CN103241743A - Reactive distillation method and equipment for preparing silane through direct disproportionation of trichlorosilane - Google Patents
Reactive distillation method and equipment for preparing silane through direct disproportionation of trichlorosilane Download PDFInfo
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- 238000007323 disproportionation reaction Methods 0.000 title claims abstract description 92
- 229910000077 silane Inorganic materials 0.000 title claims abstract description 79
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 title claims abstract description 78
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000005052 trichlorosilane Substances 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 32
- 238000000066 reactive distillation Methods 0.000 title claims abstract description 15
- 239000000047 product Substances 0.000 claims abstract description 41
- 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 claims abstract description 36
- 239000005049 silicon tetrachloride Substances 0.000 claims abstract description 36
- 239000007791 liquid phase Substances 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 239000005046 Chlorosilane Substances 0.000 claims abstract description 26
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 22
- 238000000926 separation method Methods 0.000 claims abstract description 13
- 239000012071 phase Substances 0.000 claims abstract description 11
- 239000012535 impurity Substances 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 4
- 238000005192 partition Methods 0.000 claims abstract description 4
- 238000000605 extraction Methods 0.000 claims description 48
- 238000012856 packing Methods 0.000 claims description 34
- 238000000746 purification Methods 0.000 claims description 33
- 241000282326 Felis catus Species 0.000 claims description 25
- 238000007670 refining Methods 0.000 claims description 13
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- 238000005260 corrosion Methods 0.000 claims description 6
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- 238000011068 loading method Methods 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 8
- 238000004821 distillation Methods 0.000 abstract 5
- 239000007789 gas Substances 0.000 description 17
- 238000001816 cooling Methods 0.000 description 16
- 238000010438 heat treatment Methods 0.000 description 15
- 238000005516 engineering process Methods 0.000 description 11
- 239000003921 oil Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000012850 discrimination method Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000003507 refrigerant Substances 0.000 description 3
- -1 sodium aluminum fluoride Chemical compound 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 229910007981 Si-Mg Inorganic materials 0.000 description 2
- 229910008316 Si—Mg Inorganic materials 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 235000019628 coolness Nutrition 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- VJTAZCKMHINUKO-UHFFFAOYSA-M chloro(2-methoxyethyl)mercury Chemical compound [Cl-].COCC[Hg+] VJTAZCKMHINUKO-UHFFFAOYSA-M 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
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- 238000011020 pilot scale process Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910021487 silica fume Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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Abstract
The invention relates to a reactive distillation method and equipment for preparing silane through direct disproportionation of trichlorosilane. The reactive distillation method comprises the following steps of: introducing refined trichlorosilane with the purity up to over 9N to a one-step disproportionation reaction distillation tower to prepare the silane; extracting a reaction product from the top of the disproportionation reaction distillation tower in a gas phase way, entering a silane tower by utilizing differential pressure, obtaining a chlorosilane mixture at the bottom of the tower, and entering a silicon tetrachloride tower; obtaining a high-purity liquid-phase silane product at the top of the silane tower, obtaining unreacted chlorosilane at the bottom of the tower, and returning the unreacted chlorosilane to the disproportionation reaction distillation tower; and obtaining unreacted chlorosilane at the top of the silicon tetrachloride tower, returning the unreacted chlorosilane to the disproportionation reaction distillation tower, and obtaining a silicon tetrachloride product at the bottom of the tower. Light and heavy impurities in the refined trichlorosilane raw material with the purity lower than 9N are removed after the trichlorosilane passes through a partition plate rectification tower so as to obtain trichlorosilane with the purity up to over 9N. The one-step disproportionation reaction is realized in one reaction distillation tower, the equipment is simplified, meanwhile, a great number of circular reactions for material separation are avoided, the processes are shortened, the energy is saved, and the consumption is reduced. The purity of a silane product is higher.
