CN109718780A - A kind of silicon tetrachloride adds hydrogen to prepare the preparation method of trichlorosilane catalyst - Google Patents
A kind of silicon tetrachloride adds hydrogen to prepare the preparation method of trichlorosilane catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 102
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 239000005052 trichlorosilane Substances 0.000 title claims abstract description 17
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 12
- 239000001257 hydrogen Substances 0.000 title claims abstract description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 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 27
- 239000005049 silicon tetrachloride Substances 0.000 title claims description 27
- 238000000034 method Methods 0.000 claims abstract description 49
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002002 slurry Substances 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 16
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 16
- 239000010703 silicon Substances 0.000 claims abstract description 16
- 239000007921 spray Substances 0.000 claims abstract description 16
- 230000000694 effects Effects 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 238000007493 shaping process Methods 0.000 claims abstract description 13
- 229910001593 boehmite Inorganic materials 0.000 claims abstract description 12
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims abstract description 12
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 27
- 229910052751 metal Inorganic materials 0.000 claims description 26
- 239000002184 metal Substances 0.000 claims description 26
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 18
- 239000002671 adjuvant Substances 0.000 claims description 16
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 13
- 239000000377 silicon dioxide Substances 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 229910021529 ammonia Inorganic materials 0.000 claims description 9
- 238000000465 moulding Methods 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 235000019353 potassium silicate Nutrition 0.000 claims description 6
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- 238000009826 distribution Methods 0.000 claims description 5
- 150000007524 organic acids Chemical class 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 150000003863 ammonium salts Chemical class 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 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
- 238000005507 spraying Methods 0.000 claims description 3
- 238000005406 washing Methods 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
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 2
- 239000003292 glue Substances 0.000 claims 1
- 239000003595 mist Substances 0.000 claims 1
- 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
- 230000020477 pH reduction Effects 0.000 abstract description 4
- 230000035939 shock Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 19
- 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
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 6
- 238000005984 hydrogenation reaction Methods 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 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 4
- 239000007787 solid Substances 0.000 description 4
- 239000001099 ammonium carbonate Substances 0.000 description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000011777 magnesium Substances 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
- 229910003910 SiCl4 Inorganic materials 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 235000012501 ammonium carbonate Nutrition 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000004090 dissolution Methods 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
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 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
- 238000002156 mixing Methods 0.000 description 2
- 239000011148 porous material Substances 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
- 238000001694 spray drying Methods 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
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 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
- 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
- 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 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
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 238000006298 dechlorination reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 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
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 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 invention discloses a kind of silicon tetrachlorides, and hydrogen to be added to prepare the preparation method of trichlorosilane catalyst.This method is that silicon source acid solution is carried out preliminary acidification, adds the acid solution containing active component and auxiliary agent to the further acidification of silicon source, boehmite is added later and curing agent is made into slurries；Spray shaping is carried out to slurries, then catalyst of the present invention is made in washed, dry, roasting.The catalyst prepared using the method for the present invention, with good activity and stability, and mechanical strength and wear-resisting property are good, while also increasing catalyst in fluidized bed use process with the shock of silicon powder, friction, capability, avoid " running damage " phenomenon in catalyst use process.
Description
Technical field
The present invention relates to a kind of preparation methods of hydrogenation catalyst, add hydrogen to prepare trichlorine more particularly to a kind of silicon tetrachloride
The preparation method of hydrogen Si catalyst.
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.
CN102626630A, CN105967189A divide the side for having opened a kind 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 IB, IIB, IIA and locates one of the group VIII metal other than Ni
Or it is a variety of.But the catalyst of this method preparation is powdery, in a fluidized bed using " running damage " is easy, causes catalyst loss and work
Property reduce, meanwhile, do not provide the specific surface area size of catalyst in above-mentioned patent, the activity and stability of catalyst all compared with
It is low.
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.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of silicon tetrachlorides, and hydrogen to be added to prepare the system of trichlorosilane catalyst
Preparation Method.It is concentrated using the catalyst of this method preparation with distribution of particle sizes, while activity with higher, active metal point
Property and abrasion resistance are dissipated, meets industrialization fluidized bed silicon tetrachloride and hydrogen is added to prepare trichlorosilane requirement, the catalyst is in four chlorinations
Silicon activity and stability with higher during adding hydrogen to prepare trichlorosilane.
