CN109718781A - A kind of silicon tetrachloride adds hydrogen to prepare trichlorosilane catalyst and preparation method thereof - Google Patents
A kind of silicon tetrachloride adds hydrogen to prepare trichlorosilane catalyst and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 107
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 239000005052 trichlorosilane Substances 0.000 title claims abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 15
- 239000001257 hydrogen Substances 0.000 title claims abstract description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 14
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 title claims description 29
- 239000005049 silicon tetrachloride Substances 0.000 title claims description 29
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 33
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 23
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002002 slurry Substances 0.000 claims abstract description 17
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 16
- 239000007921 spray Substances 0.000 claims abstract description 15
- 239000002671 adjuvant Substances 0.000 claims abstract description 13
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 13
- 239000010703 silicon Substances 0.000 claims abstract description 13
- 229910001593 boehmite Inorganic materials 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims abstract description 12
- 238000007493 shaping process Methods 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 230000020477 pH reduction Effects 0.000 claims abstract description 6
- 150000003839 salts Chemical class 0.000 claims abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims description 35
- 239000002184 metal Substances 0.000 claims description 35
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 20
- 239000007789 gas Substances 0.000 claims description 12
- 229910021529 ammonia Inorganic materials 0.000 claims description 9
- 229910052749 magnesium Inorganic materials 0.000 claims description 9
- 238000000465 moulding Methods 0.000 claims description 9
- 229910002651 NO3 Inorganic materials 0.000 claims description 8
- 239000012752 auxiliary agent Substances 0.000 claims description 8
- 229910052788 barium Inorganic materials 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 229910052804 chromium Inorganic materials 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 235000019353 potassium silicate Nutrition 0.000 claims description 7
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 150000003863 ammonium salts Chemical class 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 239000003599 detergent Substances 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 claims description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical group OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 239000004744 fabric Substances 0.000 claims 1
- 239000003595 mist Substances 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000000052 vinegar Substances 0.000 claims 1
- 235000021419 vinegar Nutrition 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 29
- 230000000694 effects Effects 0.000 abstract description 12
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical class Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 abstract description 6
- 239000011863 silicon-based powder Substances 0.000 abstract description 6
- 230000035939 shock Effects 0.000 abstract description 2
- 229910044991 metal oxide Inorganic materials 0.000 abstract 1
- 150000004706 metal oxides Chemical class 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 17
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 11
- 229920005591 polysilicon Polymers 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 239000010949 copper Substances 0.000 description 6
- 238000005984 hydrogenation reaction Methods 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000001099 ammonium carbonate Substances 0.000 description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- SPIFDSWFDKNERT-UHFFFAOYSA-N nickel;hydrate Chemical compound O.[Ni] SPIFDSWFDKNERT-UHFFFAOYSA-N 0.000 description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910003910 SiCl4 Inorganic materials 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 235000012501 ammonium carbonate Nutrition 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- GPATXKGIPSPFHV-UHFFFAOYSA-N Cl[SiH](Cl)Cl.Cl[Si](Cl)(Cl)Cl Chemical compound Cl[SiH](Cl)Cl.Cl[Si](Cl)(Cl)Cl GPATXKGIPSPFHV-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- KMWBBMXGHHLDKL-UHFFFAOYSA-N [AlH3].[Si] Chemical compound [AlH3].[Si] KMWBBMXGHHLDKL-UHFFFAOYSA-N 0.000 description 1
- USTOTNAAAPBEAW-UHFFFAOYSA-N [Cl].[Si](Cl)(Cl)(Cl)Cl Chemical compound [Cl].[Si](Cl)(Cl)(Cl)Cl USTOTNAAAPBEAW-UHFFFAOYSA-N 0.000 description 1
- PRKQVKDSMLBJBJ-UHFFFAOYSA-N ammonium carbonate Chemical class N.N.OC(O)=O PRKQVKDSMLBJBJ-UHFFFAOYSA-N 0.000 description 1
- 235000011162 ammonium carbonates Nutrition 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
- CSSYLTMKCUORDA-UHFFFAOYSA-N barium(2+);oxygen(2-) Chemical compound [O-2].[Ba+2] CSSYLTMKCUORDA-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000006298 dechlorination reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- VDGJOQCBCPGFFD-UHFFFAOYSA-N oxygen(2-) silicon(4+) titanium(4+) Chemical compound [Si+4].[O-2].[O-2].[Ti+4] VDGJOQCBCPGFFD-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
Abstract
The present invention provides a kind of silicon tetrachlorides, and hydrogen to be added to prepare trichlorosilane catalyst and preparation method thereof.Catalyst composition includes silica, aluminium oxide, active component and adjuvant component；On the basis of catalyst weight, alumina content is 10%~20%, and dioxide-containing silica is 15%~25%, and content of the active component in terms of metal oxide is 55%~75%, and content of the adjuvant component in terms of oxide is 0.5%~2.0%.The preparation method of the catalyst is that into silicon source, addition acid solution progress acidification adds active component, promoter soluble salt, boehmite and curing agent and deionized water is made into slurries；Slurries are formed using spray shaping mode, it is post-treated that catalyst is made.Catalyst of the present invention has good activity stability, mechanical strength and wearability, increases catalyst in fluidized bed use process with the shock of silicon powder, friction, capability, avoids " running damage " phenomenon in catalyst use process.