Description
Technical field
The present invention relates to a kind of preparation method of high purity silane, particularly relating to a kind of is raw material with the trichlorosilane directly, utilizes reaction rectification technique, and process dividing plate rectification and purification or direct disproportionation reaction rectifying prepare the method and apparatus of high purity silane.
Background technology
Silane, English name: silane, molecular formula is SiH
4Silane is widely used in industries such as semiconductor microactuator electronics IC, photovoltaic solar cell PV, liquid-crystal display LCD as a kind of important silicon source material.
At present, the mode of production of silane mainly contains three kinds: sodium aluminum fluoride method, Si-Mg alloy method and chlorosilane discrimination method.Wherein the sodium aluminum fluoride method is raw material with sodium aluminum hydride and silicon tetrafluoride, reaction synthesizing silane gas, through obtaining the above high purity electronic-grade silane gas of 6N behind follow-up absorption, the rectifying separation purification refine, U.S. MEMC company adopts this method scale operation high purity silane, domestic existing enterprise introduces this production line, but running condition is very undesirable; The Si-Mg alloy method also claims the Xiao Song method, is raw material with industrial silica fume, MAGNESIUM METAL and ammonium chloride, obtains silane through two-step reaction, because cost is higher, does not have large-scale production line so far; The chlorosilane discrimination method is many to be raw material with the trichlorosilane, through the multistep disproportionation reaction, final silane and the silicon tetrachloride of generating, cooperate the formation loop line with hydrogenation process, ejecta is few, and is favourable to environment, the material use efficiency height, no byproduct, U.S. REC company adopts this method mass preparation silane gas, and domestic temporary no enterprise adopts this technology.
It is more suitable that the good property of three kinds of technologies of comprehensive evaluation, and in conjunction with present domestic national conditions, chlorosilane discrimination method prepare the technology of silane.The technology that the chlorosilane discrimination method prepares high purity silane is proposed by UCC company the earliest, having proposed a kind of in its patent US4340574 is raw material with the trichlorosilane, utilize fixed bed to prepare the technology of silane by the multistep disproportionation reaction, wherein every grade of disproportionation reaction all need dispose corresponding rectification and purification process, long flow path, energy consumption height, many enterprises such as domestic smart merit science and technology are around many pieces of patents of this fixed bed multistep disproportionation art applications.In addition, also have the multidigit investigator that above technology has been carried out the improvement on the details, but do not have process innovation in essence.
There is certain defective in the technology that existing external chlorosilane disproportionation prepares silane, be mainly reflected in the multistep disproportionation processes of utilizing the supporting rectifying sequence of fixed bed and need at least two fixed-bed reactor and three rectifying tower, the equipment complexity, flow process is tediously long, and owing to be subjected to the lower restriction of multistep disproportionation reaction per pass conversion, need a large amount of materials circulating reaction after separating, the big energy of component separation consumes of repetition, energy consumption is higher.
Summary of the invention
The purpose of this invention is to provide the reactive distillation method and apparatus that the direct disproportionation of a kind of trichlorosilane prepares silane, is raw material with the trichlorosilane, utilizes reaction rectification technique, prepares high purity silane through dividing plate rectification and purification and disproportionation reaction rectifying.
The present invention proposes the reactive distillation method that the direct disproportionation of a kind of trichlorosilane prepares silane.Purity is reached refining trichlorosilane more than the 9N, feed the one stage disproportionation reaction fractionating tower and prepare silane; Disproportionation reaction rectifying tower cat head gas phase extraction reaction product utilizes pressure reduction to enter the silane tower, obtains chlorosilane mixture at the bottom of the tower, enters the silicon tetrachloride tower; The silane column overhead obtains high-purity liquid phase silane product, obtains unreacted chlorosilane at the bottom of the tower and returns the disproportionation reaction rectifying tower; The silicon tetrachloride column overhead obtains unreacted chlorosilane and returns the disproportionation reaction rectifying tower, obtains the silicon tetrachloride product at the bottom of the tower.