A kind of silicon tetrachloride provided by the invention adds hydrogen to prepare the preparation method of trichlorosilane catalyst, comprising:
(1) acid solution is added into silicon source；
(2) acid solution containing group VIII metal and adjuvant component M is added in the mixture obtained to step (1)；
(3) boehmite, curing agent, deionized water are added in the mixture obtained to step (2) and are configured to slurries；
(4) slurries obtained by step (3) are subjected to spray shaping, obtain spherical gel；
(5) by the washing of step (4) spherical gel, dry, roasting, catalyst is obtained.
In the method for the present invention, silicon source described in step (1) is waterglass and/or silica solution, and quality contains in terms of silica
Amount is 20%~40%, preferably 25%~35%；The preferred organic acid soln of acid solution, mass concentration is 65%~85%, excellent
Select 70%~80%.The organic acid is selected from one or more of formic acid, acetic acid, citric acid.The additional amount of the acid solution
For the pH value 4.0~7.0 for making system, preferably 5.5~6.5.
In the method for the present invention, step (2) group VIII metal is Ni and/or Co, preferably Ni.The M be Cu, Fe, Cr,
One of Mg, Ba etc. or a variety of.Wherein, adjuvant component 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 of addition
Molar ratio in terms of oxide is 1:10 ~ 10:1, preferably 2:1 ~ 8:1.
In the method for the present invention, in the acid solution containing group VIII metal and adjuvant component M described in step (2), the VIIIth
Race's source metal and the source adjuvant component M are inorganic salts, can be selected from one or more of nitrate, sulfate and chloride, excellent
Select nitrate.Make body after the acid solution containing group VIII metal and adjuvant component M is added in the mixture obtained to step (1)
The pH value of system is reduced to 1.0~4.0, preferably 2.5~3.5, and the pH value of mixture obtained by step (1) is at least made to reduce by 1.0.
In the method for the present invention, the dry weight of step (3) 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 additional amount of the active metal and auxiliary agent are with oxygen
The molar ratio of compound meter is 0.5:1.0 ~ 1.2:1.0, preferably 0.6:1.0 ~ 1.0:1.0.Silicon source is in slurries obtained by step (3) with two
The gross mass that silica meter, boehmite are in terms of aluminium oxide, active component and adjuvant component are in terms of oxide accounts for slurries gross weight
The 25%~45% of amount, preferably 30%~35%.
In the method for the present invention, spray shaping described in step (4) 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 (5) 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.
The catalyst that material added by preparation method step (1)~(3) of the invention makes meets: 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
The content of oxide meter is 55%~75%, and content of the adjuvant component in terms of the oxide of metal M is 0.5%~2.0%.
The catalyst of the method for the present invention preparation, property are as follows: specific surface area > 60m2/ g, preferably 80~150m2/g.This
In invention, specific surface area is using low temperature liquid nitrogen determination of adsorption method.
The rate of wear < 2.0wt%, preferably < 1.5wt% of the catalyst of the method for the present invention preparation.In the present invention, rate of wear is adopted
With fluidisation state tear strength tester measurement.
The size distribution of the catalyst of the method for the present invention preparation is following (with volume fraction): partial size < 150mm particle accounts for
10% hereinafter, it is preferred that 8% or less；Partial size accounts for 75%~95%, preferably 80%~92% in the particle of 150~500mm, partial size > 500mm
Particle account for 15% hereinafter, it is preferred that 12% or less.In the present invention, granularity is using laser particle analyzer measurement.
Compared with prior art, the method for the present invention has the 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, acid solution is first added into silicon source, adds containing the VIIIth race gold
Belong to the acid solution with adjuvant component M, boehmite, curing agent and water is then added and forms slurries, and uses spray shaping
Mode, make each component collaboration play a role so that preparation catalyst while having preferable intensity, and have biggish ratio
Surface area provides more reacting environment for reactant, can effectively improve catalyst activity.
