydroxide solution), first by hexamethylene,
P123 and deionized water are that the ratio of 2.4:53.7:1200 is sufficiently mixed to be put into insulating box and keeps 1h at 25 DEG C in mass ratio
After microemulsion is made, the cobalt source solution of 0.5mol/L is added in microemulsion, 10min is then ultrasonically treated, next will
0.05mol/L sodium hydroxide solution is added dropwise in microemulsion in 30min, is ultrasonically treated 10min again；It then will be through being centrifuged
It after the supernatant arrived depressurizes 25 DEG C of distillations, is centrifugated, solid is transferred in 110 DEG C of baking oven dry again after ethyl alcohol dilutes
12h is to get hollow Co nanosphere；Wherein cobalt source is Co (CH3COO)2·4H2O。
Gas chromatographic analysis is used to reaction product, calculates reaction product composition with area normalization method, it is known that cyanoethyl three
The conversion ratio of Ethoxysilane is 99.47%, and the selectivity of aminopropyl triethoxysilane is 97.93%.
Embodiment 8:
The hydrogenation reaction of the hollow Co nanosphere catalysis cyano alkoxy silane of the present embodiment prepares the side of amino silane
Method carries out according to the following steps:
One, 1.06g is taken to be packed into fixed-bed micro-reactor using the hollow Co nanosphere that P123 is synthesized as template
The flat-temperature zone of stainless steel reaction pipe, both ends are equipped with inertia quartz sand.In the item that temperature is 200 DEG C, hydrogen flow rate is 70ml/min
2h is activated under part, the water and impurity of adsorption is removed, active sites is exposed；Two, after the activation for obtaining step 1
Hollow Co nanosphere, reaction temperature is 130 DEG C, reaction pressure 4MPa, reaction mass air speed are 1.0h-1, hydrogen stream
Under conditions of speed is 10ml/min, system will be uniformly mixed according to the mass ratio of 1:0.5 with ethyl alcohol to cyanoethyl triethoxysilane
At material liquid, it is continuously injected into the catalyst bed of fixed bed reactors by Micro-metering Pumps, is reacted, amino silane is obtained；Three,
The time that product is dripped in outflow first is calculated as t=0, and acquires the product once flowed out every 1h.
Hollow Co nanosphere is synthesized by template of P123 described in the present embodiment, specific steps are as follows: by hydrogen-oxygen
Change sodium, cobalt source, hexamethylene, secondary deionized water and P123 (wherein to be weighed by 3:18.2:2.4:1425:31.9 in mass ratio
Secondary deionized water be used to prepare microemulsion, configuration cobalt source solution and configuration sodium hydroxide solution), first by hexamethylene,
P123 and deionized water are that the ratio of 2.4:31.9:1200 is sufficiently mixed to be put into insulating box and keeps 1h at 25 DEG C in mass ratio
After microemulsion is made, the cobalt source solution of 0.5mol/L is added in microemulsion, 10min is then ultrasonically treated, next will
0.05mol/L sodium hydroxide solution is added dropwise in microemulsion in 30min, is ultrasonically treated 10min again；It then will be through being centrifuged
It after the supernatant arrived depressurizes 25 DEG C of distillations, is centrifugated, solid is transferred in 110 DEG C of baking oven dry again after ethyl alcohol dilutes
12h is to get hollow Co nanosphere；Wherein cobalt source is CoSO4·7H2O。
Gas chromatographic analysis is used to reaction product, calculates reaction product composition with area normalization method, it is known that cyanoethyl three
The conversion ratio of Ethoxysilane is 100%, and the selectivity of aminopropyl triethoxysilane is 98.20%.
Embodiment 9:
The hydrogenation reaction of the hollow Co nanosphere catalysis cyano alkoxy silane of the present embodiment prepares the side of amino silane
Method carries out according to the following steps:
One, 1.06g is taken to be packed into fixed-bed micro-reactor using the hollow Co nanosphere that F127 is synthesized as template
The flat-temperature zone of stainless steel reaction pipe, both ends are equipped with inertia quartz sand.In the item that temperature is 200 DEG C, hydrogen flow rate is 70ml/min
2h is activated under part, the water and impurity of adsorption is removed, active sites is exposed；Two, after the activation for obtaining step 1
Hollow Co nanosphere, reaction temperature is 130 DEG C, reaction pressure 4MPa, reaction mass air speed are 1.0h-1, hydrogen stream
Under conditions of speed is 10ml/min, cyanoethyl trimethoxy silane will be uniformly mixed with methanol according to 1:0 mass ratio and original is made
Feed liquid is continuously injected into the catalyst bed of fixed bed reactors by Micro-metering Pumps, is reacted, obtains amino silane；It three, will stream
The time of the first drop product is calculated as t=0 out, and the product once flowed out is acquired every 1h.
Hollow Co nanosphere is synthesized by template of F127 described in the present embodiment, specific steps are as follows: by hydrogen-oxygen
It is (wherein weighed by 3:8.9:2.4:1425:36.7 in mass ratio to change sodium, cobalt source, hexamethylene, secondary deionized water and F127
Secondary deionized water be used to prepare microemulsion, configuration cobalt source solution and configuration sodium hydroxide solution), first by hexamethylene,
F127 and deionized water are that the ratio of 2.4:28.4:1200 is sufficiently mixed to be put into insulating box and keeps 1h at 25 DEG C in mass ratio
After microemulsion is made, the cobalt source solution of 0.5mol/L is added in microemulsion, 10min is then ultrasonically treated, next will
0.05mol/L sodium hydroxide solution is added dropwise in microemulsion in 30min, is ultrasonically treated 10min again；It then will be through being centrifuged
It after the supernatant arrived depressurizes 25 DEG C of distillations, is centrifugated, solid is transferred in 110 DEG C of baking oven dry again after ethyl alcohol dilutes
12h is to get hollow Co nanosphere；Wherein cobalt source is Co (CH3COO)2·4H2O。
Reaction product uses gas chromatographic analysis, calculates reaction product composition with area normalization method, it is known that three second of cyanoethyl
The conversion ratio of oxysilane is 100%, and the selectivity of aminopropyl triethoxysilane is 98.02%.