For the refining trichlorosilane raw material that is lower than below the 9N, trichlorosilane is at first through a dividing plate rectifying tower, obtains refining trichlorosilane after removing weight impurity, and purity reaches more than the 9N.
Direct disproportionation reaction of a step involved in the present invention is:
4SiHCl
3=SiH
4+3SiCl
4
The direct disproportionation of trichlorosilane of the present invention prepares the reactive distillation equipment of silane, is formed by connecting by trichlorosilane dividing plate rectifying tower (1), disproportionation reaction rectifying tower (2), silane purification tower (3) and silicon tetrachloride knockout tower (4); Material pipeline between them is connected to: the trichlorosilane feeding line connects the dividing plate rectifying tower, the trichlorosilane material pipeline of dividing plate rectifying tower side line connects the disproportionation reaction rectifying tower, disproportionation reaction rectifying tower cat head gas phase extraction pipeline connects the silane purification tower, disproportionation reaction rectifying tower bottoms material pipeline connects the silicon tetrachloride tower, the extraction of silane purification tower overhead product pipeline, silane purification tower bottoms material pipeline connects the disproportionation reaction rectifying tower, silicon tetrachloride column overhead material pipeline connects disproportionation reaction rectifying tower, product pipeline extraction at the bottom of the silicon tetrachloride Tata.
Reach refining trichlorosilane more than the 9N for material purity, raw material directly feeds disproportionation reaction rectifying tower (2), saves trichlorosilane dividing plate rectifying tower (1).
Trichlorosilane dividing plate rectifying tower (1) is partitioned column, and a vertical partition plate is set in the tower, and tower body is divided into public rectifying section, public stripping section, charging pre-separation section and product extraction section, and efficient structured packing or column plate are installed in the tower.
Disproportionation reaction rectifying tower (2) stage casing interstitital texture catalyzer is as conversion zone, structure catalyst loading height 8～30m, and last hypomere is respectively installed efficient structured packing.
Described structure catalyst is for to fill in basic anion exchange resin in the corrosion-resistant cloth bag, is partitioned into ripple packing to roll, and fills in the effect of playing reaction and rectifying in the disproportionation reaction rectifying tower (2) simultaneously.
Fill efficient structured packing in silane purification tower (3) tower.
Fill efficient structured packing in silicon tetrachloride knockout tower (4) tower.
Described trichlorosilane dividing plate rectifying tower (1) working pressure is 0.1～0.6Mpa, and tower top temperature is 45～105 ℃, and column bottom temperature is 47～115 ℃,
Described disproportionation reaction rectifying tower (2) working pressure is 0.2～0.5Mpa, and tower top temperature is 0～45 ℃, and column bottom temperature is 75～125 ℃.
Described silane purification tower (3) working pressure is 0.2～0.5Mpa, and tower top temperature is-90～-60 ℃, and column bottom temperature is 40～85 ℃.
Described silicon tetrachloride knockout tower (4) working pressure is 0.1～0.3Mpa, and tower top temperature is 79～85 ℃, and column bottom temperature is 102～110 ℃.
The present invention has the following advantages:
(1) compares with the multistep disproportionation processes of utilizing the supporting rectifying sequence of fixed bed, the characteristics of technology utilization reaction rectification technique of the present invention, continuous and the reactants separate with reaction product, impel reaction constantly to carry out to the positive reaction direction, broken the low restriction of multistep disproportionation reaction per pass conversion, in a reaction fractionating tower, realize the one stage disproportionation reaction, thin device, avoid a large amount of feed separation circulating reactions simultaneously, shortened flow process, energy-saving and cost-reducing.
(2) by rationally controlling each tower working pressure, make each column overhead column bottom temperature all control in more easy-operating scope, only disproportionation reaction rectifying tower tower top temperature needs the deep cooling media, can effectively control running cost.
(3) mode of successively purifying with trichlorosilane dividing plate rectification and purification, disproportionation reaction rectifying and silane is carried out the removal of impurities processing to silane product, makes that silane product purity is higher, can reach more than the electron gas level.