4, in the preparation method of catalyst of the present invention, organic acid soln is preferably first added into silicon source, adds the VIIIth race
The inorganic hydrochloric acid solution of metal and adjuvant component M is conducive to keep catalyst pore structure in this way, further increases catalyst
Specific surface area, and promote the dispersion of active metal, be conducive to the activity and activity stability that improve catalyst.
5, 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.
6, 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.The present invention
In, wt% is mass fraction.
Embodiment 1
The waterglass 56.8g that mass content is 35% in terms of silica is added into preparing tank, starts agitating device, then slowly add
Entering concentration is 75% citric acid solution, makes the pH value 5.5 of water glass solution after acidification, is added after being uniformly mixed into preparing tank
Six water nickel nitrate of 259.6g and 1.85g nitrate trihydrate copper, 1.05g barium nitrate are stirred to the pH value 2.5 for dissolving and making solution, then
It is 1.06mL/g, specific surface area 342m that into above-mentioned solution, adding hole, which is held,2/ g, butt are the boehmite of 70wt%
24.1g adds curing agent urea 49.6g after mixing evenly, and deionized water is added after urea all dissolution, makes in preparing tank
In slurries silicon source in terms of silica, boehmite in terms of aluminium oxide, active component and adjuvant component it is total in terms of oxide
Quality accounts for the 33% of slurries total weight, and keeping it is the slurries with certain fluidity.
The above-mentioned slurries with certain fluidity are subjected to spray shaping in spray shaping tower, set nozzle diameter as
0.8mm, the internally dry temperature of spray drying tower are 100 DEG C, and dried medium is the hot-air containing ammonia, wherein the volume of ammonia
Score is 8%, and flow direction of the dried medium in spray shaping tower is bottom-up transmission, so that material is solidified and is shunk, obtains
Spherical gel.
It is 7.0 that obtained spherical gel, which is washed with deionized to PH, and 8 hours dry at 130 DEG C, then through 550
It is roasted at DEG C 3 hours and obtains catalyst A of the present invention, catalyst property is shown in Table 1, and evaluating catalyst the results are shown in Table 2.
Embodiment 2
Citric acid is changed to acetic acid by preparation process such as embodiment 1, and curing agent is changed to six methines, four ammonium 105.1g, by three water nitre
Sour copper additional amount is changed to 2.75g, and the additional amount of barium nitrate is changed to 0.49g, prepares catalyst B of the present invention, and property is shown in Table 1, catalysis
Agent evaluation result 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 that cobalt nitrate hexahydrate is added by preparation process such as embodiment 1, and the additional amount of waterglass is changed to
43.83g prepares catalyst D of the present invention, and property is 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 magnesium nitrate hexahydrate by preparation process such as embodiment 1, the additional amount of barium nitrate this be
1.62g 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 adjusts the first time acidizing PH value of silicon source to 6.5, and the pH value of second of acidification is 3.0,
Catalyst maturing temperature is changed to 700 DEG C, and nitrate trihydrate copper additional amount is changed to 2.84g, and the additional amount of barium nitrate is changed to 0.42g,
Catalyst F of the present invention is prepared, 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, it is 62% nitric acid solution that citric acid when first time is acidified, which is changed to mass concentration, is obtained pair
Than catalyst I, catalyst property is shown in Table 1, and evaluating catalyst the results are shown in Table 2.
Embodiment 10
Preparation process such as embodiment 1, dried medium is hot-air, does not contain ammonia, obtains catalyst J, catalyst property is shown in Table
1, evaluating catalyst the results are shown in Table 2.
Comparative example 1
Preparation process such as embodiment 1 is not only added boehmite and boehmite is substituted by waterglass, compared
Catalyst K, catalyst property are 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 example catalyst L, catalyst performance
Matter is shown in Table 1, and 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,；By 40 kilograms of ammonium carbonates, 400 liters of deionized water dissolvings
Obtain 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 L.