Description
Technical field
The present invention relates to a kind of hydrogenation catalysts and preparation method thereof, add hydrogen to prepare three more particularly to a kind of silicon tetrachloride
Chlorine hydrogen Si catalyst and preparation method thereof.
Background technique
With the gradual depletion of fossil energy and problem of environmental pollution increasingly sharpens, seek it is a kind of it is free of contamination can be again
The raw energy becomes the task of top priority.Solar energy has spatter property, safety as the most abundant renewable energy compared with other energy
The advantages that property, popularity, the adequacy of resource and potential economy.Solar energy is made full use of, is realized under low-carbon mode
Sustainable development has important economy and strategic importance.
In recent years, polysilicon yield sharply increases, the main production of polysilicon have improved Siemens, silane thermal decomposition process and
Fluidized bed process, wherein improved Siemens are the mainstream technologys of current production polysilicon, are that production polysilicon is most mature, invest wind
Danger is minimum, is easiest to the technique of enlarging, and polysilicon produced is the 70%~80% of world's production.Currently, Siemens's work
The polysilicon factory of skill is all made of silicon powder and trichlorosilane is produced in the synthesis of hydrogen chloride.In synthetic product, trichlorosilane accounts for 80%,
Silicon tetrachloride accounts for 20%.It restores, is decomposed during generating high purity polycrystalline silicon product under atmosphere of the trichlorosilane in 1100 DEG C,
The nearly 6t of product by-produced tetrachlorosilane per ton.So generally using the polysilicon factory polysilicon product by-product per ton of Siemens process
The nearly 10t of silicon tetrachloride.
Silicon tetrachloride is a kind of toxic and harmful gas, is arbitrarily discharged if untreated, silicon tetrachloride will be with atmosphere
In steam combine, generate hydrogen chloride gas, environment caused seriously to pollute in addition, also result in the significant wastage of resource, is added
The production cost of great Liao enterprise.How safe handling silicon tetrachloride has become the bottleneck for restricting polysilicon development, finds effectively place
The approach for managing silicon tetrachloride is current urgent problem to be solved.Silicon tetrachloride is rationally recycled, it is same what is reduced environmental pollution
When, the production cost of enterprise is also reduced, the sustainable development of production of polysilicon enterprise is conducive to.
Mainly there are two directions for silicon tetrachloride recycling, first is that producing the production of other chemical industry using silicon tetrachloride as raw material
Product, including fume colloidal silica, organosilicon product and production optical fiber etc.；Second is that in polysilicon production process by hydrogenation of silicon tetrachloride
Trichlorosilane is converted into be recycled.The former demand is limited, cannot largely consume by-produced tetrachlorosilane, and research emphasis is concentrated
It is recycled in silicon tetrachloride.Hydrogenation of silicon tetrachloride technology is mainly hot hydrogenization method, cold hydrogenization method, plasma hydrogenization method and urges
Change hydrogenization method.Hot hydrogenization method is that silicon tetrachloride is generated trichlorosilane in 1250 DEG C of hydrogenations, and product is easily isolated, but reaction temperature
Height, energy consumption is high；Cold hydrogenization method is that production will be reacted under the conditions of silicon tetrachloride, silicon powder and hydrogen in a fluidized bed reactor 400 DEG C
Trichlorosilane, reaction temperature is relatively low, but product is difficult to separate, conversion ratio is low and reactor wear is serious；Plasma hydrogenization
Method carries out under the conditions of normal pressure and 3000 DEG C, and silicon tetrachloride maximum conversion is up to 74%, but energy consumption is very high, it is difficult to industrialize；
Catalytic hydrogenation is to pass through that catalyst is added on the basis of hot hydrogenation process, i.e., using silicon powder, hydrogen, silicon tetrachloride as raw material,
Under catalyst existence condition, under 500~550 DEG C of reaction temperature, 2.0~3.0MPa of reaction pressure, trichlorosilane, dichloro are generated
The mixture of dihydro silicon etc..