(4) be used with hydrogenation process, the silicon tetrachloride that makes disproportionation reaction generate is converted into trichlorosilane and recycles, and can make total system realize closed cycle, prepares route with other two kinds of silane and compares with the obvious advantage.
Description of drawings
Fig. 1 prepares the reactive distillation process schema of silane for the direct disproportionation of trichlorosilane.
Embodiment
Equipment connects as shown in Figure 1: be formed by connecting by trichlorosilane dividing plate rectifying tower (1), disproportionation reaction rectifying tower (2), silane purification tower (3) and silicon tetrachloride knockout tower (4).
Trichlorosilane dividing plate rectifying tower (1) is partitioned column, a vertical partition plate is set in the tower, tower body is divided into public rectifying section, public stripping section, charging pre-separation section and product extraction section, efficient structured packing or column plate are installed in the tower, realize removing the effect of weight impurity simultaneously by a partitioned column, the material of cat head extraction enrichment light impurity, the material of extraction enrichment heavy seeds at the bottom of the tower, the refining TCS product of side line extraction enters disproportionation reaction rectifying tower (2).Trichlorosilane dividing plate rectifying tower (1) working pressure is 0.1～0.6Mpa, tower top temperature is 45～105 ℃, and column bottom temperature is 47～115 ℃, under this operational condition, cat head adopts recirculated water as refrigerant, adopts low-pressure steam or low temperature thermal oil as heating agent at the bottom of the tower.
Disproportionation reaction rectifying tower (2) stage casing interstitital texture catalyzer is as conversion zone, for guaranteeing reaction conversion ratio, structure catalyst loading height 8～30m, wherein structure catalyst is for to fill in basic anion exchange resin in the corrosion-resistant cloth bag, be partitioned into ripple packing and roll, fill in the effect that to play reaction and rectifying in the disproportionation reaction rectifying tower (2) simultaneously.Last hypomere is respectively installed efficient structured packing.Refining TCS and the chlorosilane that returns enter conversion zone, through abundant Reaction Separation, cat head obtains the mixture of silane and chlorosilane, and the gas phase extraction enters silane purification tower (3), obtain reacting the STC of generation and the mixture of chlorosilane at the bottom of the tower, enter silicon tetrachloride knockout tower (4).Disproportionation reaction rectifying tower (2) working pressure is 0.2～0.5Mpa, and tower top temperature is 0～45 ℃, and column bottom temperature is 75～125 ℃, under this operational condition, cat head adopts the heat-eliminating medium cooling, adopts low-pressure steam or thermal oil as heating agent at the bottom of the tower, effectively reduces running cost.
Fill efficient structured packing in silane purification tower (3) tower, the mixture of gas phase silane and chlorosilane is by entering in the tower, and cat head obtains high purity silane, obtains chlorosilane at the bottom of the tower and returns disproportionation reaction rectifying tower (2).Silane purification tower (3) working pressure is 0.2～0.5Mpa, tower top temperature is-90～-60 ℃, column bottom temperature is 40～85 ℃, under this operational condition, cat head adopts refrigerant coolings such as ethene, freonll-11 or liquid nitrogen, adopt steam or thermal oil to heat as heating agent at the bottom of the tower, rationally reduce running cost.
Fill efficient structured packing in silicon tetrachloride knockout tower (4) tower, the mixture of STC and chlorosilane is by entering in the tower, and cat head obtains chlorosilane and returns disproportionation reaction rectifying tower (2), obtains STC at the bottom of the tower and goes out system.Silicon tetrachloride knockout tower (4) working pressure is 0.1～0.3Mpa, and tower top temperature is 79～85 ℃, and column bottom temperature is 102～110 ℃, and under this operational condition, cat head adopts recirculated water as refrigerant, adopts low-pressure steam or low temperature thermal oil as heating agent at the bottom of the tower.
Concrete application example is as follows:
Example 1:
Adjust explanation with pilot scale 10t/y high purity silane output.
