CN109748931A - A kind of preparation method and production system of high-purity ethyl orthosilicate - Google Patents

A kind of preparation method and production system of high-purity ethyl orthosilicate Download PDF

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Publication number
CN109748931A
CN109748931A CN201910119724.0A CN201910119724A CN109748931A CN 109748931 A CN109748931 A CN 109748931A CN 201910119724 A CN201910119724 A CN 201910119724A CN 109748931 A CN109748931 A CN 109748931A
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rectifying
light
hydrogen chloride
silicon tetrachloride
ethyl orthosilicate
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CN109748931B (en
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金向华
王新喜
栗鹏伟
刘晶
齐相前
师东升
夏致远
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Jinhong Gas Co ltd
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Suzhou Jinhong Gas Co Ltd
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    • 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

Abstract

The present invention provides a kind of preparation methods of high-purity ethyl orthosilicate, comprising: S1) high purity silicon tetrachloride and high straight alcohol are mixed into row reactive distillation, obtain thick ethyl orthosilicate and thick hydrogen chloride；S2 the thick ethyl orthosilicate is handled through decolorization adsorption), after alkaline adsorption processing, carries out taking off light rectification process, obtains the light component of de- light treated ethyl orthosilicate and removing；S3) de- light treated the ethyl orthosilicate is carried out de- weight rectification process, obtain high-purity ethyl orthosilicate after boron phosphorus adsorbs resin and adsorption of metal ions resin treatment.Compared with prior art, the present invention is using high purity silicon tetrachloride and high straight alcohol as raw material, keep moisture content in the reaction system few, reduce the generation of side reaction, the especially polymerization reaction of ethyl orthosilicate, the generation that silester polymer can be reduced alleviates the pressure of purification process, improves the yield of high-purity ethyl orthosilicate.

Description

A kind of preparation method and production system of high-purity ethyl orthosilicate
Technical field
The invention belongs to the preparation methods and production system of technical field of semiconductors more particularly to a kind of high-purity ethyl orthosilicate System.
Background technique
SiO2For natural oxide film, there is critically important purposes in semiconductor processing, such as shelter impurity, grid oxygen dielectric, Surface passivation and protection, device isolation, metallic conduction interlayer dielectric.Semiconductor technology forms SiO2The method master of oxide layer Have thermal oxide (for the semiconductor material that can form homeostasis oxide layer), Low Pressure Chemical Vapor Deposition (LPCVD), etc. Plasma enhanced chemical vapor sedimentation (PECVD) and aumospheric pressure cvd method (APCVD) etc., wherein due to APCVD requirement Throughput it is big, and technique generate particle it is relatively more, at present most of semiconductor technologies be rarely employed.High-purity positive silicic acid When ethyl ester (Tetraethyl Orthosilicate writes a Chinese character in simplified form TEOS, monomer) is used for LPCVD, the speed of silica membrane deposition Rate can achieve 50 à/min, and the thickness uniformity of film is less than 3%, these excellent operational characteristiies and in safety in utilization side The distinguishing feature in face, which makes it, gradually becomes the prevailing technology of cvd silicon dioxide film.
But existing high-purity ethyl orthosilicate makes to obtain by the way that the ethyl orthosilicate of technical grade is carried out the means such as purification process, Such as the Chinese patent of Publication No. CN103772424A, it is complexed by absorption, the processes such as conventional distillation, sub-boiling distillation, not only work Skill stability is poor, exists simultaneously the problems such as production efficiency is low, energy consumption is high.
Also, the ethyl orthosilicate of industrial goods substantially to pass through reactive distillation work as raw material for silicon tetrachloride and ethyl alcohol Skill obtains, by-product hydrochloric acid, multi-purpose to make coating, waterproof material, binder and refractory material, not high to the purity requirement of product, main The specific gravity of silica after wanting index to have hydrolysis.Commodity silester is according to SiO2Mass percentage difference can be there are many type Number: (the SiO of silester -282The ethyl orthosilicate that content is about 28%) and its hydrolytic polymerization after the silester-that generates 32, silester -40, silester -50.Have with silester -32, silester -40 existing for linear structure good Stability is used widely, and silester -50 is solid netted unstable structure, and stabilizer, which need to be added, to be stored.
Raw material silicon tetrachloride substantially on be that improved Siemens production polysilicon or silane coupling agent industry get rid of material, Impurity content is higher, and the ethyl orthosilicate impurity of generation is more and complicated, it is more difficult to purify.What is applied in production is not mostly positive silicic acid The monomer of ethyl ester, but the polymer of the silester of partial hydrolysis polymerization, thus it is lower to the water requirement in reaction system, permit Perhaps or the water of part is needed.Due to most widely used, therefore meeting when many synthesis of silester -32, silester -40 A certain amount of water is added or uses 95% cheaper edible alcohol, ultimately forms ethyl alcohol, triethoxysilane, three second of methyl Oxysilane, methoxyl group triethoxysilane, propyl-triethoxysilicane, ethyl orthosilicate dimer, ethyl orthosilicate trimerization Organic silicon impurities component such as body.Since the application requirement of the ethyl orthosilicate of industrial goods is lower, it is distinct from electronic semi-conductor's neck Requirement index of the domain to ethyl orthosilicate makes to purify to obtain high pure electronic grade ethyl orthosilicate using the ethyl orthosilicate of industrial goods Work also has the problems such as the rate of recovery is low to carrying out huge difficulty.
The preparation process of high purity silicon tetrachloride mainly includes rectification method, absorption method, light chlorination process etc..Rectifying is to apply at present Most wide liquid mixture separates method, has many advantages, such as that easy to operate, high degree of automation, continuous chemical conversion production, yield are big, extensively The general preparation process applied to high purity silicon tetrachloride.Rectification method is to removal such as AlCl3、BCl3、FeCl3、CuCl2、PCl3Equal poles Property impurity has preferable effect, but relatively limited to the removal of hydrogen containing foreign (such as trim,ethylchlorosilane), and reason is trimethyl The boiling point of chlorosilane is very close with silicon tetrachloride, is kept completely separate and needs very high theoretical cam curve and reflux ratio, therefore uses Traditional rectification method silicon tetrachloride relatively low mainly for the preparation of quality requirement.Solid absorption basic principle is based on chemical combination Each component chemical bond polarity difference carries out adsorbing separation in object.But it is readily incorporated impurity in adsorption process, system is caused Secondary pollution, therefore product quality is unable to get guarantee.Light chlorination process is to irradiate chlorine by ultraviolet light, and it is free to generate chlorine atom Base, chlorine atom free radical can be with SiHCl3And other hydrogen containing foreigns react, after dehydrochlorination reaction occurs for hydrogen containing foreign, with The relative volatility of silicon tetrachloride increases, to be conducive to be separated by rectification and purification, obtains optical fiber high-purity tetrachloro SiClx.Light chlorination process prepares silicon tetrachloride for optical fiber mostly still in experimental stage at present, lacks experience on probation on a large scale.By It is high in chlorine risk, and easily corrode equipment and pipeline leaks, to constrain its large-scale application.Scale system The method of standby dehydrated alcohol has molecular sieve dehydration method, extracting rectifying, azeotropic distillation and membrane separation process.And so-called work now Industry dehydrated alcohol content is 99.5%, for higher purity requirement, needs to be further purified.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is that providing a kind of high-purity ethyl orthosilicate and electron level chlorination The preparation method of hydrogen, the preparation method is simple and yield is higher.
The present invention provides the preparation methods of high-purity ethyl orthosilicate, comprising:
S1 high purity silicon tetrachloride and high straight alcohol) are mixed into row reactive distillation, obtain thick ethyl orthosilicate and thick chlorination Hydrogen；
S2 the thick ethyl orthosilicate is handled through decolorization adsorption), after alkaline adsorption processing, carries out taking off light rectifying, obtain The light component of ethyl orthosilicate and removing after taking off light rectifying；
S3 the ethyl orthosilicate taken off after light rectifying) is adsorbed into resin and adsorption of metal ions resin treatment through boron phosphorus Afterwards, de- rectifying again is carried out, high-purity ethyl orthosilicate is obtained.
Preferably, the step S1) in reactive distillation temperature be 70 DEG C~90 DEG C；Reaction pressure is 0.5~1.5bar； The step S2) in take off light rectifying temperature be 95 DEG C~130 DEG C；The pressure for taking off light rectifying is -0.6~-1bar；Reflux ratio is 1~10；The step S3) in take off again rectifying temperature be 95 DEG C~130 DEG C；The pressure of de- rectifying again is -0.6~-1bar；It returns Stream is than being 1~10.
Preferably, the thick hydrogen chloride carry out it is cooling, be adsorbed by drying after, compression, successively carry out hydrogen chloride take off light rectifying with The frivolous heavy rectifying of chlorination, obtains high-purity hydrogen chloride.
Preferably, it after compression, is adsorbed by drying, is pre-chilled for the second time, then carry out taking off light rectifying and de- rectifying again.
Preferably, the temperature of the condensation is 5 DEG C~20 DEG C；The pressure of the compression is 1.2~1.35MPa；Compression Temperature is 40 DEG C~50 DEG C；The temperature of the hydrogen chloride dehydrogenation rectifying is -30 DEG C~-24 DEG C；The hydrogen chloride takes off light rectifying Pressure is 1.18~1.22MPa；Reflux ratio is 0.5~3；The temperature of the de- rectifying again of the hydrogen chloride is -24 DEG C~-28 DEG C；Institute The pressure for stating the de- rectifying again of hydrogen chloride is 1.2~1.24MPa；Reflux ratio is 1~5.
Preferably, further includes:
Industrial alcohol is reacted with the light component removed in step S2), after filtering, ethyl alcohol is carried out and takes off light rectification process and second After the de- weight rectification process of alcohol, high straight alcohol is obtained.
Preferably, further includes:
Silicon tetrachloride progress silicon tetrachloride is taken off into light rectifying, is then adsorbed at resin and adsorption of metal ions resin through boron phosphorus After reason, carries out silicon tetrachloride and take off rectifying again, obtain high purity silicon tetrachloride.
Preferably, it is 56 DEG C~108 DEG C that the silicon tetrachloride, which takes off the temperature of light rectifying,；Pressure is 0~3bar；Take off light rectifying When remove light component amount be silicon tetrachloride quality 1/5~1/12；The temperature of the de- rectifying again of silicon tetrachloride is 56 DEG C~110 ℃；Pressure is 0~3bar；The amount that heavy constituent is removed when de- rectifying again is the 1/5~1/12 of rectifying material.
The present invention also provides a kind of production systems of high-purity ethyl orthosilicate, comprising:
High purity silicon tetrachloride storage tank；
High straight alcohol storage tank；
Reactive distillation device；The high purity silicon tetrachloride storage tank is connected with reactive distillation device respectively with high-purity ethanol storage tank；
Decolorization adsorption device；The decolorization adsorption device is connected with reactive distillation device；
Alkaline adsorption device；Alkaline matter is provided in the alkaline adsorption device；The alkaline adsorption device and decolorization adsorption device It is connected；
De-light rectification column；The dehydrogenation rectifying column is connected with alkaline adsorption device；
Boron phosphorus absorber；Boron phosphorus absorption resin is provided in the boron phosphorus absorber；The boron phosphorus absorber and dehydrogenation essence Tower is evaporated to be connected；
Adsorption of metal ions device；Adsorption of metal ions resin is provided in the adsorption of metal ions device；The metal from Sub- absorber is connected with boron phosphorus absorber；
De- heavy distillation column；The de- heavy distillation column is connected with adsorption of metal ions device.
It preferably, further include high-purity hydrogen chloride production system；The high-purity hydrogen chloride production system includes:
Graphite condenser；The graphite condenser is connected with reactive distillation device；
Hydrogen chloride adsorption dehumifier；The hydrogen chloride adsorption dehumifier is connected with graphite condenser；
Compressor；The compressor is connected with hydrogen chloride adsorption dehumifier；
Hydrogen chloride de-light rectification column；The hydrogen chloride de-light rectification column is connected with compressor；
Hydrogen chloride takes off heavy distillation column；The hydrogen chloride takes off heavy distillation column and is connected with hydrogen chloride de-light rectification column.