Due to silicon tetrachloride catalytic hydrogenation be carried out under compared with low reaction temperatures and reaction pressure, meanwhile, product is easy to point
From and keep high conversion, have become recycling silicon tetrachloride desirable route therefore urged in silicon tetrachloride catalytic hydrogenation
It the selection of agent and prepares particularly important.
CN105536789A discloses a kind of method that silicon tetrachloride hydrogenation-dechlorination prepares the catalyst of trichlorosilane.The party
Method directly mixes the amorphous silicon aluminium powder after roasting with a certain amount of stannous chloride, under an inert atmosphere high-temperature process, product
It is finished catalyst after cooling.Although the preparation method is simple and preparation cost is low, the activity for obtaining catalyst is lower.
CN102626630A, CN105967189A disclose a kind of side of preparing trichlorosilane from silicon tetrachloride through hydrogenation catalyst
Method.This method be by soluble nickel salt, metal M soluble-salt compound, be capable of providing the silicon source of silica and can sink
The precipitating reagent of shallow lake nickel and/or metal M ion contacts in a solvent, will contact products therefrom filtering, and by obtained solid successively into
Row is dry and roasts to get catalyst is arrived.Wherein M is selected from one of IB, IIB, IIA and the group VIII metal in addition to Ni
Or it is a variety of.The catalyst of this method preparation is powdery, in a fluidized bed using " running damage " is easy, causes catalyst loss and activity
It reduces.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of silicon tetrachloride add hydrogen prepare trichlorosilane catalyst and its
Preparation method.It is concentrated using the catalyst of this method preparation with distribution of particle sizes, while activity with higher, active metal
Dispersibility and abrasion resistance meet industrialization fluidized bed silicon tetrachloride and hydrogen are added to prepare trichlorosilane requirement, and the catalyst is in tetrachloro
SiClx activity and stability with higher during adding hydrogen to prepare trichlorosilane.
The present invention provides a kind of silicon tetrachlorides, and hydrogen to be added to prepare trichlorosilane catalyst, and catalyst composition includes titanium dioxide
Silicon, aluminium oxide, active component and adjuvant component, active component are group VIII metal, and adjuvant component is metal M；With catalyst
It is counted on the basis of weight, alumina content is 10%~20%, and dioxide-containing silica is 14.5%~25%, and active component is in terms of oxide
Content be 55%~75%, content of the adjuvant component in terms of the oxide of metal M be 0.5%~2.0%, the metal M be Cu,
One of Fe, Mg, Cr and Ba or a variety of.
It is bulk phase catalyst that silicon tetrachloride provided by the invention, which adds hydrogen to prepare trichlorosilane catalyst,.
In catalyst of the present invention, active component group VIII metal is Ni and/or Co, preferably Ni.
In catalyst of the present invention, adjuvant component metal M preferably uses M1 and M2, wherein M1 be one of Cu, Mg, Fe or
A variety of, preferably one of Cu, Mg or a variety of, M2 are one of Cr and Ba or a variety of, preferably Ba.The M1 and M2 with
The molar ratio of oxide meter is 1:10 ~ 10:1, preferably 2:1 ~ 8:1.
The property of catalyst of the present invention is as follows: specific surface area > 50m2/ g, preferably 60~120m2/g.In the present invention, compare table
Area is using low temperature liquid nitrogen determination of adsorption method.
The size distribution of catalyst of the present invention is following (with volume fraction): partial size < 150mm particle accounts for 10% hereinafter, excellent
Select 8% or less；Partial size accounts for 75%~95%, preferably 80%~92% in the particle of 150~500mm, and partial size > 500mm particle accounts for
15% hereinafter, it is preferred that 12% or less.In the present invention, granularity is using laser particle analyzer measurement.
The rate of wear < 2.0wt% of catalyst of the present invention, preferably < 1.5wt%.In the present invention, rate of wear is using fluidisation state mill
Damage strength tester measurement.
Another aspect of the present invention provides the preparation method that the silicon tetrachloride adds hydrogen to prepare trichlorosilane catalyst, packet
It includes:
(1) acid solution is added into silicon source and carries out acidification；
(2) soluble-salt containing group VIII metal, the solubility containing metal M are separately added into step (1) resulting material
Salt, boehmite, curing agent, deionized water, are configured to slurries；
(3) slurries obtained by step (2) are subjected to spray shaping, obtain spherical gel；
(4) by the resulting spherical gel washing of step (3), dry, roasting, catalyst is obtained.
In the method for the present invention, silicon source described in step (1) is waterglass and/or silica solution, the quality in terms of silica
Content is 20%~40%, preferably 25%~35%.The acid solution is one of nitric acid, formic acid, acetic acid, citric acid or several
Kind, preferably nitric acid, wherein the mass concentration of nitric acid is 55%~75%, preferably 60%~65%.After the silicon source carries out acidification
Its pH value is 1.0~4.0, preferably 2.5~3.5.