25.4kg/hTCS feedstock pump is sent into trichlorosilane dividing plate rectifying tower (1) middle part charging, the tower internal upper part is filled the efficient structured packing of 3m as public rectifying section, for separating of light impurity; The efficient structured packing of under-filled 3m is as public stripping section, for separating of heavy seeds; The middle part is that the dividing plate of 10m is cut apart with a tile height, and both sides fill respectively that the efficient structured packing of 9m is respectively applied to the charging pre-separation and product purification side is adopted.Trichlorosilane dividing plate rectifying tower (1) tower diameter is 150mm.Working pressure control is at 0.6Mpa, and tower top temperature is 105 ℃, and column bottom temperature is that 115 ℃ of cats head adopt the recirculated water cooling, and tower reactor adopts the low temperature heat-conducting oil heating.Under this operational condition, cat head liquid phase extraction light impurity, produced quantity is about 1kg/h, liquid phase extraction heavy seeds at the bottom of the tower, produced quantity is about 1kg/h, and the refining TCS product of side line extraction enters disproportionation reaction rectifying tower (2) in the tower, and produced quantity is 23.4kg/h.
23.4kg/h refining TCS enters disproportionation reaction rectifying tower (2), three sections 9m structure catalysts are altogether filled at the middle part in the tower, filled in the corrosion-resistant cloth bag by basic anion exchange resin, be partitioned into screen waviness packings and roll, play the effect of reactive distillation, the highly efficient structured packing of 2m is filled as rectifying section in top, reclaims unreacted chlorosilane, the highly efficient structured packing of under-filled 2m is as stripping section, initial gross separation TCS and STC.Disproportionation reaction rectifying tower (2) tower diameter is 150mm.Working pressure control is at 0.5Mpa, and tower top temperature is controlled at 45 ℃, and column bottom temperature is 125 ℃.Cat head adopts 7 degree recirculated water coolings, adopts the low temperature heat-conducting oil heating at the bottom of the tower.Under this operational condition, the total reflux of cat head liquid phase, MS and DCS mixture that gas phase extraction disproportionation reaction generates, the extraction gas flow is about 3.45kg/h, enters silane purification tower (3); Liquid phase extraction disproportionation reaction generates at the bottom of the tower STC and unreacted TCS, the extraction liquid flow rate is about 32.38kg/h, enters silicon tetrachloride knockout tower (4).
3.45kg/hMS enter silane purification tower (3) with the DCS mixed gas, fill four sections efficient structured packings of 12m altogether in the tower, gaseous products middle part charging, tower diameter is 50mm.Working pressure is 0.5Mpa, and tower top temperature is-60 ℃, and column bottom temperature is 85 ℃.Cat head adopts cooled with liquid nitrogen, adopts the low temperature heat-conducting oil heating at the bottom of the tower.Under this operational condition, cat head liquid phase extraction deep cooling high purity silane product, purity reaches more than the 9N, and the product produced quantity is about 1.38kg/h; DCS is reclaimed in the liquid phase extraction at the bottom of the tower, and produced quantity is about 2.07kg/h, returns disproportionation reaction rectifying tower (2) conversion zone middle part.
32.38kg/hTCS enter silicon tetrachloride knockout tower (4) with STC blended liquid phase product, fill four sections efficient structured packings of 12m altogether in the tower, liquid-phase product middle part charging, tower diameter is 150mm.Working pressure is 0.3Mpa, and tower top temperature is 85 ℃, and column bottom temperature is 110 ℃.Cat head adopts the recirculated water cooling, adopts the low temperature heat-conducting oil heating at the bottom of the tower.Under this operational condition, TCS is reclaimed in the extraction of cat head liquid phase, and produced quantity is about 10.36kg/h, returns disproportionation reaction rectifying tower (2) conversion zone middle part; Liquid phase extraction STC product at the bottom of the tower, produced quantity is about 22.02kg/h.
Example 2:
Adjust explanation with commercial production scale 10000t/y high purity silane output.
24.4t/hTCS feedstock pump is sent into trichlorosilane dividing plate rectifying tower (1) middle part charging, the tower internal upper part is filled the efficient structured packing of 5m as public rectifying section, for separating of light impurity; The efficient structured packing of under-filled 5m is as public stripping section, for separating of heavy seeds; The middle part is that the dividing plate of 20m is cut apart with a tile height, and both sides fill respectively that the efficient structured packing of 15m is respectively applied to the charging pre-separation and product purification side is adopted.Trichlorosilane dividing plate rectifying tower (1) tower diameter is 4.2m.Working pressure control is at 0.1Mpa, and tower top temperature is 45 ℃, and column bottom temperature is 47 ℃.Cat head adopts the recirculated water cooling, and tower reactor adopts the low-pressure steam heating.Under this operational condition, cat head liquid phase extraction light impurity, produced quantity is about 500kg/h, liquid phase extraction heavy seeds at the bottom of the tower, produced quantity is about 500kg/h, and the refining TCS product of side line extraction enters disproportionation reaction rectifying tower (2) in the tower, and produced quantity is 23.4t/h.
23.4t/h refining TCS enters disproportionation reaction rectifying tower (2), four sections 16m structure catalysts are altogether filled at the middle part in the tower, filled in the corrosion-resistant cloth bag by basic anion exchange resin, be partitioned into screen waviness packings and roll, play the effect of reactive distillation, the highly efficient structured packing of 3m is filled as rectifying section in top, reclaims unreacted chlorosilane, the highly efficient structured packing of under-filled 3m is as stripping section, initial gross separation TCS and STC.Disproportionation reaction rectifying tower (2) tower diameter is 3.4m.Working pressure control is at 0.2Mpa, and tower top temperature is controlled at 0 ℃, and column bottom temperature is 75 ℃.Cat head adopts the chilled brine cooling, adopts the low-pressure steam heating at the bottom of the tower.Under this operational condition, the total reflux of cat head liquid phase, MS and DCS mixture that gas phase extraction disproportionation reaction generates, the extraction gas flow is about 3.45t/h, enters silane purification tower (3); Liquid phase extraction disproportionation reaction generates at the bottom of the tower STC and unreacted TCS, the extraction liquid flow rate is about 32.38t/h, enters silicon tetrachloride knockout tower (4).
3.45t/hMS enter silane purification tower (3) with the DCS mixed gas, fill five sections efficient structured packings of 20m altogether in the tower, gaseous products middle part charging, tower diameter is 1m.Working pressure is 0.2Mpa, and tower top temperature is-90 ℃, and column bottom temperature is 40 ℃.Cat head adopts the ethene cooling, adopts the low-pressure steam heating at the bottom of the tower.Under this operational condition, cat head liquid phase extraction deep cooling high purity silane product, purity reaches more than the 9N, and the product produced quantity is about 1.38t/h; DCS is reclaimed in the liquid phase extraction at the bottom of the tower, and produced quantity is about 2.07t/h, returns disproportionation reaction rectifying tower (2) conversion zone middle part.
32.38t/hTCS enter silicon tetrachloride knockout tower (4) with STC blended liquid phase product, fill five sections efficient structured packings of 20m altogether in the tower, liquid-phase product middle part charging, tower diameter is 3m.Working pressure is 0.1Mpa, and tower top temperature is 79 ℃, and column bottom temperature is 102 ℃.Cat head adopts the recirculated water cooling, adopts the low-pressure steam heating at the bottom of the tower.Under this operational condition, TCS is reclaimed in the extraction of cat head liquid phase, and produced quantity is about 10.36t/h, returns disproportionation reaction rectifying tower (2) conversion zone middle part; Liquid phase extraction STC product at the bottom of the tower, produced quantity is about 22.02t/h.
Example 3:
The feed purification purity of trichlorosilane reaches more than the 9N, adjusts explanation with commercial production scale 10000t/y high purity silane output.
23.4t/h refining TCS enters disproportionation reaction rectifying tower (2), four sections 16m structure catalysts are altogether filled at the middle part in the tower, filled in the corrosion-resistant cloth bag by basic anion exchange resin, be partitioned into screen waviness packings and roll, play the effect of reactive distillation, the highly efficient structured packing of 3m is filled as rectifying section in top, reclaims unreacted chlorosilane, the highly efficient structured packing of under-filled 3m is as stripping section, initial gross separation TCS and STC.Disproportionation reaction rectifying tower (2) tower diameter is 3.4m.Working pressure control is at 0.2Mpa, and tower top temperature is controlled at 0 ℃, and column bottom temperature is 75 ℃.Cat head adopts the chilled brine cooling, adopts the low-pressure steam heating at the bottom of the tower.Under this operational condition, the total reflux of cat head liquid phase, MS and DCS mixture that gas phase extraction disproportionation reaction generates, the extraction gas flow is about 3.45t/h, enters silane purification tower (3); Liquid phase extraction disproportionation reaction generates at the bottom of the tower STC and unreacted TCS, the extraction liquid flow rate is about 32.38t/h, enters silicon tetrachloride knockout tower (4).
3.45t/hMS enter silane purification tower (3) with the DCS mixed gas, fill five sections efficient structured packings of 20m altogether in the tower, gaseous products middle part charging, tower diameter is 1m.Working pressure is 0.2Mpa, and tower top temperature is-90 ℃, and column bottom temperature is 40 ℃.Cat head adopts the ethene cooling, adopts the low-pressure steam heating at the bottom of the tower.Under this operational condition, cat head liquid phase extraction deep cooling high purity silane product, purity reaches more than the 9N, and the product produced quantity is about 1.38t/h; DCS is reclaimed in the liquid phase extraction at the bottom of the tower, and produced quantity is about 2.07t/h, returns disproportionation reaction rectifying tower (2) conversion zone middle part.
32.38t/hTCS enter silicon tetrachloride knockout tower (4) with STC blended liquid phase product, fill five sections efficient structured packings of 20m altogether in the tower, liquid-phase product middle part charging, tower diameter is 3m.Working pressure is 0.1Mpa, and tower top temperature is 79 ℃, and column bottom temperature is 102 ℃.Cat head adopts the recirculated water cooling, adopts the low-pressure steam heating at the bottom of the tower.Under this operational condition, TCS is reclaimed in the extraction of cat head liquid phase, and produced quantity is about 10.36t/h, returns disproportionation reaction rectifying tower (2) conversion zone middle part; Liquid phase extraction STC product at the bottom of the tower, produced quantity is about 22.02t/h.
The direct disproportionation of trichlorosilane that the present invention proposes prepares the reactive distillation method and apparatus of silane, be described by embodiment, person skilled obviously can be changed or suitably change and combination system and method as herein described in not breaking away from content of the present invention, spirit and scope, realizes technology of the present invention.Special needs to be pointed out is, the replacement that all are similar and change apparent to those skilled in the artly, they are regarded as being included in spirit of the present invention, scope and the content.
Claims (10)
1. the direct disproportionation of trichlorosilane prepares the reactive distillation method of silane, it is characterized in that purity is reached refining trichlorosilane more than the 9N, feeds the one stage disproportionation reaction fractionating tower and prepares silane; Disproportionation reaction rectifying tower cat head gas phase extraction reaction product utilizes pressure reduction to enter the silane tower, obtains chlorosilane mixture at the bottom of the tower, enters the silicon tetrachloride tower; The silane column overhead obtains high-purity liquid phase silane product, obtains unreacted chlorosilane at the bottom of the tower and returns the disproportionation reaction rectifying tower; The silicon tetrachloride column overhead obtains unreacted chlorosilane and returns the disproportionation reaction rectifying tower, obtains the silicon tetrachloride product at the bottom of the tower.