The present invention provides a kind of preparation methods of high-purity ethyl orthosilicate, comprising: S1) by high purity silicon tetrachloride with it is high-purity Ethyl alcohol mixing carries out reactive distillation, obtains thick ethyl orthosilicate and thick hydrogen chloride；S2) the thick ethyl orthosilicate is inhaled through decoloration Attached processing carries out taking off light rectification process after alkaline adsorption processing, obtains light group of de- light treated ethyl orthosilicate and removing Point；S3) de- light treated the ethyl orthosilicate is carried out after boron phosphorus adsorbs resin and adsorption of metal ions resin treatment De- weight rectification process, obtains high-purity ethyl orthosilicate.Compared with prior art, the present invention is using high purity silicon tetrachloride and high-purity second Alcohol keeps moisture content in the reaction system few as raw material, reduces the poly- of the generation of side reaction, especially ethyl orthosilicate Reaction is closed, the generation of silester polymer can be reduced, alleviate the pressure of purification process, improve high-purity ethyl orthosilicate Yield.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of high-purity ethyl orthosilicate production system provided by the invention；
Fig. 2 is the structural schematic diagram of high-purity ethyl orthosilicate production system provided by the invention；
Fig. 3 is the structural schematic diagram of high purity silicon tetrachloride production system provided by the invention；
Fig. 4 is the structural schematic diagram of high straight alcohol production system provided by the invention；
Fig. 5 is the structural schematic diagram of high-purity hydrogen chloride production system provided by the invention；.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical scheme in the embodiment of the invention is clearly and completely described, Obviously, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based in the present invention Embodiment, every other embodiment obtained by those of ordinary skill in the art without making creative efforts, all Belong to the scope of protection of the invention.
The present invention provides a kind of preparation methods of high-purity ethyl orthosilicate, comprising: S1) by high purity silicon tetrachloride with it is high-purity Ethyl alcohol mixing carries out reactive distillation, obtains thick ethyl orthosilicate and thick hydrogen chloride；S2) the thick ethyl orthosilicate is inhaled through decoloration Attached processing carries out taking off light rectifying after alkaline adsorption processing, the light component of ethyl orthosilicate and removing after obtaining taking off light rectifying； S3) ethyl orthosilicate taken off after light rectifying is taken off after boron phosphorus adsorbs resin and adsorption of metal ions resin treatment Rectifying again obtains high-purity ethyl orthosilicate.
Wherein, the present invention is not particularly limited the source of all raw materials, can for it is commercially available be also self-control.
In the present invention, the high purity silicon tetrachloride is preferably prepared according to the following steps: silicon tetrachloride is carried out de- light essence It evaporates, then after boron phosphorus adsorbs resin and adsorption of metal ions resin treatment, carries out de- rectifying again, obtain high purity silicon tetrachloride.
Silicon tetrachloride is carried out to take off light rectifying；The silicon tetrachloride is polysilicon well known to those skilled in the art or silane The by-produced tetrachlorosilane of coupling agent has no special limitation；It is described to take off light rectifying silicon tetrachloride is preferably used to take off light rectifying Tower carries out；The silicon tetrachloride is preferably fed in the middle and upper part of silicon tetrachloride de-light rectification column；It is described take off light rectifying preferably plus Press rectifying；The temperature for taking off light rectifying is preferably 56 DEG C~108 DEG C, more preferably 70 DEG C~95 DEG C；It is described to take off light rectifying Pressure be preferably 0~3bar, more preferably 0.5~2bar.Trichlorosilane in silicon tetrachloride, three can be removed by being taken off light rectifying The light components such as boron chloride, dichlorosilane, light component can recycle after condensing；The amount of removing light component is tetrachloro when taking off light rectifying The 1/5~1/12 of SiClx quality, more preferably 1/7~1/10；The temperature of overhead condensation when taking off light rectifying is preferably 30 DEG C ~50 DEG C；The reflux ratio for taking off light rectifying is preferably 1~10, and more preferably 4~8, it is further preferably 6~8.
After taking off light rectifying, resin is adsorbed using boron phosphorus and adsorption of metal ions resin is handled；The boron phosphorus absorption tree Rouge is that boron phosphorus well known to those skilled in the art adsorbs resin, has no special limitation, is preferably macropore chela in the present invention Close absorption resin, the LSC-700, the MARATHON A of DOW of more preferably blue dawn science and technology；The adsorption of metal ions resin is this Adsorption of metal ions resin known to the technical staff of field has no special limitation, and preferably macropore chelates in the present invention Adsorb resin, the LSC-100, the MARATHON MSC of DOW of more preferably blue dawn science and technology.Resin and metal ion are adsorbed through boron phosphorus Absorption resin adsorption processing can remove the impurity such as boron phosphorus and metal ion in silicon tetrachloride.
After boron phosphorus adsorbs resin and adsorption of metal ions resin treatment, de- rectifying again is carried out, high purity silicon tetrachloride is obtained. The de- rectifying again preferably uses silicon tetrachloride to take off heavy distillation column and carries out；The feed inlet that the silicon tetrachloride takes off heavy distillation column is preferred Positioned at the middle and lower part of tower；The de- rectifying again is preferably compression rectification；The temperature of the de- rectifying again is preferably 56 DEG C~110 DEG C, more preferably 70 DEG C~95 DEG C；The pressure of the de- rectifying again is preferably 0~3bar, more preferably 0.5~2bar；By De- rectifying again can remove phosphorus oxychloride, phosphorus trichloride, phosphorus pentachloride, dimethyldichlorosilane, methyl trichlorine in silicon tetrachloride The heavy components such as silane take off the recyclable recycling of heavy constituent of the removing of rectifying again；The preferably de- weight essence of the amount of the removing heavy constituent Evaporate the 1/5~1/12 of quality of material, more preferably 1/7~1/10；The temperature of overhead condensation is preferably 30 when the de- rectifying again DEG C~50 DEG C；The reflux ratio of the de- rectifying again is preferably 1~10, and more preferably 4~8, it is further preferably 6~8.The present invention obtains High purity silicon tetrachloride (containing the trimethyl silane with its azeotropic) purity be 5N or more.
The present invention avoids the cumbersome process route for abolishing silicon tetrachloride azeotropic in terms of silicon tetrachloride purifying, makes and four The trim,ethylchlorosilane and ethyl alcohol of silicon chloride azeotropic carry out esterification, the trimethoxy Ethoxysilane of generation, and boiling point is It 75 DEG C, with the boiling-point difference of ethyl orthosilicate away from big, easily separates, can be removed in the de- light rectifying of purifying ethyl orthosilicate, Simplify process flow.
The method of prepare with scale dehydrated alcohol has molecular sieve dehydration method, extracting rectifying, azeotropic distillation and UF membrane Method.But so-called industry anhydrous ethanol content is 99.5% now, for higher purity requirement, needs to be further purified.This hair High straight alcohol described in bright is preferably prepared according to the following steps: industrial alcohol is reacted with the light component removed in step S2), is filtered Afterwards, it carries out ethyl alcohol and takes off light rectification process with after the de- weight rectification process of ethyl alcohol, obtain high straight alcohol.The light component of removing is mainly second Alcohol, the trimethylethoxysilane generated with a small amount of ethyl orthosilicate and with the trim,ethylchlorosilane of silicon tetrachloride azeotropic, The impurity such as methyltriethoxysilane, ethyl orthosilicate, trimethylethoxysilane, three ethoxy of methyl in the light component of removing Base silane etc. is reacted with the water in industrial alcohol, silica and ethyl alcohol is generated, to remove the water in industrial alcohol；The filtering Method be method well known to those skilled in the art, have no special limitation, Bag filter preferably used in the present invention Device carries out, the solid impurities such as silica generated except dereaction；The ethyl alcohol takes off light rectification process and preferably uses ethyl alcohol de- light Rectifying column carries out；The feed inlet of the ethyl alcohol de-light rectification column is preferably placed at middle and upper part；It is preferred that the ethyl alcohol takes off light rectification process For atmospheric distillation；The temperature that the ethyl alcohol takes off light rectifying is preferably 77 DEG C~79 DEG C；It can be removed in ethyl alcohol by taking off light rectifying The light components such as ether, methanol, recycling after the light component of removing is condensable；The amount of removing light component is excellent when ethyl alcohol takes off light rectification process It is selected as taking off 1/5~1/25, more preferably the 1/10~1/15 of light rectifying material；When ethyl alcohol takes off light rectifying, the condensation temperature of tower top Preferably 30 DEG C~50 DEG C；The reflux ratio that the ethyl alcohol takes off light rectifying is preferably 1~10, and more preferably 4~8, further preferably for 6~ 8；Ethyl alcohol, which takes off after light rectification process, will preferably take off the ethyl alcohol after light rectification process after being adsorbed by drying processing, carry out the de- weight of ethyl alcohol After rectification process, high straight alcohol is obtained；The de- weight rectification process of the ethyl alcohol preferably uses ethyl alcohol to take off heavy distillation column and carries out；The second The feed inlet that alcohol takes off heavy distillation column is preferably placed at middle and lower part；The de- weight rectification process of the ethyl alcohol is preferably atmospheric distillation；It is described de- The temperature of weight rectification process is preferably 78 DEG C~80 DEG C；Propyl alcohol in ethyl alcohol, isobutanol, different can be removed by de- weight rectification process The heavy constituent of the heavy constituents such as amylalcohol, removing may be recovered；The amount that the ethyl alcohol takes off the heavy constituent removed when weight rectification process is excellent It is selected as 1/5~1/25, more preferably the 1/10~1/15 of de- rectifying material again；When ethyl alcohol takes off rectifying again, the temperature of overhead condensation Preferably 30 DEG C~50 DEG C；The reflux ratio of the de- rectifying again of the ethyl alcohol is preferably 1~10, and more preferably 4~8, further preferably for 6~ 8.The purity of the high straight alcohol obtained after de- weight rectification process is up to 5N or more.
The present invention takes off the water in the light component removed when light rectifying and technical grade dehydrated alcohol by using ethyl orthosilicate Reaction generates silica and ethyl alcohol, the moisture in ethanol raw material can be removed while improving ethyl alcohol utilization rate.
High purity silicon tetrachloride and high straight alcohol are mixed into row reactive distillation；The reactive distillation is preferably in reactive distillation device Middle progress；The reactive distillation device includes conversion zone and the rectifying section above conversion zone；The high purity silicon tetrachloride into Discharge position is preferably placed at the side-lower i.e. conversion zone of rectifying section；The feed entrance point of the high straight alcohol is preferably placed in rectifying section Portion；The molar ratio of high purity silicon tetrachloride and high straight alcohol is preferably 1:(4.0~4.8), more preferably 1:(4.3~4.5)；It is described Reactive distillation preferably carries out under the conditions of micro-positive pressure；The temperature of the reactive distillation is preferably 70 DEG C~90 DEG C, more preferably 77 DEG C~82 DEG C；The pressure of the reactive distillation is preferably 0.5~1.5bar, more preferably 0.8~1.2bar；The conversion zone is excellent Choosing is provided with helix(ribbon type) agitator；Blender can be such that material digs upwards when reaction, make wherein light component substance rising, especially Hydrogen chloride makes reaction be conducive to positive reaction direction and carries out, improve four so that the HCl separation for obtaining reaction, is discharged hydrogen chloride The reaction efficiency of silicon chloride and ethyl alcohol.To avoid material waste, the light component that reactive distillation generates is through gas-liquid separation, separation reaction The thick hydrogen chloride and liquid silicon tetrachloride generated, liquid silicon tetrachloride, which continues back in conversion zone, to be reacted.Reactive distillation obtains The ethyl orthosilicate arrived is enriched with since boiling point is higher in conversion zone bottom.The high purity silicon tetrachloride and the preferred side of high straight alcohol It feeds side and carries out reactive distillation；The feed flow rate of the high purity silicon tetrachloride preferably 100~200kg/h；The high straight alcohol Feed flow rate is preferably 130~260kg/h；Isothermal holding is preferably carried out after charging；The time of the isothermal holding is preferred For 30~60min, more preferably 40~50min；Fully reacting can be made by carrying out isothermal holding, can also remove free chlorine well Change hydrogen；After isothermal holding, pressure is preferably down to 0 or negative pressure, can more thoroughly remove free hydrogen chloride, is obtained slightly just Silester.