In the method for the present invention, group VIII metal described in step (2) is Ni and/or Co, preferably Ni.Group VIII metal can
Soluble is selected from one or more of nitrate, sulfate and chloride, preferably nitrate.The metal M be Cu, Fe, Mg,
One of Cr and Ba or a variety of, it is preferred to use M1 and M2, wherein M1 is one of Cu, Fe, Mg or a variety of, preferably Cu,
One of Mg or a variety of, M2 are one of Cr and Ba or a variety of, preferably Ba.The soluble-salt of metal M be nitrate and
One of sulfate is a variety of, preferably nitrate.
In the method for the present invention, the dry weight of step (2) described boehmite is 70% or more, is converted through high-temperature roasting
For γ-Al2O3Property afterwards is as follows: Kong Rongwei 0.95mL/g or more, and preferably 0.95 ~ 1.2mL/g of Kong Rongwei, specific surface area is
330m2/ g or more, preferably specific surface area are 330 ~ 400m2/g.The curing agent is one of urea, organic ammonium salt or a variety of.
The organic ammonium salt is six methines, four ammonium.The additional amount of the curing agent and the molar ratio of the active metal and auxiliary agent are
0.5:1.0 ~ 1.2:1.0, preferably 0.6:1.0 ~ 1.0:1.0；In slurries obtained by step (2) silicon source in terms of silica, intend thin water
The gross mass that aluminium stone is in terms of aluminium oxide, active component and adjuvant component are in terms of oxide accounts for the 25%~45% of slurries total weight, excellent
Select 30%~35%.
In the method for the present invention, spray shaping described in step (3) is press spray molding.The spray shaping is spraying
It being carried out in molding tower, nozzle diameter 0.3mm~1.2mm, preferably 0.6mm~1.0mm, spraying pressure is 0.5 ~ 1.5MPa, by
The molding and hot gas medium counter current contacting that nozzle sprays, the temperature of hot gas medium are 70~200 DEG C, preferably 90~120
DEG C, gas medium uses ammonia-containing gas, can use the air containing ammonia, wherein NH3Volume fraction be 5% ~ 10%.
In the method for the present invention, washing described in step (4) is with deionized water by spherical gel detergent to neutrality；It is described
Drying condition are as follows: it is 4~10 hours dry at 80~200 DEG C, it is 6~8 hours dry preferably at 100~150 DEG C；The roasting
Condition are as follows: roast 3~8 hours at 500~900 DEG C, roasted 3~5 hours preferably at 550~700 DEG C.
Compared with prior art, the invention has the following advantages that
1, catalyst of the present invention uses aluminium silicon composite material for carrier component, in auxiliary agent and active metal component and carrier component
Under synergistic effect, catalytic mechanical intensity and wear-resisting property are not only increased, further improves active metal and auxiliary agent group
The dispersion degree divided, the activity and stability of catalyst are significantly improved, and are more advantageous to catalyst in fluidized-bed process
Using increasing shock, the friction, capability of catalyst and silicon powder, avoid " run about damage " phenomenon in catalyst use process.
2, catalyst of the present invention preferably uses two kinds of auxiliary agents of M1 and M2, further improves the synergistic effect of two kinds of auxiliary agents
The dispersion degree of active metal and the wear-resisting property of catalyst further improve the activity and activity stability of catalyst.
3, in the preparation method of catalyst of the present invention, first silicon source is acidified, active component is then added, adjuvant component, intends
Boehmite, curing agent and water form slurries, and by the way of spray shaping, and each component collaboration is made to play a role, so that system
Standby catalyst has biggish specific surface area while having preferable intensity, provides more reacting environment for reactant,
Catalyst activity can be effectively improved.
4, in the preparation method of catalyst of the present invention, spray shaping is using pressure forming and using ammonia-containing gas and molding
Object counter current contacting makes molding carry out being formed by curing ball under the double action that external ammonia and internal curing agent are pyrolyzed in this way
Shape gel, makes catalyst not only in this way and has good and uniform spherical, has good abrasion resistance, but also have good
Pore structure, be conducive to silicon tetrachloride be hydrogenated to trichlorosilane reaction progress, catalyst it is with higher activity and stablize
Property.
5, the molding of catalyst and active metal load are integrated in one, shorten by the preparation method of catalyst of the present invention
The preparation flow of catalyst.
Specific embodiment
Technical solution of the present invention is further illustrated by the following examples, but is not limited to following embodiment.