The property of table 1 embodiment and comparative catalyst
| Catalyst number | A | B | C | D | E | F |
| Catalyst shape | Microballoon | Microballoon | Microballoon | Microballoon | Microballoon | Microballoon |
| Specific surface area, m2/g | 88 | 82 | 89 | 81 | 92 | 80 |
| Attrition of catalyst, wt% | 0.80 | 0.79 | 0.80 | 0.83 | 0.81 | 0.81 |
| Catalyst composition, wt% | ||||||
| Al2O3 | 16.72 | 16.83 | 16.78 | 16.74 | 16.82 | 16.65 |
| SiO2 | 19.40 | 19.81 | 19.62 | 15.32 | 19.86 | 19.61 |
| NiO or CoO | 62.66 | 62.15 | 62.39 | 66.74 | 62.09 | 62.55 |
| M1 oxide | 0.62 | 0.88 | 0.61 | 0.61 | 0.29 | 0.95 |
| M2 oxide | 0.60 | 0.33 | 0.60 | 0.59 | 0.94 | 0.24 |
| Size distribution, % | ||||||
| <150μm | 2.7 | 3.0 | 2.0 | 3.1 | 2.4 | 2.4 |
| 150~500 μm | 90.3 | 89.8 | 89.0 | 90.1 | 90.1 | 89.8 |
| >500μm | 7.0 | 7.2 | 9.0 | 6.8 | 7.5 | 7.8 |
The property of continued 1 embodiment and comparative catalyst
| Catalyst number | G | H | I | J | K | L |
| Catalyst shape | Microballoon | Microballoon | Microballoon | Microballoon | Microballoon | It is amorphous |
| Specific surface area, m2/g | 87 | 86 | 74 | 61 | 34 | 31 |
| Attrition of catalyst, wt% | 0.83 | 0.77 | 0.90 | 3.6 | 2.3 | 4.8 |
| Catalyst composition, wt% | ||||||
| Al2O3 | 16.82 | 16.82 | 16.72 | 16.72 | 0 | 0 |
| SiO2 | 19.52 | 19.53 | 19.40 | 19.40 | 36.12 | 49.7 |
| NiO or CoO | 63.04 | 63.05 | 62.66 | 62.66 | 62.66 | 40.2 |
| M1 oxide | 0.62 | - | 0.62 | 0.62 | 0.62 | 10.1 |
| M2 oxide | - | 0.60 | 0.60 | 0.60 | 0.60 | |
| Size distribution, % | ||||||
| <150μm | 1.9 | 2.0 | 3.4 | 15.2 | 2.8 | - |
| 150~500 μm | 88.7 | 88.7 | 88.4 | 81.4 | 89.9 | - |
| >500μm | 9.4 | 9.3 | 8.2 | 3.4 | 7.3 | - |
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 evaluation result of table
| Catalyst 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 | 28.9 | 28.7 | 37.5 | 37.3 |
| B | 29.2 | 29.1 | 37.8 | 37.7 |
| C | 28.3 | 28.0 | 36.5 | 36.1 |
| D | 28.5 | 28.1 | 37.0 | 36.0 |
| E | 28.2 | 27.9 | 36.4 | 36.0 |
| F | 29.0 | 28.8 | 37.4 | 37.3 |
| G | 27.7 | 27.0 | 36.2 | 35.6 |
| H | 27.4 | 27.1 | 36.0 | 35.7 |
| I | 28.0 | 27.6 | 36.3 | 35.9 |
| J | 26.4 | 22.5 | 32.9 | 30.7 |
| K | 22.3 | 21.6 | 31.4 | 30.9 |
| L | 22.5 | 21.2 | 31.5 | 29.9 |
Claims (14)
1. a kind of silicon tetrachloride adds hydrogen to prepare the preparation method of trichlorosilane catalyst, it is characterised in that the following steps are included:
(1) acid solution is added into silicon source；
(2) acid solution containing group VIII metal and adjuvant component M is added in the mixture obtained to step (1)；
(3) boehmite, curing agent, deionized water are added in the mixture obtained to step (2) and are configured to slurries；
(4) slurries obtained by step (3) are subjected to spray shaping, obtain spherical gel；
(5) by the washing of step (4) spherical gel, dry, roasting, catalyst is obtained.
2. according to the method for claim 1, it is characterised in that: silicon source described in step (1) is that waterglass and/or silicon are molten
Glue, mass content is 20%~40%, preferably 25%~35% in terms of silica；The acid solution is organic acid soln, matter
Measuring concentration is 65%~85%, preferably 70%~80%；The organic acid is selected from one or more of formic acid, acetic acid, citric acid.