2. the method for claim 1 is characterized in that trichlorosilane at first through a dividing plate rectifying tower, removes to obtain refining trichlorosilane behind the weight impurity, and purity reaches more than the 9N.
3. method as claimed in claim 1 or 2 is characterized in that described disproportionation reaction rectifying tower (2) working pressure is 0.2～0.5Mpa, and tower top temperature is 0～45 ℃, and column bottom temperature is 75～125 ℃.
4. method as claimed in claim 1 or 2 is characterized in that described silane purification tower (3) working pressure is 0.2～0.5Mpa, and tower top temperature is-90～-60 ℃, and column bottom temperature is 40～85 ℃.
5. method as claimed in claim 1 or 2 is characterized in that described silicon tetrachloride knockout tower (4) working pressure is 0.1～0.3Mpa, and tower top temperature is 79～85 ℃, and column bottom temperature is 102～110 ℃.
6. realize that the direct disproportionation of the described trichlorosilane of claim 1 prepares the reactive distillation equipment of silane, it is characterized in that being formed by connecting by disproportionation reaction rectifying tower (2), silane purification tower (3) and silicon tetrachloride knockout tower (4); Material pipeline between them is connected to: trichlorosilane material pipeline connects the disproportionation reaction rectifying tower, disproportionation reaction rectifying tower cat head gas phase extraction pipeline connects the silane purification tower, disproportionation reaction rectifying tower bottoms material pipeline connects the silicon tetrachloride tower, the extraction of silane purification tower overhead product pipeline, silane purification tower bottoms material pipeline connects the disproportionation reaction rectifying tower, silicon tetrachloride column overhead material pipeline connects disproportionation reaction rectifying tower, product pipeline extraction at the bottom of the silicon tetrachloride Tata.
7. realize that the direct disproportionation of the described trichlorosilane of claim 2 prepares the reactive distillation equipment of silane, it is characterized in that being formed by connecting by trichlorosilane dividing plate rectifying tower (1), disproportionation reaction rectifying tower (2), silane purification tower (3) and silicon tetrachloride knockout tower (4); Material pipeline between them is connected to: the trichlorosilane feeding line connects the dividing plate rectifying tower, the trichlorosilane material pipeline of dividing plate rectifying tower side line connects the disproportionation reaction rectifying tower, disproportionation reaction rectifying tower cat head gas phase extraction pipeline connects the silane purification tower, disproportionation reaction rectifying tower bottoms material pipeline connects the silicon tetrachloride tower, the extraction of silane purification tower overhead product pipeline, silane purification tower bottoms material pipeline connects the disproportionation reaction rectifying tower, silicon tetrachloride column overhead material pipeline connects disproportionation reaction rectifying tower, product pipeline extraction at the bottom of the silicon tetrachloride Tata.
8. equipment as claimed in claim 7, it is characterized in that trichlorosilane dividing plate rectifying tower (1) is partitioned column, a vertical partition plate is set in the tower, tower body is divided into public rectifying section, public stripping section, charging pre-separation section and product extraction section, efficient structured packing or column plate are installed in the tower.
9. as claim 6 or 7 described equipment, it is characterized in that disproportionation reaction rectifying tower (2) stage casing interstitital texture catalyzer as conversion zone, structure catalyst loading height 8～30m, last hypomere is respectively installed efficient structured packing.
10. as claim 6 or 7 described equipment, it is characterized in that described structure catalyst is for to fill in basic anion exchange resin in the corrosion-resistant cloth bag, be partitioned into ripple packing and roll, fill in the effect of playing reaction and rectifying in the disproportionation reaction rectifying tower (2) simultaneously.
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| CN112758936A (en) * | 2020-12-31 | 2021-05-07 | 内蒙古兴洋科技有限公司 | System and method for simultaneously producing electronic-grade silane and electronic-grade monochlorosilane |
| CN115043869A (en) * | 2022-06-08 | 2022-09-13 | 宁夏福瑞硅烷材料有限公司 | Method for preparing high-purity vinyl trimethoxy silane |
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