Embodiment 1
The waterglass 57.1g that mass content is 35% in terms of silica is added into preparing tank, starts agitating device, then slowly add
Entering mass concentration is 62% nitric acid solution, makes the pH value 2.5 of water glass solution after acidification, is added after being uniformly mixed into preparing tank
It is as follows to enter six water nickel nitrate of 266.7g, 1.82g nitrate trihydrate copper, 1.0g barium nitrate, boehmite 21.4g(property: Kong Rongwei
0.985mL/g, specific surface area 363m2/ g, butt 72wt%), curing agent urea 53.6g and deionized water, in gained slurries
Waterglass in terms of silica, boehmite in terms of aluminium oxide, nickel nitrate in terms of nickel oxide, copper nitrate is in terms of copper oxide and nitre
Gross mass of the sour barium in terms of barium monoxide accounts for the 33% of slurries total weight.
The above-mentioned slurries with certain fluidity are subjected to spray shaping in spray shaping tower, set nozzle diameter as
0.8mm, spraying pressure are 1.0MPa, and the molding sprayed by nozzle is contacted with hot air inversion containing ammonia, the hot air containing ammonia
Temperature is 100 DEG C, NH in air containing ammonia3Volume fraction be 7%, material solidifies and shrinks, and obtains spherical gel；
Obtained spherical gel is washed with deionized to neutrality, and 8 hours dry at 130 DEG C, then through being roasted at 600 DEG C
Obtain catalyst A of the present invention within 3 hours, catalyst property is shown in Table 1, and evaluating catalyst the results are shown in Table 2.
Embodiment 2
Curing agent urea 53.6g is changed to six methines, four ammonium 124g, nitrate trihydrate copper is added by preparation process such as embodiment 1
Amount is changed to 2.62g, and the additional amount of barium nitrate is changed to 0.56g, preparation catalyst B of the present invention, and property is shown in Table 1, evaluating catalyst knot
Fruit is shown in Table 2.
Embodiment 3
Nozzle diameter is changed to 1.0mm by preparation process such as embodiment 1, and the internally dry temperature of spray drying tower is 120 DEG C, preparation
Catalyst C of the present invention, property are shown in Table 1, and evaluating catalyst the results are shown in Table 2.
Embodiment 4
Six water nickel nitrates are changed to cobalt nitrate hexahydrate by preparation process such as embodiment 1, and the additional amount of waterglass is changed to 43.8g, system
Standby catalyst D of the present invention, property are shown in Table 1, and evaluating catalyst the results are shown in Table 2.
Embodiment 5
The nitrate trihydrate copper of addition is changed to that magnesium nitrate hexahydrate is added by preparation process such as embodiment 1, and boehmite additional amount is
21.83g prepares catalyst E of the present invention, and property is shown in Table 1, and evaluating catalyst the results are shown in Table 2.
Embodiment 6
Preparation process such as embodiment 1, is changed to 700 DEG C for catalyst maturing temperature, and nitrate trihydrate copper additional amount is changed to 2.90g,
The additional amount of barium nitrate be changed to 0.39g, prepare catalyst F of the present invention, property is shown in Table 1, and evaluating catalyst the results are shown in Table 2.
Embodiment 7
Preparation process such as embodiment 1 is only added without auxiliary agent barium nitrate, prepares catalyst G of the present invention, and property is shown in Table 1, catalyst
Evaluation result is shown in Table 2.
Embodiment 8
Preparation process such as embodiment 1 is only added without auxiliary agent copper nitrate, prepares catalyst H of the present invention, and property is shown in Table 1, catalyst
Evaluation result is shown in Table 2.
Embodiment 9
Preparation process such as embodiment 1, only dried medium is hot-air, does not contain ammonia, obtains catalyst I, catalyst property
It is shown in Table 1, evaluating catalyst the results are shown in Table 2.
Comparative example 1
Preparation process such as embodiment 1, only that boehmite is not added, and boehmite is substituted by waterglass, is obtained pair
Than catalyst J, catalyst property is shown in Table 1, and evaluating catalyst the results are shown in Table 2.
Comparative example 2
Catalyst is prepared using the preparation method of embodiment 2 in CN105967189A, obtains comparative catalyst K, catalyst property
It is shown in Table 1, evaluating catalyst the results are shown in Table 2.Specific preparation process is as follows:
By 42.5 kilograms of six water nickel chlorides and 18 kilograms of nitrate trihydrate copper dissolution in deionized water, be configured to 500 liters it is molten
80 kilograms of silica solution that solid content is 20 weight % are added in Xiang Shangshu mixing salt solution, is uniformly mixed and obtains slurries, use is dense for liquid
It is 5 that the sodium hydrate aqueous solution that degree is 5 weight %, which adjusts the pH value of slurries,；40 kilograms of ammonium carbonates are water-soluble with 400 liters of deionizations
Solution obtains ammonium carbonate solution；
Above-mentioned slurries and ammonium carbonate solution being added in 2000 liters of reaction kettle and is contacted, the temperature of contact is 80 DEG C,
Adjusting pH with the sodium hydrate aqueous solution that concentration is 5 weight % makes the pH value of contact be 7, and after contacting 4h, solid is obtained by filtration,
It will be roasted 6 hours at 500 DEG C in muffle furnace after obtained solid drying, obtain catalyst K.