Embodiment 10:
The hydrogenation reaction of the hollow Co nanosphere catalysis cyano alkoxy silane of the present embodiment prepares the side of amino silane
Method carries out according to the following steps:
One, 1.06g is taken to be packed into fixed-bed micro-reactor using the hollow Co nanosphere that F127 is synthesized as template
The flat-temperature zone of stainless steel reaction pipe, both ends are equipped with inertia quartz sand.In the item that temperature is 200 DEG C, hydrogen flow rate is 70ml/min
2h is activated under part, the water and impurity of adsorption is removed, active sites is exposed；Two, after the activation for obtaining step 1
Hollow Co nanosphere, reaction temperature is 130 DEG C, reaction pressure 4MPa, reaction mass air speed are 1.0h-1, hydrogen stream
Under conditions of speed is 10ml/min, cyanoethyl trimethoxy silane will be uniformly mixed with methanol according to 1:0.5 mass ratio and be made
Material liquid is continuously injected into the catalyst bed of fixed bed reactors by Micro-metering Pumps, is reacted, obtains amino silane；Three, will
The time of outflow the first drop product is calculated as t=0, and the product once flowed out is acquired every 1h.
Hollow Co nanosphere is synthesized by template of F127 described in the present embodiment, specific steps are as follows: by hydrogen-oxygen
It is (wherein weighed by 3:8.9:2.4:1425:36.7 in mass ratio to change sodium, cobalt source, hexamethylene, secondary deionized water and F127
Secondary deionized water be used to prepare microemulsion, configuration cobalt source solution and configuration sodium hydroxide solution), first by hexamethylene,
F127 and deionized water are that the ratio of 2.4:28.4:1200 is sufficiently mixed to be put into insulating box and keeps 1h at 25 DEG C in mass ratio
After microemulsion is made, the cobalt source solution of 0.5mol/L is added in microemulsion, 10min is then ultrasonically treated, next will
0.05mol/L sodium hydroxide solution is added dropwise in microemulsion in 30min, is ultrasonically treated 10min again；It then will be through being centrifuged
It after the supernatant arrived depressurizes 25 DEG C of distillations, is centrifugated, solid is transferred in 110 DEG C of baking oven dry again after ethyl alcohol dilutes
12h is to get hollow Co nanosphere；Wherein cobalt source is Co (CH3COO)2·4H2O。
Reaction product uses gas chromatographic analysis, calculates reaction product composition with area normalization method, it is known that cyanoethyl front three
The conversion ratio of oxysilane is 100%, and the selectivity of aminopropyl trimethoxysilane is 97.82%.
Claims (1)
1. the preparation method of amino silane, it is characterised in that method includes the following steps:
One, the preparation of hollow Co nanosphere, is with SiO2Microballoon is templated synthesis, specific steps are as follows:
1. by ammonium hydroxide, cobalt source, secondary deionized water and SiO2Microballoon is 5:(3.9~7.2 in mass ratio): 750:(8.9~13.3)
It weighs, wherein the cobalt source is Co (CH3COO)2·4H2O or CoSO4·7H2O, the SiO2The diameter of microballoon is 10~40nm,
The concentration of the ammonium hydroxide is 0.05mol/L；
2. first by SiO2Microballoon and secondary deionized water are mixed and made into sol solutions, and cobalt source is dissolved in secondary deionized water and obtains 0.3
Then the cobalt source solution of 0.3~0.6mol/L is added in sol solutions by the cobalt source solution of~0.6mol/L, and ultrasonic treatment 10~
Then ammonium hydroxide is added dropwise in sol solutions by 30min in 2~3h, be ultrasonically treated 30~60min again；
3. being then centrifuged for, centrifuged solid is successively washed 3~5 times in secondary deionized water and ethyl alcohol, after centrifugation
It is molten that solid is transferred to 550~700 DEG C of 3~5h of roasting, the sodium hydroxide by the solid after roasting in 5~10mol/L in Muffle furnace
In liquid at 90~110 DEG C processing 12~for 24 hours, be centrifugated again after secondary deionized water dilutes, by solid repeated washing-from
The heart three times after, by solid be transferred in baking oven dry to get hollow Co nanosphere；
Wherein step 1. the weighed secondary deionized water of institute for step 2. in prepare sol solutions and configuration cobalt source solution；
Two, prepare material liquid: will to cyano alkoxy silane with alcohol according to mass ratio 1:(0~0.5) be uniformly mixed, obtain raw material
Liquid；
Three, hydrogenation reaction: by the hollow Co nanosphere Catalyst packing of step 1 preparation to the flat-temperature zone of fixed bed reactors
It is interior, 40~120min is activated under conditions of temperature is 150~400 DEG C, hydrogen flow rate is 50~100mL/min, is then used
Be continuously injected into mode material liquid prepared by step 2 is injected into fixed bed reactors, then temperature be 100~200 DEG C,
Pressure is 3~7MPa, mass space velocity is 0.5~3.0h-1, hydrogen flow rate be 5~30mL/min under conditions of react 4~100h,
Up to amino silane；
Temperature 3. dry described in step is 110 DEG C in step 1, and the dry time is 12h；
Alcohol described in step 2 is methanol or ethyl alcohol.
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