3. according to the method for claim 1, it is characterised in that: the additional amount of the acid solution is to make the pH value of system
4.0~7.0, preferably 5.5~6.5.
4. according to the method for claim 1, it is characterised in that: step (2) group VIII metal is Ni and/or Co, excellent
Selecting Ni, the M is one of Cu, Fe, Cr, Mg, Ba or a variety of.
5. according to the method for claim 1, it is characterised in that: the adjuvant component M use M1 and M2, wherein M1 be Cu,
One of 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, preferably
Ba；Molar ratio of the M1 and M2 of addition in terms of oxide is 1:10 ~ 10:1, preferably 2:1 ~ 8:1.
6. according to method described in claim 1 or 3, it is characterised in that: contain group VIII metal and auxiliary agent described in step (2)
In the acid solution of component M, group VIII metal source and the source adjuvant component M are inorganic salts, and the inorganic salts are nitrate, sulfuric acid
One or more of salt and chloride, preferably nitrate；It is added in the mixture obtained to step (1) and contains group VIII metal
With so that the pH value of system is reduced to 1.0~4.0, preferably 2.5~3.5 after the acid solution of adjuvant component M, and at least make step
(1) pH value of gained mixture reduces by 1.0.
7. according to the method for claim 1, it is characterised in that: the dry weight of step (3) described boehmite is 70%
More than, γ-Al is converted into through high-temperature roasting2O3Property afterwards is as follows: Kong Rongwei 0.95mL/g or more, and preferably Kong Rongwei 0.95 ~
1.2mL/g, specific surface area 330m2/ g or more, preferably specific surface area are 330 ~ 400m2/g。
8. according to the method for claim 1, it is characterised in that: the curing agent be one of urea, organic ammonium salt or
A variety of, the organic ammonium salt is six methines, four ammonium；The addition of the additional amount of the curing agent and the active metal and auxiliary agent
The molar ratio measured in terms of oxide is 0.5:1.0 ~ 1.2:1.0, preferably 0.6:1.0 ~ 1.0:1.0.
9. according to the method for claim 1, it is characterised in that: in slurries obtained by step (3) silicon source in terms of silica, intend
The gross mass that boehmite is in terms of aluminium oxide, active component and adjuvant component are in terms of oxide account for slurries gross mass 25%~
45%, preferably 30%~35%.
10. according to method described in claim 1 or 6, it is characterised in that: spray shaping described in step (4) 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 is ammonia-containing gas, preferably containing the air of ammonia, wherein NH3Volume
Score is 5% ~ 10%.
11. according to the method for claim 1, it is characterised in that: drying condition described in step (5) are as follows: at 80~200 DEG C
Lower drying 4~10 hours, it is 6~8 hours dry preferably at 100~150 DEG C；The roasting condition are as follows: at 500~900 DEG C
Roasting 3~8 hours, roasts 3~5 hours preferably at 550~700 DEG C.
12. according to the method for claim 1, it is characterised in that: the catalyst that material added by step (1)~(3) makes
Meet: on the basis of the weight of catalyst, alumina content is 10%~20%, and dioxide-containing silica is 14.5%~25%, activity
Content of the component in terms of the oxide of group VIII metal is 55%~75%, and content of the adjuvant component in terms of the oxide of metal M is
0.5%~2.0%.
13. according to method described in claim 1 or 10, it is characterised in that: the property of gained catalyst is as follows: specific surface area >
60m2/ g, preferably 80~150m2/g；The rate of wear < 2.0wt% of gained catalyst, preferably < 1.5wt%.
14. according to method described in claim 1 or 10, it is characterised in that: the size distribution situation of gained catalyst is as follows, with
Volume fraction: partial size < 150mm particle accounts for 10% hereinafter, it is preferred that 8% or less；Partial size accounts for 75% in the particle of 150~500mm~
95%, preferably 80%~92%, partial size > 500mm particle account for 15% hereinafter, it is preferred that 12% or less.
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| 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 |
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| 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 |
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