The property of 1 embodiment of table and the catalyst of comparative example preparation
| Catalyst number | A | B | C | D | E | F |
| Catalyst shape | Microballoon | Microballoon | Microballoon | Microballoon | Microballoon | Microballoon |
| Specific surface area, m2/g | 78.1 | 79.0 | 80.5 | 82.2 | 80.9 | 70.2 |
| Attrition of catalyst, wt% | 0.85 | 0.85 | 0.80 | 0.84 | 0.79 | 0.81 |
| Catalyst composition, wt% | ||||||
| Al2O3 | 15.12 | 15.13 | 15.23 | 15.31 | 15.71 | 15.30 |
| SiO2 | 19.41 | 19.45 | 19.56 | 15.70 | 19.86 | 19.51 |
| NiO or CoO | 64.30 | 64.21 | 64.04 | 67.82 | 63.55 | 63.99 |
| M1 oxide | 0.61 | 0.86 | 0.60 | 0.60 | 0.29 | 0.96 |
| M2 oxide | 0.56 | 0.35 | 0.57 | 0.57 | 0.59 | 0.24 |
| Size distribution, % | ||||||
| <150μm | 2.8 | 3.0 | 1.6 | 3.1 | 2.6 | 2.7 |
| 150~500 μm | 90.1 | 89.7 | 88.9 | 90.0 | 90.0 | 89.5 |
| >500μm | 7.1 | 7.3 | 9.5 | 6.9 | 7.4 | 7.8 |
The property of 1 embodiment of continued and the catalyst of comparative example preparation
| Catalyst number | G | H | I | J | K |
| Catalyst shape | Microballoon | Microballoon | Microballoon | Microballoon | It is amorphous |
| Specific surface area, m2/g | 77.0 | 77.3 | 66.1 | 33.5 | 31.4 |
| Attrition of catalyst, wt% | 0.91 | 0.86 | 4.31 | 1.56 | 4.8 |
| Catalyst composition, wt% | |||||
| Al2O3 | 15.21 | 15.21 | 15.12 | 0 | 0 |
| SiO2 | 19.52 | 19.51 | 19.41 | 34.53 | 49.7 |
| NiO or CoO | 64.66 | 64.72 | 64.3 | 64.3 | 40.2 |
| M1Oxide | 0.61 | - | 0.61 | 0.61 | 10.1 |
| M2Oxide | - | 0.56 | 0.56 | 0.56 | - |
| Size distribution, % | |||||
| <150μm | 1.8 | 1.7 | 17.5 | 2.9 | - |
| 150~500 μm | 88.6 | 88.5 | 79.3 | 89.9 | - |
| >500μm | 9.6 | 9.8 | 3.2 | 7.2 | - |
Catalyst activity evaluation uses fixed bed evaluating apparatus, Catalyst packing 10g, reaction pressure 1.2MPa, H2/SiCl4
(molar ratio) is 25, silicon powder/SiCl4(molar ratio) is 10, gas hourly space velocity 30000h-1, reaction temperature be respectively 400 DEG C and
450 DEG C, evaluation result is shown in Table 2.
2 catalyst activity of table and estimation of stability result
| Number | Conversion ratio (400 DEG C, 10 hours), % | Conversion ratio (400 DEG C, 150 hours), % | Conversion ratio (450 DEG C, 10 hours), % | Conversion ratio (450 DEG C, 150 hours), % |
| A | 28.6 | 28.3 | 36.9 | 36.6 |
| B | 28.9 | 28.7 | 37.3 | 37.2 |
| C | 27.8 | 27.4 | 36.2 | 35.7 |
| D | 28.3 | 27.8 | 36.8 | 36.3 |
| E | 27.9 | 27.5 | 36.1 | 35.8 |
| F | 28.8 | 28.5 | 36.8 | 36.7 |
| G | 27.3 | 26.6 | 36.0 | 35.3 |
| H | 27.0 | 26.5 | 35.8 | 35.2 |
| I | 26.1 | 20.6 | 32.8 | 28.3 |
| J | 22.1 | 21.0 | 31.3 | 30.2 |
| K | 22.5 | 21.2 | 31.5 | 29.9 |
Claims (15)
1. a kind of silicon tetrachloride adds hydrogen to prepare trichlorosilane catalyst, it is characterised in that the catalyst composition include silica,
Aluminium oxide, active component and adjuvant component, active component are group VIII metal, and adjuvant component is metal M；With the weight of catalyst
On the basis of count, alumina content be 10%~20%, dioxide-containing silica be 14.5%~25%, active component is with group VIII metal oxygen
The content of compound meter is 55%~75%, and content of the adjuvant component in terms of the oxide of metal M is 0.5%~2.0%, the metal M
For one of Cu, Fe, Mg, Cr and Ba or a variety of.