Thick ethyl orthosilicate is carried out decolorization adsorption processing to handle with alkaline adsorption；The decolorization adsorption processing preferably uses Active carbon carries out；The alkaline adsorption processing is preferably carried out using alkaline adsorption substance, is more preferably carried out using calcium oxide, through alkali Property adsorption treatment can thoroughly remove free hydrogen chloride while can also remove the moisture in thick ethyl orthosilicate.
Then it carries out taking off light rectifying；It is described to take off light rectifying and carried out preferably in de-light rectification column；Through decolorization adsorption handle with Treated that thick ethyl orthosilicate is preferably fed from the middle and upper part of de-light rectification column for alkaline adsorption；The temperature for taking off light rectifying is excellent It is selected as 95 DEG C~130 DEG C, more preferably 100 DEG C~120 DEG C；The pressure for taking off light rectifying is preferably -0.6~-1bar, and more Preferably -0.7~-0.9bar；The temperature of overhead condensation when taking off light rectifying is preferably 20 DEG C~40 DEG C；Take off returning for light rectifying Stream is further preferably 4~6 than preferably 1~10, more preferably 1~6；It can be removed in thick ethyl orthosilicate not by taking off light rectifying Ethyl alcohol, methyltriethoxysilane, methoxyl group triethoxysilane, triethoxychlorosilane, the triethoxysilicane alkyl of reaction Trimethylethoxysilane (form the trim,ethylchlorosilane of azeotropic with silicon tetrachloride and ethyl alcohol carries out esterification generation) etc. Light component since the main component in light component is ethyl alcohol, therefore carries out ethyl alcohol recycling after light component is condensed.
The ethyl orthosilicate after light rectifying will be taken off and carry out boron phosphorus absorption resin and adsorption of metal ions resin treatment；The boron It is preferably macropore chelating absorption resin that phosphorus, which adsorbs resin, the LSC-700, the MARATHON A of DOW of more preferably blue dawn science and technology；Institute Stating adsorption of metal ions resin is preferably macropore chelating absorption resin, the LSC-100 of more preferably blue dawn science and technology, DOW's MARATHON MSC；The ethyl orthosilicate taken off after light rectifying carries out boron phosphorus absorption resin and adsorption of metal ions resin treatment When flow velocity be preferably 1-4BV/H, more preferably 2.5BV/H；Resin and adsorption of metal ions resin treatment are adsorbed by boron phosphorus Can depth remove boron phosphorus and the impurity such as metal ion in ethyl orthosilicate.
De- rectifying again is finally carried out, high-purity ethyl orthosilicate is obtained.The de- rectifying again preferably in de- heavy distillation column into Row；When de- rectifying again, the ethyl orthosilicate after boron phosphorus adsorbs resin and adsorption of metal ions resin treatment is preferably in de- weight essence Evaporate the middle and lower part charging of tower；The temperature of the de- rectifying again is preferably 95 DEG C~130 DEG C, more preferably 100 DEG C~120 DEG C；Institute The pressure for stating de- rectifying again is preferably -0.6~-1bar, more preferably -0.7~-0.9bar；Tower top is cold when the de- rectifying again Solidifying temperature is preferably 20 DEG C~50 DEG C；The reflux ratio of de- rectifying again is preferably 1~10, and more preferably 1~6, further preferably for 4~ 6；Propyl-triethoxysilicane, ethyl orthosilicate dimer, positive silicic acid second in ethyl orthosilicate can be removed by de- rectifying again The heavy constituents such as ester tripolymer, these heavy constituents may be recovered；The ethyl orthosilicate that tower top obtains after de- rectifying again preferably also passes through High-purity ethyl orthosilicate is obtained after crossing condensation, compositional purity may be up to 5N or more, and the indexs such as metal ion reach 9N.
The present invention starts with from the purifying of raw material, changes the ethyl orthosilicate produced in the past with the silicon tetrachloride of polysilicon by-product Impurity is more, and easy purification does not obtain the process route of high-purity ethyl orthosilicate, and fairly simple process flow can obtain high pure Silester also improves the application range of product while the industries such as solution polysilicon silicon tetrachloride more than needed and adds Value.
To improve value-added content of product, the present invention preferably cools down thick hydrogen chloride obtained in step S1), it is dry to adsorb After dry, compression successively carries out dehydrogenation rectifying and de- rectifying again, obtains high-purity hydrogen chloride.
Thick hydrogen chloride is cooled down；The temperature of the cooling is preferably 5 DEG C~20 DEG C, more preferably 10 DEG C~15 DEG C； The high-boiling-point impurities such as silicon tetrachloride in thick hydrogen chloride can be removed by condensation；The cold source of the cooling preferably freezes unit, cold Matchmaker is ethylene glycol；Its pressure is preferably 1.1~1.2bar.
Thick hydrogen chloride after cooling is adsorbed by drying, and is removed moisture therein, is then compressed；The pressure of the compression is excellent It is selected as 1.2~1.35MPa, more preferably 1.25~1.3MPa, is further preferably 1.28MPa；The temperature of the compression is preferably 40 DEG C~50 DEG C, more preferably 45 DEG C.
After compression, preferably compressed hydrogen chloride is adsorbed by drying for the second time, is pre-chilled；The pre-cooling afterchlorinate hydrogen Pressure is preferably 1.18~1.24MPa, more preferably 1.2~1.23MPa, is further preferably 1.21MPa；The temperature of afterchlorinate hydrogen is pre-chilled Preferably -30 DEG C~-24 DEG C, more preferably -27 DEG C of degree.
Hydrogen chloride after pre-cooling is carried out to take off light rectifying and de- rectifying again；It is described to take off light rectifying preferably in hydrogen chloride lightness-removing column Middle progress；Hydrogen chloride after pre-cooling is preferably fed in the middle and upper part of hydrogen chloride lightness-removing column；The pressure for taking off light rectifying is preferably 1.2~1.24MPa, more preferably 1.22MPa；Preferably -24 DEG C~-28 DEG C of the temperature for taking off light rectifying, more preferably -26 ℃；The pressure of the lightness-removing column overhead condensation is preferably 1.18~1.22MPa；The temperature of overhead condensation is preferably -29 DEG C~-30 DEG C, more preferably -29.4 DEG C；Reflux ratio is preferably 0.5~3, and more preferably 1~2；By taking off light rectifying except in de-chlorine hydride The light components impurity such as hydrogen and nitrogen；The de- rectifying again preferably carries out in hydrogen chloride weight-removing column；Chlorination after taking off light rectifying Hydrogen is preferably fed in the middle and lower part of hydrogen chloride weight-removing column；The pressure of the de- rectifying again is preferably 1.2~1.24MPa, more preferably For 1.22MPa；The temperature of the de- rectifying again is preferably -24 DEG C~-28 DEG C, more preferably -26 DEG C；It can be removed by de- rectifying again Remove CO2、SiCl4Etc. heavy constituents；The temperature of overhead condensation is preferably -26~-27 DEG C when the de- rectifying again, and more preferably -26.5 ℃；Pressure is preferably 1.19~1.21MPa, more preferable 1.2MPa；Reflux ratio is preferably 1~5, and more preferably 3~4.
After de- rectifying again, high-purity 5N hydrogen chloride liquid can be obtained in tower top.
The present invention compared with hydrochloric acid, deepens technique road with the by-product obtained using silicon tetrachloride production ethyl orthosilicate in the past Line obtains the hydrogen chloride of electron level, improves value-added content of product.
The present invention, as raw material, makes moisture content pole in the reaction system using high purity silicon tetrachloride and high straight alcohol It is few, the polymerization reaction of the generation of side reaction, especially ethyl orthosilicate is reduced, the generation of silester polymer can be reduced, subtracted The light pressure of purification process, improves the yield of high-purity ethyl orthosilicate.
And since high-purity ethyl orthosilicate is to the more demanding of boron phosphorus and metal ion, thus it is pure in raw material silicon tetrachloride During change, using boron phosphorus absorption resin and adsorption of metal ions resin, the impurity such as boron phosphorus and metal ion are removed, and just Boron phosphorus absorption resin and adsorption of metal ions resin are reused in silester purifying process, depth removes boron phosphorus and metal The impurity such as ion improve to obtain the purity of high-purity ethyl orthosilicate.
The present invention also provides a kind of production systems of high-purity ethyl orthosilicate, comprising:
High purity silicon tetrachloride storage tank；
High straight alcohol storage tank；
Reactive distillation device；The high purity silicon tetrachloride storage tank is connected with reactive distillation device respectively with high straight alcohol storage tank；
Decolorization adsorption device；The decolorization adsorption device is connected with reactive distillation device；
Alkaline adsorption device；Alkaline matter is provided in the alkaline adsorption device；The alkaline adsorption device and decolorization adsorption device It is connected；
De-light rectification column；The dehydrogenation rectifying column is connected with alkaline adsorption device；
Boron phosphorus absorber；Boron phosphorus absorption resin is provided in the boron phosphorus absorber；The boron phosphorus absorber and dehydrogenation essence Tower is evaporated to be connected；
Adsorption of metal ions device；Adsorption of metal ions resin is provided in the adsorption of metal ions device；The metal from Sub- absorber is connected with boron phosphorus absorber；
De- heavy distillation column；The de- heavy distillation column is connected with adsorption of metal ions device.
Referring to FIG. 1 to FIG. 5, Fig. 1 and Fig. 2 is the structural representation of high-purity ethyl orthosilicate production system provided by the invention Figure, wherein V02 is high straight alcohol storage tank, and P07 is high straight alcohol feed pump, and V05 is high purity silicon tetrachloride storage tank, and P08 is high-purity Silicon tetrachloride feeding pump, R01 are reactive distillation device, and P09 is reactive distillation device discharging pump, and S04 is decolorization adsorption device, and V07 is thick Ethyl orthosilicate storage tank, F02 are gas-liquid separator, and C01 is corrosion resistant fan, and V08 is thick hydrogen chloride storage tank, and P10 is positive silicic acid Ethyl ester de-light rectification column feed pump, S05 are alkaline adsorption device, and T05 is ethyl orthosilicate de-light rectification column, and E09 is positive silicic acid second The reboiler of ester de-light rectification column, E10 are the condenser of ethyl orthosilicate de-light rectification column, and P11 is the de- light essence of ethyl orthosilicate The discharging pump of tower is evaporated, S06 is boron phosphorus absorber, and S07 is adsorption of metal ions device, and T06 is that ethyl orthosilicate takes off heavy distillation column, E11 is the reboiler that ethyl orthosilicate takes off heavy distillation column, and E12 is the condenser that ethyl orthosilicate takes off heavy distillation column, and P12 is positive silicon Acetoacetic ester takes off the discharging pump of heavy distillation column, and V09 is high-purity ethyl orthosilicate storage tank, and V10 is ethyl orthosilicate accumulator tank；Fig. 3 is The structural schematic diagram of high purity silicon tetrachloride production system, wherein V04 is silicon tetrachloride storage tank, and P04 is that silicon tetrachloride takes off light rectifying The feed pump of tower, T03 are silicon tetrachloride de-light rectification column, and E05 is the reboiler of silicon tetrachloride de-light rectification column, and E06 is tetrachloro The condenser of SiClx de-light rectification column, P05 are the discharging pump of silicon tetrachloride de-light rectification column, and S02 is the second boron phosphorus absorber, S03 is the second adsorption of metal ions device, and T04 is that silicon tetrachloride takes off heavy distillation column, and E07 is that silicon tetrachloride takes off boiling again for heavy distillation column Device, E08 are the condenser that silicon tetrachloride takes off heavy distillation column, and P06 is the discharging pump that silicon tetrachloride takes off heavy distillation column, and V05 is high-purity Silicon tetrachloride storage tank, V06 are silicon tetrachloride accumulator tank；Fig. 4 is the structural representation of high straight alcohol production system provided by the invention Figure, wherein V01 is ethanol raw material storage tank, and F01 is filter, and P01 is the feed pump of ethyl alcohol de-light rectification column, and E01 is de- for ethyl alcohol The reboiler of light rectifying column, E02 are the condenser of ethyl alcohol de-light rectification column, and P02 is the discharging pump of ethyl alcohol de-light rectification column, S01 For adsorption dehumifier, T02 is that ethyl alcohol takes off heavy distillation column, and E03 is the reboiler that ethyl alcohol takes off heavy distillation column, and E04 is the de- weight essence of ethyl alcohol The condenser of tower is evaporated, P03 is the discharging pump that ethyl alcohol takes off heavy distillation column, and V02 is high straight alcohol storage tank, and V03 is that ethyl alcohol recycles storage tank； Fig. 5 is the structural schematic diagram of high-purity hydrogen chloride production system provided by the invention, and wherein V08 is thick hydrogen chloride storage tank, and C02 is resistance to Corrode blower, V11 is surge tank, and E13 is graphite condenser, and S08 is hydrogen chloride adsorption dehumifier, and C03 is compressor, and S09 is Second hydrogen chloride adsorption dehumifier, E14 are forecooler, and T07 is hydrogen chloride de-light rectification column, and E15 is the condensation of de-light rectification column Device, T08 are that hydrogen chloride takes off heavy distillation column, and E16 is the condenser that hydrogen chloride takes off heavy distillation column, and P13 is that hydrogen chloride takes off heavy distillation column Discharging pump, V12 be high-purity hydrogen chloride storage tank, V13 be hydrogen chloride accumulator tank.
According to the present invention, it is also preferable to include high purity silicon tetrachloride production systems for the production system；The high purity silicon tetrachloride Production system includes: silicon tetrachloride de-light rectification column；Second boron phosphorus absorber；Boron phosphorus is provided in the second boron phosphorus absorber Adsorb resin；The second boron phosphorus absorber is connected with silicon tetrachloride de-light rectification column；Second adsorption of metal ions device；It is described Adsorption of metal ions resin is provided in second adsorption of metal ions device；The second adsorption of metal ions device and the second boron phosphorus are inhaled Adnexa is connected；Silicon tetrachloride takes off heavy distillation column；The silicon tetrachloride takes off heavy distillation column and is connected with the second adsorption of metal ions device It is logical；The discharge port that the silicon tetrachloride takes off heavy distillation column is connected with high purity silicon tetrachloride storage tank.
In the present invention, it is also preferable to include silicon tetrachloride raw material storage tanks for the high purity silicon tetrachloride production system；Described four Silicon chloride raw material storage tank is connected with silicon tetrachloride de-light rectification column, more preferably passes through feed pump and silicon tetrachloride de-light rectification column It is connected, is further preferably connected by feed pump with the middle and upper part of silicon tetrachloride de-light rectification column.
It is also preferable to include silicon tetrachloride recycling cans for the high purity silicon tetrachloride production system；The silicon tetrachloride takes off light rectifying Tower takes off heavy distillation column with silicon tetrachloride and is connected respectively with silicon tetrachloride accumulator tank, de- for recycling silicon tetrachloride de-light rectification column The light component and silicon tetrachloride removed take off the heavy constituent of heavy distillation column removing.
The tower bottom that the silicon tetrachloride takes off heavy distillation column is provided with reboiler, and tower top is provided with condenser, the de- heavy essence It evaporates tower and is connected by condenser with high purity silicon tetrachloride storage tank；Partially extraction is used as production to the substance of rectifying after condenser condenses Product are partly refluxed to silicon tetrachloride and take off in heavy distillation column.
It is also preferable to include high straight alcohol production systems for high-purity ethyl orthosilicate production system provided by the invention；It is described high-purity Ethyl alcohol production system preferably includes ethanol raw material storage tank；The ethanol raw material storage tank is connected with de-light rectification column；Take off light rectifying The light component of tower removing enters in ethanol raw material storage tank reacts with industrial alcohol therein, to remove the moisture in ethyl alcohol；Filtering Device；The filter is connected with ethanol raw material storage tank；The filter is filter well known to those skilled in the art, Special limitation is had no, is preferably cloth envelop collector in the present invention；Ethyl alcohol de-light rectification column；The ethyl alcohol de-light rectification column and mistake Filter is connected, and the middle and upper part of preferred alcohol de-light rectification column is connected (the i.e. feed inlet of ethyl alcohol de-light rectification column with filter Positioned at middle and upper part)；Adsorption dehumifier；The adsorption dehumifier is connected with ethyl alcohol de-light rectification column；Ethyl alcohol takes off heavy distillation column；Institute It states the de- heavy distillation column of ethyl alcohol to be connected with adsorption dehumifier, the middle and lower part that preferred alcohol takes off heavy distillation column is connected with adsorption dehumifier Logical (feed inlet that i.e. ethyl alcohol takes off heavy distillation column is located at middle and lower part)；The ethyl alcohol takes off heavy distillation column and is connected with high straight alcohol storage tank It is logical, preferably it is connected by ethyl alcohol condenser with high straight alcohol storage tank.
According to the present invention, it is also preferable to include ethyl alcohol accumulator tanks for the high straight alcohol production system；The ethyl alcohol takes off light rectifying Tower takes off heavy distillation column with ethyl alcohol and is connected respectively with ethyl alcohol accumulator tank, and the light component removed in ethyl alcohol de-light rectification column and ethyl alcohol are de- The heavy constituent of heavy distillation column removing is recycled by ethyl alcohol accumulator tank.
In the present invention, the reactive distillation device includes conversion zone and the rectifying section for being located at conversion zone top；It is described high-purity Silicon tetrachloride storage tank is preferably connected with conversion zone, more preferably passes through high purity silicon tetrachloride feed pump；The high straight alcohol storage tank It is preferred that being connected with rectifying section, more preferably it is connected by high straight alcohol feed pump with rectifying section；The conversion zone is preferably provided with There is helix(ribbon type) agitator.
The decolorization adsorption device is preferably connected with the conversion zone of reactive distillation device；It is preferably provided in the decolorization adsorption device Active charcoal.
Ethyl orthosilicate after decolorization enters in alkaline adsorption device；Basic species are provided in the alkaline adsorption device Matter is preferably provided with calcium oxide.Alkaline matter is also adsorbed by drying while free hydrogen chloride in removing ethyl orthosilicate Remove moisture therein.
Through alkaline adsorption device, treated that ethyl orthosilicate enters in de-light rectification column；The alkaline adsorption device preferably with it is de- The middle and upper part of light rectifying column is connected (i.e. the feed inlet of de-light rectification column is located at middle and upper part)；The tower top of the de-light rectification column with Ethanol raw material storage tank is connected；The tower bottom of the de-light rectification column is provided with reboiler, and tower top is provided with condenser；It is described de- light Rectifying column is connected by condenser with ethanol raw material storage tank, i.e., the condensed material parts of condenser are as light component extraction portion Reflux is divided to continue rectifying.
The tower bottom of the de-light rectification column is connected with boron phosphorus absorber；The absorption of boron phosphorus is provided in the boron phosphorus absorber Resin.
The boron phosphorus absorber is connected with adsorption of metal ions device；Be provided in the adsorption of metal ions device metal from Son absorption resin.
The adsorption of metal ions device is connected with de- heavy distillation column, is preferably connected with the middle and lower part of de- heavy distillation column, The feed inlet of i.e. de- heavy distillation column is located at middle and lower part.
It is also preferable to include high-purity ethyl orthosilicate storage tanks for high-purity ethyl orthosilicate production system provided by the invention；The height Pure silester storage tank is connected with de- heavy distillation column, is preferably connected with the tower top of de- heavy distillation column；The de- rectifying again The tower bottom of tower is provided with reboiler, and tower top is provided with condenser, and the material of rectifying is branched to high-purity by condenser condensation rear portion Partial reflux continues rectifying in ethyl orthosilicate storage tank.
It is also preferable to include ethyl orthosilicate accumulator tanks for high-purity ethyl orthosilicate production system provided by the invention；The positive silicon Acetoacetic ester accumulator tank is connected with de- heavy distillation column, is preferably connected with the tower bottom of de- heavy distillation column.
According to the present invention, it is also preferable to include high-purity hydrogen chloride production systems；The high-purity hydrogen chloride production system includes: stone Black condenser；The graphite condenser is connected with reactive distillation device；Hydrogen chloride adsorption dehumifier；The hydrogen chloride is adsorbed by drying Device is connected with graphite condenser；Compressor；The compressor is connected with hydrogen chloride adsorption dehumifier；Hydrogen chloride takes off light rectifying Tower；The hydrogen chloride de-light rectification column is connected with compressor；Hydrogen chloride takes off heavy distillation column；The hydrogen chloride take off heavy distillation column with Hydrogen chloride de-light rectification column is connected.
High-purity hydrogen chloride production system provided by the invention preferably includes thick hydrogen chloride storage tank；The graphite condenser passes through Thick hydrogen chloride storage tank is connected with reactive distillation device, is preferably connected by thick hydrogen chloride storage tank with the rectifying section of reactive distillation device It is logical.
It is also preferable to include gas-liquid separators；The thick hydrogen chloride storage tank is connected by gas-liquid separator with reactive distillation device Logical, through gas-liquid separator gas-liquid separation, the silicon tetrachloride of liquid returns in reactive distillation device that the reaction was continued, and thick hydrogen chloride then enters In thick hydrogen chloride storage tank.
The gas-liquid separator preferably passes through corrosion resistant fan and is connected with thick hydrogen chloride storage tank.
The thick hydrogen chloride storage tank preferably passes through surge tank and is connected with graphite condenser.
The graphite condenser is connected with hydrogen chloride adsorption dehumifier；De-chlorine hydride is removed by hydrogen chloride adsorption dehumifier In moisture.
The hydrogen chloride adsorption dehumifier is connected with compressor, is compressed using compressor to hydrogen chloride.
It is also preferable to include the second hydrogen chloride adsorption dehumifiers for high-purity hydrogen chloride production system provided by the invention；Described second Hydrogen chloride Dry Absorber is connected with compressor, and the water in de-chlorine hydride is further removed using the second hydrogen chloride adsorption dehumifier Point.
It is also preferable to include forecoolers for high-purity hydrogen chloride production system provided by the invention；The forecooler and the second hydrogen chloride Drier is connected.Hydrogen chloride is cooled down in forecooler.
The forecooler is connected with hydrogen chloride de-light rectification column, is preferably connected with the middle and upper part of hydrogen chloride de-light rectification column Logical, i.e., the feed inlet of hydrogen chloride de-light rectification column is located at middle and upper part.
The hydrogen chloride de-light rectification column takes off heavy distillation column with hydrogen chloride and is connected, and preferably takes off heavy distillation column with hydrogen chloride Middle and lower part is connected, i.e., the feed inlet that hydrogen chloride takes off heavy distillation column is located at middle and lower part.
According to the present invention, it is also preferable to include high-purity hydrogen chloride storage tank, the high-purity hydrogen chloride storage tank and the de- weight essence of hydrogen chloride Tower is evaporated to be connected.
According to the present invention, it is also preferable to include chlorination hydrogen retrieval storage tank, the hydrogen chloride de-light rectification column and the de- weight of hydrogen chloride Rectifying column is connected with chlorination hydrogen retrieval storage tank respectively, for recycling the light component and hydrogen chloride of the removing of hydrogen chloride de-light rectification column The heavy constituent of de- heavy distillation column removing.
In order to further illustrate the present invention, with reference to embodiments to a kind of high-purity ethyl orthosilicate provided by the invention Preparation method and production system are described in detail.
Reagent used in following embodiment is commercially available；Boron phosphorus used absorption resin is blue dawn science and technology in embodiment LSC-700 macropore chelating absorption resin；Adsorption of metal ions resin is the LSC-100 macropore chelating absorption resin of blue dawn science and technology.
Embodiment
Material (predominantly ethyl alcohol, the band that outsourcing industrial alcohol and de-light rectification column T05 overhead condenser E10 are condensed Trimethylethoxysilane, the methyl for having a small amount of ethyl orthosilicate and being generated with the trim,ethylchlorosilane of silicon tetrachloride azeotropic The impurity such as triethoxysilane) enter ethanol raw material storage tank V01, ethyl orthosilicate, trimethylethoxysilane, three ethoxy of methyl Base silane etc. is reacted with the water in industrial alcohol, generates silica and ethyl alcohol, and to remove the water in ethanol raw material, ethyl alcohol is former Expect that storage tank V01 removes the solid impurities such as silica through cloth envelop collector F01, then feeds delivery pump P01 from ethyl alcohol through ethyl alcohol The middle and upper part of de-light rectification column T01 tower is fed, and carries out atmospheric distillation, and rectification temperature is preferably 77 DEG C~79 DEG C, is removed in ethyl alcohol Ether, methanol lighter component, lighter component after overhead condenser condenses enter ethyl alcohol accumulator tank V03, ethyl alcohol de-light rectification column T01 It is preferably the 1/5~1/25 of rectifying material, more preferably 1/10~1/15 that the amount of low boiling component is removed when rectifying.Ethyl alcohol is de- light Rectifying column T01 kettle material part is after ethyl alcohol de-light rectification column T01 discharging pump P02 is delivered to adsorption dehumifier F01 drying and dehydrating Heavy distillation column T02 is taken off into ethyl alcohol, is fed from the middle and lower part of tower, atmospheric distillation is carried out, rectification temperature is preferably 78 DEG C~80 DEG C, Heavy components, the heavy components such as propyl alcohol, isobutanol, isoamyl alcohol in removing ethyl alcohol take off heavy distillation column discharging pump P03 through ethyl alcohol and enter second Alcohol accumulator tank V03, it is preferably the 1/5 of rectifying material that ethyl alcohol, which removes the amount of low (height) boiling point component when taking off heavy distillation column T02 rectifying, ~1/25, more preferably 1/10~1/15.High straight alcohol takes off heavy distillation column condenser E04 to high straight alcohol storage tank V02 through ethyl alcohol, The high-purity ethyl alcohol component purity purified at this time is 5N or more.
The by-produced tetrachlorosilane of polysilicon or silane coupling agent is defeated through silicon tetrachloride feeding from silicon tetrachloride raw material storage tank V04 It send pump P04 to feed from the middle and upper part of silicon tetrachloride de-light rectification column T03 tower, carries out compression rectification, rectification temperature is preferably 56 DEG C ~108 DEG C, most preferably 70 DEG C~95 DEG C；Pressure is preferably 0~3.0bar, more preferably 0.5~2bar；Remove silicon tetrachloride In the lighter components such as trichlorosilane, boron chloride, dichlorosilane, lighter component enters silicon tetrachloride after overhead condenser condenses Accumulator tank V06, remove when silicon tetrachloride de-light rectification column T03 rectifying low boiling component amount be preferably rectifying material 1/5~ 1/12, more preferably 1/7~1/10.De-light rectification column T03 kettle material part is defeated through silicon tetrachloride de-light rectification column discharging pump P05 It send to the second boron phosphorus absorber S02 and the second adsorption of metal ions device S03, removes boron phosphorus and the metal ion etc. in silicon tetrachloride Impurity takes off heavy distillation column T04 subsequently into silicon tetrachloride, feeds from the middle and lower part of tower, carries out compression rectification, and rectification temperature is preferred It is 56 DEG C~110 DEG C, most preferably 70 DEG C~95 DEG C；Pressure is preferably 0~3.0bar, more preferably 0.5~2bar, removing four The heavy components such as phosphorus oxychloride, phosphorus trichloride, phosphorus pentachloride, dimethyldichlorosilane, methyl trichlorosilane in silicon chloride, recombination Part takes off heavy distillation column discharging pump P06 through silicon tetrachloride and enters silicon tetrachloride accumulator tank V06, and silicon tetrachloride takes off heavy distillation column T04 essence The amount that low (height) boiling point component is removed when evaporating is preferably the 1/5~1/12 of rectifying material, more preferably 1/7~1/10.High-purity four Silicon chloride takes off heavy distillation column condenser E08 to high purity silicon tetrachloride storage tank V05 through silicon tetrachloride, high-purity four chlorination purified at this time Silicon (containing the trim,ethylchlorosilane with its azeotropic) component purity is 5N or more.
It pumps P08 from the reacted silicon tetrachloride feeding of high purity silicon tetrachloride storage tank V05 to feed to reactive distillation device R01, charging Position is the side-lower of rectifying section；Then from the high reacted ethyl alcohol feed pump P07 of straight alcohol storage tank V02 to reactive distillation device R01 Charging, feed entrance point are in the middle part of rectifying section.Micro-positive pressure reaction is carried out, reactor helix(ribbon type) agitator, helical-ribbon type stirs when reaction It is next that device digs material upwards, makes the wherein rising of lighter component substance, especially hydrogen chloride.Reaction pressure preferably 0.5~1.5bar, More preferable 0.8~1.2bar；Preferably 70~90 DEG C of reaction temperature, more preferably 77~82 DEG C；SiCl4With C2H5The molar ratio of OH It is preferred that 1:4.0 to 1:4.8, more preferable 1:4.3 to 1:4.5.React the hydrogen chloride generated through gas-liquid separator F02, gas-liquid separation, The silicon tetrachloride of liquid is left in reactor that the reaction was continued, and the thick hydrogen chloride after separation is compressed to thick chlorine through corrosion resistant fan C01 Change hydrogen storage tank V08.Obtained ethyl orthosilicate is reacted since boiling point is higher, is enriched in reactor bottom, is kept the temperature after charging It is preferred that 30~60min, more preferable 40~50min make fully reacting, and free hydrogen chloride is removed well, after reaction Decompression power is down to 0 or negative pressure, the free hydrogen chloride of removing more thoroughly.After reaction by reactive distillation device R01 it is thick just Silester carries out decoloration purifying through delivery pump P09 to active carbon decolorization adsorption device S04, subsequently into thick ethyl orthosilicate storage tank V07.Thick ethyl orthosilicate, through feeding delivery pump P10, is alkalinity through calcium oxide depickling absorber from thick ethyl orthosilicate storage tank V07 Absorber S05 thoroughly removes free hydrogen chloride, feeds from the middle and upper part of ethyl orthosilicate de-light rectification column T05 tower to it, The temperature of rectifying is preferably 95 DEG C~130 DEG C, most preferably 100 DEG C~120 DEG C；Pressure is preferably -0.6~-1.0bar, more excellent It is selected as -0.7~-0.9bar；The temperature of tower top when taking off light rectifying is preferably 20 DEG C~40 DEG C；The reflux ratio for taking off light rectifying is excellent Select 1~10, more preferably 4~6；Unreacted ethyl alcohol, methyltriethoxysilane, methoxyl group three in removing ethyl orthosilicate Ethoxysilane, triethoxychlorosilane, triethoxysilane and trimethylethoxysilane (form azeotropic with silicon tetrachloride Trim,ethylchlorosilane and ethyl alcohol carry out esterification generation) etc. lighter components.Since the main component in lighter component is ethyl alcohol, therefore Lighter component is condensed through overhead condenser E10 to ethanol raw material storage tank V01, ethyl alcohol recycling is carried out.Ethyl orthosilicate takes off light rectifying Tower T05 kettle material is delivered to boron phosphorus resin adsorption device F02 and metal ion through ethyl orthosilicate de-light rectification column discharging pump P11 Resin adsorption device F03, depth remove the impurity such as boron phosphorus and metal ion, take off heavy distillation column T06 subsequently into ethyl orthosilicate, Through feeding from the middle and lower part of tower, the temperature of rectifying is preferably 95 DEG C~130 DEG C, most preferably 100 DEG C~120 DEG C；Pressure is preferred For -0.6~-1.0bar, more preferably -0.7~-0.9bar；The temperature of tower top is preferably 20 DEG C -50 DEG C when de- rectifying again；It is de- The reflux ratio of rectifying is preferably 1~10 again, and more preferably 4~6；Remove the propyl-triethoxysilicane, just in ethyl orthosilicate The heavy components such as silester dimer, ethyl orthosilicate tripolymer, heavy component discharge through tower bottom discharging pump P12 to ethyl orthosilicate Accumulator tank V10, tower top condense to obtain high-purity ethyl orthosilicate through condenser E12, and component purity may be up to 5N or more, metal from The indexs such as son reach 9N；In terms of silicon tetrachloride, the yield of high-purity ethyl orthosilicate is up to 80% or more.
Material carries out being delivered to surge tank V11, graphite condenser through corrosion resistant fan C02 in thick hydrogen chloride storage tank V08 E13, preferably 5 DEG C~20 DEG C of condensation temperature, more preferable 10 DEG C~15 DEG C, condensation removes the high-boiling-point impurities such as silicon tetrachloride, cold source To freeze unit, pressure preferably 1.1~1.2bar is purified through hydrogen chloride adsorption dehumifier S08, is compressed through compressor C03, pressure It is preferred that 1.2~1.35MPa, more preferable 1.28MPa, preferably 40~50 DEG C of temperature, more preferable 45 DEG C；Thick hydrogen chloride passes through after compression Second hydrogen chloride adsorption dehumifier S09 is further purified, and subsequently into forecooler E14, cools down, material after pre-cooling Pressure preferably 1.18~1.24MPa, more preferable 1.21MPa, temperature is -30~-24 DEG C preferred, and more preferably -27 DEG C；Enter after pre-cooling Hydrogen chloride de-light rectification column carries out rectifying, the charging of tower middle and upper part, pressure preferably 1.2~1.24MPa, more preferable 1.22MPa, temperature It is preferred that -24~-28 DEG C, more preferably -26 DEG C, overhead condenser pressure preferably 1.18~1.22MPa, more preferable 1.2MPa, temperature It is preferred that -29~-30 DEG C, more preferably -29.7 DEG C, reflux ratio 0.5~3, more preferably 1~2, overhead extraction hydrogen, nitrogen etc. are light Component impurity；Tower reactor, which discharges, takes off heavy distillation column T08, the charging of tower middle and lower part to hydrogen chloride；Tower reactor pressure preferably 1.2~1.24MPa, More preferable 1.22MPa, preferably -24~-28 DEG C of temperature, more preferably -26 DEG C, tower reactor produces CO2、SiCl4Equal heavy components；Tower top is cold Condenser pressure preferably 1.19~1.21MPa, more preferable 1.2MPa, temperature is -26~-27 DEG C preferred, and more preferably -26.5 DEG C, reflux Than 1~5, more preferably 3~4, condensation obtains high-purity 5N electronic grade hydrogen chloride liquid, condensed hydrogen chloride to high-purity hydrogen chloride Storage tank is collected.In terms of silicon tetrachloride, the yield of high-purity hydrogen chloride is up to 70% or more.
Embodiment 1
Material (predominantly ethyl alcohol, the band that outsourcing industrial alcohol and de-light rectification column T05 overhead condenser E10 are condensed Trimethylethoxysilane, the methyl for having a small amount of ethyl orthosilicate and being generated with the trim,ethylchlorosilane of silicon tetrachloride azeotropic The impurity such as triethoxysilane) enter ethanol raw material storage tank V01, ethyl orthosilicate, trimethylethoxysilane, three ethoxy of methyl Base silane etc. is reacted with the water in industrial alcohol, generates silica and ethyl alcohol, and to remove the water in ethanol raw material, ethyl alcohol is former Expect that storage tank V01 removes the solid impurities such as silica through cloth envelop collector F01, then feeds delivery pump P01 from ethyl alcohol through ethyl alcohol The middle and upper part of de-light rectification column T01 tower is fed, and carries out atmospheric distillation, and rectification temperature is 78 DEG C, removes ether, methanol in ethyl alcohol Lighter component, lighter component enter ethyl alcohol accumulator tank V03 after overhead condenser condenses, and when ethyl alcohol de-light rectification column T01 rectifying removes The amount of low boiling component is preferably the 1/10 of rectifying material；The reflux ratio that ethyl alcohol takes off light rectifying is 6.Ethyl alcohol de-light rectification column T01 Kettle material part is de- into ethyl alcohol after ethyl alcohol de-light rectification column T01 discharging pump P02 is delivered to adsorption dehumifier F01 drying and dehydrating Heavy distillation column T02 is fed from the middle and lower part of tower, carries out atmospheric distillation, and rectification temperature is 79 DEG C, removes the propyl alcohol, different in ethyl alcohol The heavy components such as butanol, isoamyl alcohol, heavy component take off heavy distillation column discharging pump P03 through ethyl alcohol and enter ethyl alcohol accumulator tank V03, the de- weight of ethyl alcohol It is preferably the 1/10 of rectifying material that the amount of high boiling component is removed when rectifying column T02 rectifying；The reflux ratio of the de- rectifying again of ethyl alcohol is 6.High straight alcohol takes off heavy distillation column condenser E04 to high straight alcohol storage tank V02 through ethyl alcohol, and the high-purity ethyl alcohol component purified at this time is pure Degree is 5N or more.
The by-produced tetrachlorosilane of polysilicon or silane coupling agent is defeated through silicon tetrachloride feeding from silicon tetrachloride raw material storage tank V04 It send pump P04 to feed from the middle and upper part of silicon tetrachloride de-light rectification column T03 tower, carries out compression rectification, rectification temperature is 89 DEG C；Reflux Than being 6；Pressure is 1.5bar；The lighter components such as trichlorosilane, boron chloride, dichlorosilane in removing silicon tetrachloride, light group Enter silicon tetrachloride accumulator tank V06 part after overhead condenser condenses, when silicon tetrachloride de-light rectification column T03 rectifying removes low boiling The amount of point component is preferably the 1/10 of rectifying material.De-light rectification column T03 kettle material part goes out through silicon tetrachloride de-light rectification column Material pump P05 is delivered to the second boron phosphorus absorber S02 and the second adsorption of metal ions device S03, boron phosphorus in removing silicon tetrachloride and The impurity such as metal ion take off heavy distillation column T04 subsequently into silicon tetrachloride, feed from the middle and lower part of tower, carry out compression rectification, essence Evaporating temperature is 89 DEG C；Pressure is 1.5bar, reflux ratio 6；Remove phosphorus oxychloride in silicon tetrachloride, phosphorus trichloride, phosphoric The heavy components such as phosphorus, dimethyldichlorosilane, methyl trichlorosilane, heavy component through silicon tetrachloride take off heavy distillation column discharging pump P06 into Enter silicon tetrachloride accumulator tank V06, it is preferably rectifying object that silicon tetrachloride, which removes the amount of high boiling component when taking off heavy distillation column T04 rectifying, The 1/10 of material.High purity silicon tetrachloride takes off heavy distillation column condenser E08 to high purity silicon tetrachloride storage tank V05 through silicon tetrachloride, at this time High purity silicon tetrachloride (containing the trim,ethylchlorosilane with its azeotropic) the component purity of purifying is 5N or more.
It pumps P08 from the reacted silicon tetrachloride feeding of high purity silicon tetrachloride storage tank V05 to feed to reactive distillation device R01, charging Position is the side-lower of rectifying section；Then from the high reacted ethyl alcohol feed pump P07 of straight alcohol storage tank V02 to reactive distillation device R01 Charging, feed entrance point are in the middle part of rectifying section.Micro-positive pressure reaction is carried out, reactor helix(ribbon type) agitator, helical-ribbon type stirs when reaction It is next that device digs material upwards, makes the wherein rising of lighter component substance, especially hydrogen chloride.Reaction pressure is 1.2bar；Reaction temperature Degree is 82 DEG C；SiCl4With C2H5The molar ratio of OH is 1:4.5.The hydrogen chloride generated is reacted through gas-liquid separator F02, gas-liquid point It is left in reactor that the reaction was continued from, the silicon tetrachloride of liquid, the thick hydrogen chloride after separation is compressed to slightly through corrosion resistant fan C01 Hydrogen chloride storage tank V08.Obtained ethyl orthosilicate is reacted since boiling point is higher, is enriched in reactor bottom, is protected after charging Warm 50min makes fully reacting, and removes free hydrogen chloride well, depressurizes power after reaction and is down to 0 (gauge pressure), more thorough The free hydrogen chloride of the removing at bottom.After reaction by the thick ethyl orthosilicate in reactive distillation device R01 through delivery pump P09 to work Property carbon decoloring absorber S04 carries out decoloration purifying, subsequently into thick ethyl orthosilicate storage tank V07.Thick ethyl orthosilicate is from slightly just Silester storage tank V07, through calcium oxide depickling absorber, that is, alkaline adsorption device S05, thoroughly removes trip through feeding delivery pump P10 From hydrogen chloride, fed from the middle and upper part of ethyl orthosilicate de-light rectification column T05 tower to it, the temperature of rectifying is 110 DEG C；Pressure For -0.9bar；The temperature of tower top when taking off light rectifying is preferably 20 DEG C；Take off the reflux ratio 6 of light rectifying；Remove ethyl orthosilicate In unreacted ethyl alcohol, methyltriethoxysilane, methoxyl group triethoxysilane, triethoxychlorosilane, triethoxy Silane and trimethylethoxysilane (form the trim,ethylchlorosilane of azeotropic with silicon tetrachloride and ethyl alcohol carry out esterification generation ) etc. lighter components.Since the main component in lighter component is ethyl alcohol, therefore lighter component is condensed through overhead condenser E10 to ethyl alcohol Raw material storage tank V01 carries out ethyl alcohol recycling.Ethyl orthosilicate de-light rectification column T05 kettle material takes off light rectifying through ethyl orthosilicate Tower discharging pump P11 is delivered to boron phosphorus resin adsorption device F02 and metal ion resin adsorption device F03, and depth removes boron phosphorus and gold Belong to the impurity such as ion, takes off heavy distillation column T06, the middle and lower part charging of Jing Congta subsequently into ethyl orthosilicate, the temperature of rectifying is 116℃；Pressure is -0.82bar；The temperature of tower top is 40 DEG C when de- rectifying again；The reflux ratio of de- rectifying again is 6；Remove positive silicon The heavy components such as propyl-triethoxysilicane, ethyl orthosilicate dimer, ethyl orthosilicate tripolymer in acetoacetic ester, heavy component warp Tower bottom discharging pump P12 discharges to ethyl orthosilicate accumulator tank V10, and tower top condenses to obtain high-purity ethyl orthosilicate through condenser E12, Component purity may be up to 5N or more, and the indexs such as metal ion reach 9N.In terms of silicon tetrachloride, the yield of high-purity ethyl orthosilicate is 84%.
Material carries out being delivered to surge tank V11, graphite condenser through corrosion resistant fan C02 in thick hydrogen chloride storage tank V08 E13, condensation temperature are preferably 10 DEG C, and condensation removes the high-boiling-point impurities such as silicon tetrachloride, and cold source is freezing unit, and pressure is 1.2bar is purified through hydrogen chloride adsorption dehumifier S08, is compressed through compressor C03, pressure 1.28MPa, and temperature is 45 DEG C；Slightly Hydrogen chloride is further purified through the second hydrogen chloride adsorption dehumifier S09 after compression, subsequently into forecooler E14, is cooled down Cooling, the pressure of material is 1.21MPa after pre-cooling, and temperature is -27 DEG C；Enter hydrogen chloride de-light rectification column after pre-cooling and carries out essence It evaporates, the charging of tower middle and upper part, pressure 1.22MPa, temperature is -26 DEG C, and overhead condenser pressure is 1.2MPa, and temperature is -29.7 DEG C, reflux ratio 2, the lighter components impurity such as overhead extraction hydrogen, nitrogen；Tower reactor, which discharges, takes off heavy distillation column T08 to hydrogen chloride, in tower Lower part charging；Tower reactor pressure is 1.22MPa, and excellent temperature is -26 DEG C, and tower reactor produces CO2、SiCl4Equal heavy components；Overhead condenser Pressure is 1.2MPa, and temperature is -26.5 DEG C, and reflux ratio 3, condensation obtains high-purity 5N electronic grade hydrogen chloride liquid, condensed chlorine Change hydrogen to high-purity hydrogen chloride storage tank to collect.In terms of silicon tetrachloride, the yield of high-purity hydrogen chloride is 78%.
High-purity ethyl orthosilicate obtained in embodiment 1 is detected, obtains the results are shown in Table 1.
The testing result of the high-purity ethyl orthosilicate of 1 embodiment of table 1
High-purity hydrogen chloride gas obtained in embodiment 1 is detected, obtains the results are shown in Table 2.
The testing result of 2 embodiment of table, 1 high-purity hydrogen chloride gas
Embodiment 2
Material (predominantly ethyl alcohol, the band that outsourcing industrial alcohol and de-light rectification column T05 overhead condenser E10 are condensed Trimethylethoxysilane, the methyl for having a small amount of ethyl orthosilicate and being generated with the trim,ethylchlorosilane of silicon tetrachloride azeotropic The impurity such as triethoxysilane) enter ethanol raw material storage tank V01, ethyl orthosilicate, trimethylethoxysilane, three ethoxy of methyl Base silane etc. is reacted with the water in industrial alcohol, generates silica and ethyl alcohol, and to remove the water in ethanol raw material, ethyl alcohol is former Expect that storage tank V01 removes the solid impurities such as silica through cloth envelop collector F01, then feeds delivery pump P01 from ethyl alcohol through ethyl alcohol The middle and upper part of de-light rectification column T01 tower is fed, and carries out atmospheric distillation, and rectification temperature is preferably 77 DEG C~79 DEG C, is removed in ethyl alcohol Ether, methanol lighter component, lighter component after overhead condenser condenses enter ethyl alcohol accumulator tank V03, ethyl alcohol de-light rectification column T01 It is preferably the 1/10 of rectifying material that the amount of low boiling component is removed when rectifying；The reflux ratio that ethyl alcohol takes off light rectifying is 8.Ethyl alcohol is de- light Rectifying column T01 kettle material part is after ethyl alcohol de-light rectification column T01 discharging pump P02 is delivered to adsorption dehumifier F01 drying and dehydrating Heavy distillation column T02 is taken off into ethyl alcohol, is fed from the middle and lower part of tower, atmospheric distillation is carried out, rectification temperature is 79 DEG C, is removed in ethyl alcohol Heavy components, the heavy component such as propyl alcohol, isobutanol, isoamyl alcohol take off heavy distillation column discharging pump P03 through ethyl alcohol and enter ethyl alcohol accumulator tank V03, it is preferably the 1/10 of rectifying material that ethyl alcohol, which removes the amount of high boiling component when taking off heavy distillation column T02 rectifying,；The de- weight essence of ethyl alcohol The reflux ratio evaporated is 8.High straight alcohol takes off heavy distillation column condenser E04 to high straight alcohol storage tank V02 through ethyl alcohol, the height purified at this time Straight alcohol component purity is 5N or more.
The by-produced tetrachlorosilane of polysilicon or silane coupling agent is defeated through silicon tetrachloride feeding from silicon tetrachloride raw material storage tank V04 It send pump P04 to feed from the middle and upper part of silicon tetrachloride de-light rectification column T03 tower, carries out compression rectification, rectification temperature is 95 DEG C；Reflux Than being 8；Pressure is 2bar,；Remove the lighter components such as trichlorosilane, boron chloride, the dichlorosilane in silicon tetrachloride, lighter component Enter silicon tetrachloride accumulator tank V06 after overhead condenser condenses, when silicon tetrachloride de-light rectification column T03 rectifying removes low boiling point The amount of component is preferably the 1/10 of rectifying material.De-light rectification column T03 kettle material part discharges through silicon tetrachloride de-light rectification column Pump P05 is delivered to the second boron phosphorus absorber S02 and the second adsorption of metal ions device S03, removes boron phosphorus and gold in silicon tetrachloride Belong to the impurity such as ion, take off heavy distillation column T04 subsequently into silicon tetrachloride, fed from the middle and lower part of tower, carries out compression rectification, rectifying Temperature is 95 DEG C；Pressure is 2bar, reflux ratio 8；Phosphorus oxychloride, phosphorus trichloride, phosphorus pentachloride, two in removing silicon tetrachloride The heavy components such as dimethyl dichlorosilane (DMCS), methyl trichlorosilane, heavy component take off heavy distillation column discharging pump P06 through silicon tetrachloride and enter tetrachloro SiClx accumulator tank V06, it is preferably the 1/ of rectifying material that silicon tetrachloride, which removes the amount of high boiling component when taking off heavy distillation column T04 rectifying, 10.High purity silicon tetrachloride takes off heavy distillation column condenser E08 to high purity silicon tetrachloride storage tank V05 through silicon tetrachloride, purifies at this time High purity silicon tetrachloride (containing the trim,ethylchlorosilane with its azeotropic) component purity is 5N or more.
It pumps P08 from the reacted silicon tetrachloride feeding of high purity silicon tetrachloride storage tank V05 to feed to reactive distillation device R01, charging Position is the side-lower of rectifying section；Then from the high reacted ethyl alcohol feed pump P07 of straight alcohol storage tank V02 to reactive distillation device R01 Charging, feed entrance point are in the middle part of rectifying section.Micro-positive pressure reaction is carried out, reactor helix(ribbon type) agitator, helical-ribbon type stirs when reaction It is next that device digs material upwards, makes the wherein rising of lighter component substance, especially hydrogen chloride.Reaction pressure is 1.3bar；Reaction temperature Degree is 84 DEG C；SiCl4With C2H5The molar ratio of OH is 1:4.2.The hydrogen chloride generated is reacted through gas-liquid separator F02, gas-liquid point It is left in reactor that the reaction was continued from, the silicon tetrachloride of liquid, the thick hydrogen chloride after separation is compressed to slightly through corrosion resistant fan C01 Hydrogen chloride storage tank V08.Obtained ethyl orthosilicate is reacted since boiling point is higher, is enriched in reactor bottom, is protected after charging Warm 50min makes fully reacting, and removes free hydrogen chloride well, depressurizes power after reaction and is down to 0 (gauge pressure), more thorough The free hydrogen chloride of the removing at bottom.After reaction by the thick ethyl orthosilicate in reactive distillation device R01 through delivery pump P09 to work Property carbon decoloring absorber S04 carries out decoloration purifying, subsequently into thick ethyl orthosilicate storage tank V07.Thick ethyl orthosilicate is from slightly just Silester storage tank V07, through calcium oxide depickling absorber, that is, alkaline adsorption device S05, thoroughly removes trip through feeding delivery pump P10 From hydrogen chloride, fed from the middle and upper part of ethyl orthosilicate de-light rectification column T05 tower to it, the temperature of rectifying is 110 DEG C；Pressure For -0.9bar；The temperature of tower top when taking off light rectifying is 35 DEG C；Take off the reflux ratio 6 of light rectifying；It removes in ethyl orthosilicate Unreacted ethyl alcohol, methyltriethoxysilane, methoxyl group triethoxysilane, triethoxychlorosilane, triethoxysilane And trimethylethoxysilane (form the trim,ethylchlorosilane of azeotropic with silicon tetrachloride and ethyl alcohol carries out esterification generation) Equal lighter components.Since the main component in lighter component is ethyl alcohol, therefore lighter component is condensed through overhead condenser E10 to ethanol raw material Storage tank V01 carries out ethyl alcohol recycling.Ethyl orthosilicate de-light rectification column T05 kettle material goes out through ethyl orthosilicate de-light rectification column Material pump P11 is delivered to boron phosphorus resin adsorption device F02 and metal ion resin adsorption device F03, depth removing boron phosphorus and metal from The impurity such as son take off heavy distillation column T06 subsequently into ethyl orthosilicate, and the middle and lower part charging of Jing Congta, the temperature of rectifying is 116 ℃；Pressure is -0.82bar；The temperature of tower top is 40 DEG C when de- rectifying again；The reflux ratio of de- rectifying again is 6；Remove positive silicic acid second The heavy components such as propyl-triethoxysilicane, ethyl orthosilicate dimer, ethyl orthosilicate tripolymer in ester, heavy component is through tower bottom Discharging pump P12 discharges to ethyl orthosilicate accumulator tank V10, and tower top condenses to obtain high-purity ethyl orthosilicate, group through condenser E12 Part purity may be up to 5N or more, and the indexs such as metal ion reach 9N.In terms of silicon tetrachloride, the yield of high-purity ethyl orthosilicate is 85%.
Material carries out being delivered to surge tank V11, graphite condenser through corrosion resistant fan C02 in thick hydrogen chloride storage tank V08 E13, condensation temperature are preferably 10 DEG C, and condensation removes the high-boiling-point impurities such as silicon tetrachloride, and cold source is freezing unit, and pressure is 1.2bar is purified through hydrogen chloride adsorption dehumifier S08, is compressed through compressor C03, pressure 1.28MPa, and temperature is 45 DEG C；Slightly Hydrogen chloride is further purified through the second hydrogen chloride adsorption dehumifier S09 after compression, subsequently into forecooler E14, is cooled down Cooling, the pressure of material is 1.21MPa after pre-cooling, and temperature is -27 DEG C；Enter hydrogen chloride de-light rectification column after pre-cooling and carries out essence It evaporates, the charging of tower middle and upper part, pressure 1.22MPa, temperature is -26 DEG C, and overhead condenser pressure is 1.2MPa, and temperature is -29.7 DEG C, reflux ratio 2, the lighter components impurity such as overhead extraction hydrogen, nitrogen；Tower reactor, which discharges, takes off heavy distillation column T08 to hydrogen chloride, in tower Lower part charging；Tower reactor pressure is 1.22MPa, and excellent temperature is -26 DEG C, and tower reactor produces CO2、SiCl4Equal heavy components；Overhead condenser Pressure is 1.2MPa, and temperature is -26.5 DEG C, and reflux ratio 3, condensation obtains high-purity 5N electronic grade hydrogen chloride liquid, condensed chlorine Change hydrogen to high-purity hydrogen chloride storage tank to collect.In terms of silicon tetrachloride, the yield of high-purity hydrogen chloride is 77%.
High-purity ethyl orthosilicate obtained in embodiment 2 is detected, obtains the results are shown in Table 3.
The testing result of the high-purity ethyl orthosilicate of 3 embodiment of table 2
High-purity hydrogen chloride gas obtained in embodiment 2 is detected, obtains the results are shown in Table 4.
The testing result of the advanced hydrogen chloride gas of 4 embodiment of table 2
Embodiment 3
Material (predominantly ethyl alcohol, the band that outsourcing industrial alcohol and de-light rectification column T05 overhead condenser E10 are condensed Trimethylethoxysilane, the methyl for having a small amount of ethyl orthosilicate and being generated with the trim,ethylchlorosilane of silicon tetrachloride azeotropic The impurity such as triethoxysilane) enter ethanol raw material storage tank V01, ethyl orthosilicate, trimethylethoxysilane, three ethoxy of methyl Base silane etc. is reacted with the water in industrial alcohol, generates silica and ethyl alcohol, and to remove the water in ethanol raw material, ethyl alcohol is former Expect that storage tank V01 removes the solid impurities such as silica through cloth envelop collector F01, then feeds delivery pump P01 from ethyl alcohol through ethyl alcohol The middle and upper part of de-light rectification column T01 tower is fed, and carries out atmospheric distillation, and rectification temperature is preferably 77 DEG C~79 DEG C, is removed in ethyl alcohol Ether, methanol lighter component, lighter component after overhead condenser condenses enter ethyl alcohol accumulator tank V03, ethyl alcohol de-light rectification column T01 It is preferably the 1/10 of rectifying material that the amount of low boiling component is removed when rectifying；The reflux ratio that ethyl alcohol takes off light rectifying is 6.Ethyl alcohol is de- light Rectifying column T01 kettle material part is after ethyl alcohol de-light rectification column T01 discharging pump P02 is delivered to adsorption dehumifier F01 drying and dehydrating Heavy distillation column T02 is taken off into ethyl alcohol, is fed from the middle and lower part of tower, atmospheric distillation is carried out, rectification temperature is 79 DEG C, is removed in ethyl alcohol Heavy components, the heavy component such as propyl alcohol, isobutanol, isoamyl alcohol take off heavy distillation column discharging pump P03 through ethyl alcohol and enter ethyl alcohol accumulator tank V03, it is preferably the 1/10 of rectifying material that ethyl alcohol, which removes the amount of high boiling component when taking off heavy distillation column T02 rectifying,；The de- weight essence of ethyl alcohol The reflux ratio evaporated is 6.High straight alcohol takes off heavy distillation column condenser E04 to high straight alcohol storage tank V02 through ethyl alcohol, the height purified at this time Straight alcohol component purity is 5N or more.
The by-produced tetrachlorosilane of polysilicon or silane coupling agent is defeated through silicon tetrachloride feeding from silicon tetrachloride raw material storage tank V04 It send pump P04 to feed from the middle and upper part of silicon tetrachloride de-light rectification column T03 tower, carries out compression rectification, rectification temperature is 89 DEG C；Reflux Than being 6；Pressure is 1.5bar；The lighter components such as trichlorosilane, boron chloride, dichlorosilane in removing silicon tetrachloride, light group Enter silicon tetrachloride accumulator tank V06 part after overhead condenser condenses, when silicon tetrachloride de-light rectification column T03 rectifying removes low boiling The amount of point component is preferably the 1/10 of rectifying material.De-light rectification column T03 kettle material part goes out through silicon tetrachloride de-light rectification column Material pump P05 is delivered to the second boron phosphorus absorber S02 and the second adsorption of metal ions device S03, boron phosphorus in removing silicon tetrachloride and The impurity such as metal ion take off heavy distillation column T04 subsequently into silicon tetrachloride, feed from the middle and lower part of tower, carry out compression rectification, essence Evaporating temperature is 89 DEG C；Pressure is 1.5bar, reflux ratio 6；Remove phosphorus oxychloride in silicon tetrachloride, phosphorus trichloride, phosphoric The heavy components such as phosphorus, dimethyldichlorosilane, methyl trichlorosilane, heavy component through silicon tetrachloride take off heavy distillation column discharging pump P06 into Enter silicon tetrachloride accumulator tank V06, it is preferably rectifying object that silicon tetrachloride, which removes the amount of high boiling component when taking off heavy distillation column T04 rectifying, The 1/10 of material.High purity silicon tetrachloride takes off heavy distillation column condenser E08 to high purity silicon tetrachloride storage tank V05 through silicon tetrachloride, at this time High purity silicon tetrachloride (containing the trim,ethylchlorosilane with its azeotropic) the component purity of purifying is 5N or more.
It pumps P08 from the reacted silicon tetrachloride feeding of high purity silicon tetrachloride storage tank V05 to feed to reactive distillation device R01, charging Position is the side-lower of rectifying section；Then from the high reacted ethyl alcohol feed pump P07 of straight alcohol storage tank V02 to reactive distillation device R01 Charging, feed entrance point are in the middle part of rectifying section.Micro-positive pressure reaction is carried out, reactor helix(ribbon type) agitator, helical-ribbon type stirs when reaction It is next that device digs material upwards, makes the wherein rising of lighter component substance, especially hydrogen chloride.Reaction pressure is 1.1bar；Reaction temperature Degree is 80 DEG C；SiCl4With C2H5The molar ratio of OH is 1:4.5.The hydrogen chloride generated is reacted through gas-liquid separator F02, gas-liquid point It is left in reactor that the reaction was continued from, the silicon tetrachloride of liquid, the thick hydrogen chloride after separation is compressed to slightly through corrosion resistant fan C01 Hydrogen chloride storage tank V08.Obtained ethyl orthosilicate is reacted since boiling point is higher, is enriched in reactor bottom, is protected after charging Warm 50min makes fully reacting, and removes free hydrogen chloride well, depressurizes power after reaction and is down to 0 (gauge pressure), more thorough The free hydrogen chloride of the removing at bottom.After reaction by the thick ethyl orthosilicate in reactive distillation device R01 through delivery pump P09 to work Property carbon decoloring absorber S04 carries out decoloration purifying, subsequently into thick ethyl orthosilicate storage tank V07.Thick ethyl orthosilicate is from slightly just Silester storage tank V07, through calcium oxide depickling absorber, that is, alkaline adsorption device S05, thoroughly removes trip through feeding delivery pump P10 From hydrogen chloride, fed from the middle and upper part of ethyl orthosilicate de-light rectification column T05 tower to it, the temperature of rectifying is 110 DEG C；Pressure For -0.9bar；30 DEG C of temperature of tower top when taking off light rectifying；Take off the reflux ratio 6 of light rectifying；It removes in ethyl orthosilicate not The ethyl alcohol of reaction, methyltriethoxysilane, methoxyl group triethoxysilane, triethoxychlorosilane, triethoxysilane and Trimethylethoxysilane (form the trim,ethylchlorosilane of azeotropic with silicon tetrachloride and ethyl alcohol carries out esterification generation) etc. Lighter component.Since the main component in lighter component is ethyl alcohol, therefore lighter component is condensed through overhead condenser E10 to ethanol raw material and is stored up Slot V01 carries out ethyl alcohol recycling.Ethyl orthosilicate de-light rectification column T05 kettle material discharges through ethyl orthosilicate de-light rectification column Pump P11 is delivered to boron phosphorus resin adsorption device F02 and metal ion resin adsorption device F03, and depth removes boron phosphorus and metal ion Equal impurity take off heavy distillation column T06 subsequently into ethyl orthosilicate, and the middle and lower part charging of Jing Congta, the temperature of rectifying is 116 DEG C； Pressure is -0.82bar；The temperature of tower top is 40 DEG C when de- rectifying again；The reflux ratio of de- rectifying again is 6；Remove ethyl orthosilicate In heavy components, the heavy component such as propyl-triethoxysilicane, ethyl orthosilicate dimer, ethyl orthosilicate tripolymer go out through tower bottom Material pump P12 discharges to ethyl orthosilicate accumulator tank V10, and tower top condenses to obtain high-purity ethyl orthosilicate, component through condenser E12 Purity may be up to 5N or more, and the indexs such as metal ion reach 9N.In terms of silicon tetrachloride, the yield of high-purity ethyl orthosilicate is 82%.
Material carries out being delivered to surge tank V11, graphite condenser through corrosion resistant fan C02 in thick hydrogen chloride storage tank V08 E13, condensation temperature are preferably 10 DEG C, and condensation removes the high-boiling-point impurities such as silicon tetrachloride, and cold source is freezing unit, and pressure is 1.2bar is purified through hydrogen chloride adsorption dehumifier S08, is compressed through compressor C03, pressure 1.28MPa, and temperature is 45 DEG C；Slightly Hydrogen chloride is further purified through the second hydrogen chloride adsorption dehumifier S09 after compression, subsequently into forecooler E14, is cooled down Cooling, the pressure of material is 1.21MPa after pre-cooling, and temperature is -27 DEG C；Enter hydrogen chloride de-light rectification column after pre-cooling and carries out essence It evaporates, the charging of tower middle and upper part, pressure 1.22MPa, temperature is -26 DEG C, and overhead condenser pressure is 1.2MPa, and temperature is -29.7 DEG C, reflux ratio 2, the lighter components impurity such as overhead extraction hydrogen, nitrogen；Tower reactor, which discharges, takes off heavy distillation column T08 to hydrogen chloride, in tower Lower part charging；Tower reactor pressure is 1.22MPa, and excellent temperature is -26 DEG C, and tower reactor produces CO2、SiCl4Equal heavy components；Overhead condenser Pressure is 1.2MPa, and temperature is -26.5 DEG C, and reflux ratio 3, condensation obtains high-purity 5N electronic grade hydrogen chloride liquid, condensed chlorine Change hydrogen to high-purity hydrogen chloride storage tank to collect.In terms of silicon tetrachloride, the yield of high-purity hydrogen chloride is 75%.
High-purity ethyl orthosilicate obtained in embodiment 3 is detected, obtains the results are shown in Table 5.
The testing result of the high-purity ethyl orthosilicate of 5 embodiment of table 3
High-purity hydrogen chloride gas obtained in embodiment 3 is detected, obtains the results are shown in Table 6.
The testing result of 6 embodiment of table, 3 high-purity hydrogen chloride gas

Claims (10)

1. a kind of preparation method of high-purity ethyl orthosilicate characterized by comprising
S1 high purity silicon tetrachloride and high straight alcohol) are mixed into row reactive distillation, obtain thick ethyl orthosilicate and thick hydrogen chloride；
S2 the thick ethyl orthosilicate is handled through decolorization adsorption), after alkaline adsorption processing, carries out taking off light rectifying, is obtained de- light The light component of ethyl orthosilicate and removing after rectifying；
S3) by the ethyl orthosilicate taken off after light rectifying after boron phosphorus adsorbs resin and adsorption of metal ions resin treatment, into The de- rectifying again of row, obtains high-purity ethyl orthosilicate.
2. preparation method according to claim 1, which is characterized in that the step S1) in reactive distillation temperature be 70 DEG C~90 DEG C；Reaction pressure is 0.5~1.5bar；The step S2) in take off light rectifying temperature be 95 DEG C~130 DEG C；It is de- light The pressure of rectifying is -0.6~-1bar；Reflux ratio is 1~10；The step S3) in take off again rectifying temperature be 95 DEG C~130 ℃；The pressure of de- rectifying again is -0.6~-1bar；Reflux ratio is 1~10.
3. preparation method according to claim 1, which is characterized in that after the thick hydrogen chloride carries out cooling, is adsorbed by drying, Compression successively carries out hydrogen chloride and takes off light rectifying and the frivolous heavy rectifying of chlorination, obtains high-purity hydrogen chloride.
4. preparation method according to claim 3, which is characterized in that it after compression, is adsorbed by drying, is pre-chilled for the second time, It carries out taking off light rectifying and de- rectifying again again.
5. preparation method according to claim 3, which is characterized in that the temperature of the condensation is 5 DEG C~20 DEG C；The pressure The pressure of contracting is 1.2~1.35MPa；The temperature of compression is 40 DEG C~50 DEG C；The temperature of the hydrogen chloride dehydrogenation rectifying is -30 DEG C ~-24 DEG C；The pressure that the hydrogen chloride takes off light rectifying is 1.18~1.22MPa；Reflux ratio is 0.5~3；The de- weight of the hydrogen chloride The temperature of rectifying is -24 DEG C~-28 DEG C；The pressure of the de- rectifying again of the hydrogen chloride is 1.2~1.24MPa；Reflux ratio is 1~5.
6. preparation method according to claim 1, which is characterized in that further include:
Industrial alcohol is reacted with the light component removed in step S2), after filtering, progress ethyl alcohol takes off light rectification process and ethyl alcohol is de- After weight rectification process, high straight alcohol is obtained.
7. preparation method according to claim 1, which is characterized in that further include:
Silicon tetrachloride progress silicon tetrachloride is taken off into light rectifying, then adsorbs resin and adsorption of metal ions resin treatment through boron phosphorus Afterwards, it carries out silicon tetrachloride and takes off rectifying again, obtain high purity silicon tetrachloride.
8. preparation method according to claim 7, which is characterized in that the temperature that the silicon tetrachloride takes off light rectifying is 56 DEG C ~108 DEG C；Pressure is 0~3bar；The amount of light component is removed when taking off light rectifying as the 1/5~1/12 of silicon tetrachloride quality；Tetrachloro The temperature of the de- rectifying again of SiClx is 56 DEG C~110 DEG C；Pressure is 0~3bar；The amount that heavy constituent is removed when de- rectifying again is rectifying The 1/5~1/12 of material.
9. a kind of production system of high-purity ethyl orthosilicate characterized by comprising
High purity silicon tetrachloride storage tank；
High straight alcohol storage tank；
Reactive distillation device；The high purity silicon tetrachloride storage tank is connected with reactive distillation device respectively with high-purity ethanol storage tank；
Decolorization adsorption device；The decolorization adsorption device is connected with reactive distillation device；
Alkaline adsorption device；Alkaline matter is provided in the alkaline adsorption device；The alkaline adsorption device is connected with decolorization adsorption device It is logical；
De-light rectification column；The dehydrogenation rectifying column is connected with alkaline adsorption device；
Boron phosphorus absorber；Boron phosphorus absorption resin is provided in the boron phosphorus absorber；The boron phosphorus absorber and dehydrogenation rectifying column It is connected；
Adsorption of metal ions device；Adsorption of metal ions resin is provided in the adsorption of metal ions device；The metal ion is inhaled Adnexa is connected with boron phosphorus absorber；
De- heavy distillation column；The de- heavy distillation column is connected with adsorption of metal ions device.
10. production system according to claim 9, which is characterized in that further include high-purity hydrogen chloride production system；The height Pure hydrogen chloride production system includes:
Graphite condenser；The graphite condenser is connected with reactive distillation device；
Hydrogen chloride adsorption dehumifier；The hydrogen chloride adsorption dehumifier is connected with graphite condenser；
Compressor；The compressor is connected with hydrogen chloride adsorption dehumifier；
Hydrogen chloride de-light rectification column；The hydrogen chloride de-light rectification column is connected with compressor；
Hydrogen chloride takes off heavy distillation column；The hydrogen chloride takes off heavy distillation column and is connected with hydrogen chloride de-light rectification column.
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CN117398707A (en) * 2023-09-07 2024-01-16 湖北兴福电子材料股份有限公司 Electronic grade hexamethyldisilazane purification device and purification method

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CN110857274A (en) * 2018-08-13 2020-03-03 东营市海科新源化工有限责任公司 Preparation method and device of dioctyl carbonate
CN110255501A (en) * 2019-07-11 2019-09-20 金宏气体电子材料（淮安）有限责任公司 A kind of electronic grade high-purity hydrogen chloride preparation method
CN111217845A (en) * 2020-03-04 2020-06-02 大连恒坤新材料有限公司 Method and device for purifying ethyl borate
CN113121583A (en) * 2021-04-21 2021-07-16 洛阳中硅高科技有限公司 Preparation device and preparation method of electronic-grade ethyl orthosilicate
CN114507250A (en) * 2022-01-12 2022-05-17 湖北江瀚新材料股份有限公司 Synthesis process of electronic-grade ethyl orthosilicate and electronic-grade ethyl polysilicate
CN115304632A (en) * 2022-07-21 2022-11-08 湖北新蓝天新材料股份有限公司 Preparation method and application of electronic-grade tetraalkoxysilane
CN115304632B (en) * 2022-07-21 2023-08-29 湖北新蓝天新材料股份有限公司 Preparation method and application of electronic-grade tetraalkoxysilane
CN115571892A (en) * 2022-10-25 2023-01-06 中船(邯郸)派瑞特种气体股份有限公司 Purification method of electronic-grade boron trichloride
CN116903653A (en) * 2023-07-11 2023-10-20 大连恒坤新材料有限公司 Preparation method and production system of high-purity ethyl silicate
CN117398707A (en) * 2023-09-07 2024-01-16 湖北兴福电子材料股份有限公司 Electronic grade hexamethyldisilazane purification device and purification method

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