2. catalyst described in accordance with the claim 1, it is characterised in that: group VIII metal is Ni and/or Co, preferably Ni.
3. catalyst described in accordance with the claim 1, it is characterised in that: adjuvant component metal M uses M1 and M2, and wherein M1 is
One of Cu, Mg, Fe or a variety of, preferably one of Cu, Mg or a variety of, M2 be one of Cr and Ba or a variety of, it is excellent
It is selected as Ba；Molar ratio of the M1 and M2 in terms of oxide is 1:10 ~ 10:1, preferably 2:1 ~ 8:1.
4. according to catalyst described in claim 1 or 3, it is characterised in that: the property of the catalyst is as follows: specific surface area >
50m2/ g, preferably 60~120m2/g。
5. according to catalyst described in claim 1 or 3, it is characterised in that: the granularity of the catalyst is scored with volume fraction
Cloth is as follows: partial size < 150mm particle accounts for 10% hereinafter, it is preferred that 8% or less；Particle of the partial size in 150~500mm accounts for 75%~95%,
Preferably 80%~92%, partial size > 500mm particle account for 15% hereinafter, it is preferred that 12% or less.
6. according to catalyst described in claim 1 or 3, it is characterised in that: the rate of wear < 2.0wt% of the catalyst, preferably
< 1.5wt%.
7. the preparation method that a kind of any silicon tetrachloride of claim 1~6 adds hydrogen to prepare trichlorosilane catalyst, packet
It includes:
(1) acid solution is added into silicon source and carries out acidification；
(2) soluble-salt containing group VIII metal, the solubility containing metal M are separately added into step (1) resulting material
Salt, boehmite, curing agent, deionized water, are configured to slurries；
(3) slurries obtained by step (2) are subjected to spray shaping, obtain spherical gel；
(4) by the resulting spherical gel washing of step (3), dry, roasting, catalyst is obtained.
8. preparation method according to claim 7, it is characterised in that silicon source described in step (1) is waterglass and/or silicon
Colloidal sol, the mass content in terms of silica are 20%~40%, preferably 25%~35%；The acid solution is nitric acid, formic acid, vinegar
One or more of acid and citric acid, preferably nitric acid, wherein the mass concentration of nitric acid is 55%~75%, preferably 60%~65%.
9. preparation method according to claim 7, it is characterised in that after silicon source described in step (1) carries out acidification,
Its pH value is 1.0~4.0, preferably 2.5~3.5.
10. preparation method according to claim 7, it is characterised in that group VIII metal described in step (2) be Ni and/or
Co, preferably Ni；The soluble-salt of group VIII metal is selected from one or more of nitrate, sulfate and chloride, preferably nitre
Hydrochlorate；The metal M is one of Cu, Fe, Mg, Cr and Ba or a variety of；The soluble-salt of metal M is nitrate and sulfuric acid
One of salt is a variety of, preferably nitrate.
11. preparation method according to claim 7, it is characterised in that the dry weight of step (2) described boehmite
It is 70% or more, is converted into γ-Al through high-temperature roasting2O3Property afterwards is as follows: Kong Rongwei 0.95mL/g or more, preferably Kong Rongwei
0.95 ~ 1.2mL/g, specific surface area 330m2/ g or more, preferably specific surface area are 330 ~ 400m2/g。
12. preparation method according to claim 7, it is characterised in that step (2) curing agent is urea, organic ammonium salt
One of or it is a variety of, the organic ammonium salt be six methines, four ammonium；The additional amount of the curing agent and the active metal and
The molar ratio of auxiliary agent is 0.5:1.0 ~ 1.2:1.0, preferably 0.6:1.0 ~ 1.0:1.0.
13. preparation method according to claim 7, it is characterised in that silicon source is in slurries obtained by step (2) with silica
Meter, the gross mass that boehmite is in terms of aluminium oxide, active component and adjuvant component are in terms of oxide account for the 25% of slurries total weight
~45%, preferably 30%~35%.
14. preparation method according to claim 7, it is characterised in that spray shaping described in step (3) is pressure-type spray
Mist molding；The spray shaping carries out in spray shaping tower, nozzle diameter 0.3mm~1.2mm, preferably 0.6mm~1.0mm,
Spraying pressure is 0.5 ~ 1.5MPa, the molding and hot gas medium counter current contacting sprayed by nozzle, the temperature of hot gas medium
Degree is 70~200 DEG C, and preferably 90~120 DEG C, gas medium uses ammonia-containing gas, it is preferred to use the air containing ammonia, wherein NH3's
Volume fraction is 5% ~ 10%.
15. preparation method according to claim 7, it is characterised in that washing described in step (4) is will with deionized water
Spherical gel detergent is to neutrality；The drying condition are as follows: it is 4~10 hours dry at 80~200 DEG C, preferably at 100~150 DEG C
Lower drying 6~8 hours；The roasting condition are as follows: roast 3~8 hours at 500~900 DEG C, preferably roasted at 550~700 DEG C
It burns 3~5 hours.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114054035A (en) * | 2021-11-30 | 2022-02-18 | 新特能源股份有限公司 | Catalyst for catalyzing silicon tetrachloride conversion and preparation method thereof |
| CN114349485A (en) * | 2022-01-11 | 2022-04-15 | 无锡特科精细陶瓷有限公司 | Preparation method of high-strength alumina ceramic |
| CN115845910A (en) * | 2022-12-09 | 2023-03-28 | 武汉新硅科技潜江有限公司 | Method for synthesizing trichlorosilane from silicon tetrachloride |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1110248A (en) * | 1994-04-05 | 1995-10-18 | 中国科学院兰州化学物理研究所 | Catalyst for converting methane into synthetic gas and its process |
| CN101134906A (en) * | 2006-08-30 | 2008-03-05 | 中国石油天然气股份有限公司 | Method for improving solid content of catalytic cracking catalyst slurry |
| CN101829592A (en) * | 2009-03-10 | 2010-09-15 | 中国石油天然气股份有限公司 | Preparation method of fluidizing, catalyzing and cracking catalyst with high solid content |
| CN101913991A (en) * | 2010-08-20 | 2010-12-15 | 南化集团研究院 | Recycling method of butanol and octanol waste liquid through hydrocracking and catalyst |
| CN102114426A (en) * | 2010-12-23 | 2011-07-06 | 内蒙古工业大学 | Special catalyst for cold hydrogenation of silicon tetrachloride and preparation method thereof |
| CN103007995A (en) * | 2012-12-17 | 2013-04-03 | 四川大学 | Composite catalyst for preparing trichlorosilane through catalytic hydrogenation of silicon tetrachloride |
-
2017
- 2017-10-27 CN CN201711019755.6A patent/CN109718781B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1110248A (en) * | 1994-04-05 | 1995-10-18 | 中国科学院兰州化学物理研究所 | Catalyst for converting methane into synthetic gas and its process |
| CN101134906A (en) * | 2006-08-30 | 2008-03-05 | 中国石油天然气股份有限公司 | Method for improving solid content of catalytic cracking catalyst slurry |
| CN101829592A (en) * | 2009-03-10 | 2010-09-15 | 中国石油天然气股份有限公司 | Preparation method of fluidizing, catalyzing and cracking catalyst with high solid content |
| CN101913991A (en) * | 2010-08-20 | 2010-12-15 | 南化集团研究院 | Recycling method of butanol and octanol waste liquid through hydrocracking and catalyst |
| CN102114426A (en) * | 2010-12-23 | 2011-07-06 | 内蒙古工业大学 | Special catalyst for cold hydrogenation of silicon tetrachloride and preparation method thereof |
| CN103007995A (en) * | 2012-12-17 | 2013-04-03 | 四川大学 | Composite catalyst for preparing trichlorosilane through catalytic hydrogenation of silicon tetrachloride |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114054035A (en) * | 2021-11-30 | 2022-02-18 | 新特能源股份有限公司 | Catalyst for catalyzing silicon tetrachloride conversion and preparation method thereof |
| CN114349485A (en) * | 2022-01-11 | 2022-04-15 | 无锡特科精细陶瓷有限公司 | Preparation method of high-strength alumina ceramic |
| CN114349485B (en) * | 2022-01-11 | 2023-01-10 | 无锡特科精细陶瓷有限公司 | Preparation method of high-hardness alumina ceramic |
| CN115845910A (en) * | 2022-12-09 | 2023-03-28 | 武汉新硅科技潜江有限公司 | Method for synthesizing trichlorosilane from silicon tetrachloride |
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Effective date of registration: 20231009 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |