CN107162003A - A kind of hydrogenation of silicon tetrachloride technique and trichlorosilane prepare high-purity silicon technology - Google Patents

A kind of hydrogenation of silicon tetrachloride technique and trichlorosilane prepare high-purity silicon technology Download PDF

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CN107162003A
CN107162003A CN201710522320.7A CN201710522320A CN107162003A CN 107162003 A CN107162003 A CN 107162003A CN 201710522320 A CN201710522320 A CN 201710522320A CN 107162003 A CN107162003 A CN 107162003A
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micro
microchannel
passage reaction
heater
micro passage
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于志远
何燕清
佘建峰
刘于航
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/08—Compounds containing halogen
    • C01B33/107—Halogenated silanes
    • C01B33/1071—Tetrachloride, trichlorosilane or silicochloroform, dichlorosilane, monochlorosilane or mixtures thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/02—Silicon
    • C01B33/021—Preparation
    • C01B33/027—Preparation by decomposition or reduction of gaseous or vaporised silicon compounds other than silica or silica-containing material
    • C01B33/03—Preparation by decomposition or reduction of gaseous or vaporised silicon compounds other than silica or silica-containing material by decomposition of silicon halides or halosilanes or reduction thereof with hydrogen as the only reducing agent

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Abstract

The present invention is that a kind of hydrogenation of silicon tetrachloride technique and trichlorosilane prepare high-purity silicon technology.A kind of trichlorosilane prepares high-purity silicon technology, including：(1) trichlorosilane gas and hydrogen are heated and mixed into microchannel hybrid heater, the mixed gas after must heating；(2) mixed gas after heating is sent into micro passage reaction, heats and react in the presence of a catalyst, obtain reacted mixture；(3) after reacted mixture is cooled to, solid and gas separation is carried out, the mixed gas after HIGH-PURITY SILICON and cooling is obtained；Each component in mixed gas after cooling is separated and recovered to utilize.The present invention also disclosed a kind of hydrogenation of silicon tetrachloride technique.A kind of hydrogenation of silicon tetrachloride technique of the present invention and trichlorosilane prepare high-purity silicon technology, compared with traditional handicraft, and the conversion ratio of silicon tetrachloride and trichlorosilane can reach more than 50%；The technique is combined with micro- chemical process, so as to improve conversion ratio, production technology security, reduce energy consumption.

Description

A kind of hydrogenation of silicon tetrachloride technique and trichlorosilane prepare high-purity silicon technology
Technical field
High-purity silicon technology is prepared present invention relates particularly to a kind of hydrogenation of silicon tetrachloride technique and trichlorosilane.
Background technology
With the fast development of photovoltaic industry, the raw material polysilicon of solar cell occurs in that seriously supply falls short of demand, this pole China's polysilicon industry development upsurge is excited greatly, domestic production of polysilicon producer continues to increase, and scale constantly expands.Current state The process that interior most polysilicon producers use is Siemens's improved method production polysilicon, but one ton of polysilicon of production 12-16 tons of silicon tetrachloride as by-product will be generated, silicon tetrachloride is the poisonous liquid of water white transparency, with unpleasant asphyxiating gas Taste, easily with water reaction generation silica and hydrogen chloride.The polysilicon factory of 5000t/a scales will produce the four of 60,000-8 ten thousand tons Silicon chloride, if so many silicon tetrachloride cannot be effectively utilized, not only increases production cost, influences the performance of enterprises, very To polluting the environment, the clean development of whole polysilicon industry is less useful for.Processing fundamental solution to silicon tetrachloride is hydrogen Change, convert it into trichlorosilane, return to system circulation utilization.Because the companies such as external Mitsubishi, Wacker are to high-end hydrogen The block of change technology, present most domestic enterprise is also without ripe method for hydrogenation, how continuously and stably by silicon tetrachloride It is converted into trichlorosilane and returns to polycrystalline silicon production system, the important bottleneck as the polysilicon industry development of restriction China.Current state The restoring method of interior silicon tetrachloride mainly has heat hydrogenation and cold two kinds of hydrogenation, both traditional hydrogenation of silicon tetrachloride techniques, hydrogenation During silicon tetrachloride be not all very be converted into trichlorosilane, the real silicon tetrachloride for participating in reaction only accounts for small Part, the silicon tetrachloride of highest only 25% is hydrogenated.Therefore, the tail gas out of hydrogenation furnace out also containing substantial amounts of hydrogen and Silicon tetrachloride, trichlorosilane and hydrogen chloride, these tail gas are sent in retracting device, each component are separated, hydrogen is returned Return in hydrogenation, hydrogen chloride sends to participation trichlorosilane synthesis, and (wherein silicon tetrachloride accounts for major part to chlorosilane, and remaining is three Chlorine hydrogen silicon) it is sent to after rectifying separating-purifying, silicon tetrachloride returns to hydrogenation, and trichlorosilane is sent to hydrogen reduction and produces polysilicon.
Cold method for hydrogenation uses following reaction principle：3SiCl4+Si+2H2=4SiHCl3.This method is to utilize Silicon tetrachloride, silica flour and hydrogen react in higher temperature, the fluidized bed furnace of pressure, generation trichlorosilane (really trichlorosilane, The gaseous mixture of silicon tetrachloride, hydrogen etc. is, it is necessary to send rectifying separating-purifying after condensing).According to foreign countries, its conversion ratio is up to 25% or so.This method for hydrogenation is as a result of industrial silica fume, therefore obtained product purity is not high, it is necessary to carry out further Rectification and purification, can just obtain finally be available for hydrogen reduction to use dichloro hydrogen silicon, this just increases energy consumption；And due to the reaction Temperature is higher, and reaction pressure is also higher (more than ten atmospheric pressure), and the requirement to equipment is also very high.In addition, silica flour is in course of reaction In be in boiling-like, because the hardness of silica flour is very big, serious friction is caused to the inwall of fluidized bed furnace, makes inwall thinning, shorten boiling Rise the life-span of stove.
The method of another hydrogenation of silicon tetrachloride was gradually developed both at home and abroad in recent years, i.e. " heat hydrogenation ", it reacts former Reason is as follows：3SiCl4+3H2=3SiHCl3+ 3HCl (high temperature+catalyst)；By the mixing of the silicon tetrachloride necessarily matched and hydrogen Gas sends into reacting furnace, is reacted at high temperature, obtains trichlorosilane, while generating hydrogen chloride.Whole process is gone back with hydrogenation Original reaction generation polysilicon is much like, and, it is necessary to prepare the evaporator of vapour gas mixture, hydrogenation stove is also much like with reduction furnace, What is only obtained is trichlorosilane rather than polysilicon.Heat hydrogenation flow be：Silicon tetrachloride and hydrogen enter evaporator, shape Into gaseous mixture, gaseous mixture reacts into hydrogenation furnace, obtains the gases such as trichlorosilane and hydrogen chloride, is carried out into device for recovering tail gas Separation and recovery.
The vapour mixture preparation process of preparation with the hydrogen reduction of gaseous mixture is identical, and silicon tetrachloride is similar into one and changed In the container of hot device, evaporation is heated wherein, is mixed with the hydrogen being passed through in container, form mixed gas.In order to be wanted Seek the gaseous mixture of proportioning (mol ratio), it is necessary to which the pressure of evaporating temperature and container to silicon tetrachloride is controlled, make it in rule In the range of fixed value, simply both control parameters are different.Obtained silicon tetrachloride and the gaseous mixture of hydrogen enter hydrogenation furnace In, red-hot heater surface reacts in hydrogenation furnace, generation trichlorosilane and hydrogen chloride.The silicon tetrachloride of this process Be not all very be converted into trichlorosilane, the real silicon tetrachloride for participating in reaction only accounts for fraction.Therefore, from hydrogenation Tail gas in stove out also contains substantial amounts of hydrogen and silicon tetrachloride, and trichlorosilane and hydrogen chloride, and these tail gas are sent to In retracting device, and each component is separated, hydrogen is returned in hydrogenation, hydrogen chloride is sent to participation trichlorosilane and closed Into chlorosilane (wherein silicon tetrachloride accounts for major part, and remaining is trichlorosilane) is sent to after rectifying separating-purifying, and silicon tetrachloride is returned Hydrogenation, trichlorosilane is sent to hydrogen reduction and produces polysilicon.
Compared with cold method for hydrogenation, the hot hydrogenation temperature of silicon tetrachloride is high, and converting silicon tetrachloride rate only has 18%, cold hydrogen Change method has 25%, less than cold method for hydrogenation.But, either hot method for hydrogenation or cold method for hydrogenation, all in the presence of certain Problem, hot method for hydrogenation reaction temperature is high, process flow is complicated, device operation difficulty is big, and conversion ratio is low, high energy consumption；And The method that the cold hydrogenation technology of part producer leans on Introduced From Abroad, lacks independent research and development capacity, handles silicon tetrachloride ability, operation Problem is relatively more.
The reaction principle that polysilicon is made in trichlorosilane is：SiHCl3+H2=Si+3HCl；Its process and the hot hydrogen of silicon tetrachloride Change process is much like, but the condition in reaction, equipment and some other aspect still have larger difference, with regard to hot hydrogenation process For.
(1) source of silicon tetrachloride raw material：In polysilicon factory, silicon tetrachloride is topmost accessory substance, and yield is very Greatly, such as in trichlorosilane synthesis, while generation trichlorosilane, the silicon tetrachloride of generation 20% is will be about, is also had in addition Hydro-reduction will also produce substantial amounts of silicon tetrachloride, and unconverted four chlorination of hot hydrogenation while generating polysilicon Silicon.These silicon tetrachlorides confuse other chlorosilanes after device for recovering tail gas condensation is reclaimed, all in rectification section separating-purifying, Pure silicon tetrachloride is obtained as the raw material of heat hydrogenation.
(2) preparation of vapour mixture：Vapour mixture enter hydrogenation stove in, more than 1000 DEG C at a high temperature of instead Should.Because silicon tetrachloride can also generate polysilicon with hydrogen reaction, but need to avoid such case from occurring herein, otherwise exist A polysilicon will be deposited on the heater of hydrogenation furnace, influence is brought on heater and the use for hydrogenating body of heater, and make tetrachloro SiClx is reduced to the conversion ratio of trichlorosilane.Root it was found that when silicon tetrachloride and hydrogen proportioning within the specific limits when, and control Reaction temperature pressure needed for system, you can avoid the generation of polysilicon, and reaction is carried out towards the direction of generation trichlorosilane. Therefore the operation of the evaporator before is particularly important, and operation to stablize and parameter is reasonable, with the required proportioning that ensures to obtain Vapour gas mixture enters hydrogenation furnace.
(3) hot hydrogenation furnace is much like with reduction furnace, there is similar furnace binding.But there is also many differences.① Heater.The heater of reduction furnace is silicon core, and polysilicon is deposited upon on silicon core, and silicon core is gradually thicker to turn into final products polycrystalline Silicon rod.The heater of hydrogenation furnace is made up of a kind of special material, and it provides the temperature needed for reaction, and reacts also on its surface Carry out, but solid matter is not deposited on above.2. reduction furnace belongs to batch production, when the silicon rod in stove grows into institute Need that reaction will be stopped after diameter, after silicon rod is taken out, be reloaded into silicon core, carry out the growth of a new stove.Hydrogenation furnace is continuity Production, once gaseous mixture is passed through in stove, just no longer stop because its product and need not by stove open can just obtain, produce Product (trichlorosilane) are continuously discharged together with silicon tetrachloride and hydrogen, HCl from outlet pipe.Unless equipment is examined Repair, otherwise will not blowing out.3. due to the good conductor of the inherently electricity of the heater in hydrogenation furnace, rather than the same cold resistance of silicon core High not easy conductive, thus hydrogenation furnace startup need not be special such as high voltage startup or pipeline start up by preheating device.4. the stove of hydrogenation furnace Cylinder cooling water temperature is less than the furnace tube coolant water temperature of reduction furnace.5. the air inlet of hydrogenation furnace is from top air inlet, from bottom outlet.
Likewise, hydrogen reduction prepares the shortcomings of polysilicon process has low conversion ratio, high energy consumption.
In view of this, it is necessary to propose a kind of high conversion rate, the tetrachloro silicane hydrogenation process of less energy consumption, and trichlorosilane The technique for preparing silicon.
The content of the invention
It is an object of the invention to provide a kind of hydrogenation of silicon tetrachloride technique, the high conversion rate of the technique, less energy consumption, and It is more safe and environment-friendly.
To achieve these goals, the technical scheme used for：
A kind of hydrogenation of silicon tetrachloride technique, comprises the following steps：
(1) silicon tetrachloride gas and hydrogen are pressed into 0.2-0.5：1 mol ratio enters microchannel hybrid heater and heated simultaneously Mixing, heating-up temperature is 100-700 DEG C, the mixed gas after must heating；Should by the mixed gas feeding microchannel plate after heating Device, heats and is reacted under the catalysis of catalyst, heating-up temperature is 700-1300 DEG C, obtains reacted mixed gas；Will reaction Mixed gas afterwards is cooled to 250-350 DEG C, the mixed gas after must cooling down；The catalyst is aluminum oxide；
Or silicon tetrachloride gas and hydrogen are pressed into 0.1-0.3：1 mol ratio is heated and mixed into microchannel hybrid heater Close, heating-up temperature is 100-800 DEG C, the mixed gas after must heating；Should by the mixed gas feeding microchannel plate after heating Device, heats and is reacted under the catalysis of catalyst, heating-up temperature is 700-1400 DEG C, obtains reacted mixture；Will reaction Mixture afterwards is cooled to after 250-350 DEG C, is separated by solid and gas, obtains the mixed gas after HIGH-PURITY SILICON and cooling；The catalysis Agent is aluminum oxide；
(2) cool down after mixed gas enter reclaim separator, each component is separated, obtain hydrogen, hydrogen chloride and Chlorosilane gas；Hydrogen returns to step (1), and chlorosilane is sent to after rectifying separating-purifying, obtains silicon tetrachloride and trichlorosilane, Silicon tetrachloride returns to step (1).
Further, in the step (1), the mol ratio of silicon tetrachloride gas and hydrogen is 1：3, the gaseous mixture after heating Temperature is 600 DEG C；Reacted mixed gas temperature is 1200-1300 DEG C；
Or in the step (1), the mol ratio of silicon tetrachloride gas and hydrogen is 1：6, the mixed gas temperature after heating For 600 DEG C；Reacted mixture temperature is 1360-1400 DEG C.
Further, the microchannel hybrid heater is placed in electrically heated heater；
Wherein, the heater sets lagging facility and temperature automatically controlled facility；
The microchannel hybrid heater include micro-channel mixer unit and heater element, micro-channel mixer unit and Heater element is in arranged for interval；The micro-channel mixer unit includes the micro-channel mixer substrate no less than 1；It is described micro- Channel mixer substrate includes the microchannel no less than 1；The width of the microchannel is 10-500 microns, and depth is 10-300 Micron；
The micro passage reaction is placed in electrically heated heater；
Wherein, the heater sets lagging facility and temperature automatically controlled facility；
The micro passage reaction includes micro passage reaction unit and heater element, micro passage reaction unit and heating Device is in arranged for interval；The micro passage reaction unit includes the micro passage reaction substrate no less than 1；The microchannel Reactor substrate includes the microchannel no less than 1；The width of the microchannel is 10-500 microns, and depth is that 10-300 is micro- Rice.
Further, in the microchannel hybrid heater, the micro-channel mixer unit includes 10-100 pieces Micro-channel mixer substrate；The width of the microchannel is 200 microns, and depth is 100 microns；The microchannel hybrid heater Material be sapphire, carborundum, ceramics and corrosion resisting alloy in one kind；
In the micro passage reaction, the micro passage reaction unit includes the micro passage reaction base of 10-100 pieces Piece；The width of the microchannel is 200 microns, and depth is 100 microns；The material of the micro passage reaction is sapphire, carbon One kind in SiClx, ceramics and corrosion resisting alloy.
Further, in the microchannel hybrid heater, the micro-channel mixer unit includes 20 micro- logical Road blender substrate；The material of the microchannel hybrid heater is sapphire；
The micro passage reaction unit includes the micro passage reaction substrate of 20；The material of the micro passage reaction For sapphire.
High-purity silicon technology is prepared it is a further object of the invention to provide a kind of trichlorosilane, the high conversion rate of the technique, Less energy consumption, and it is more safe and environment-friendly.
To achieve these goals, the technical scheme used for：
A kind of trichlorosilane prepares high-purity silicon technology, it is characterised in that comprise the following steps：
(1) trichlorosilane gas and hydrogen are heated and mixed into microchannel hybrid heater, heating-up temperature be 100- 800 DEG C, the mixed gas after must heating；The mol ratio of the trichlorosilane gas and hydrogen is 0.2-0.5：1；
(2) mixed gas after heating is sent into micro passage reaction, is heated to 1000-1300 DEG C, and in catalyst In the presence of react, obtain reacted mixture；The catalyst is aluminum oxide；
(3) reacted mixture is cooled to after 250-350 DEG C, separated by solid and gas, obtained after HIGH-PURITY SILICON and cooling Mixed gas；Mixed gas after cooling, which enters, reclaims separator, and each component is separated, hydrogen, hydrogen chloride and chlorine is obtained Silane gas；Hydrogen returns to step (1)；Chlorosilane is sent to after rectifying separating-purifying, obtains trichlorosilane and silicon tetrachloride, three Chlorine hydrogen silicon returns to step (1).
Further, in the step (1), the mol ratio of trichlorosilane gas and hydrogen is 1:3-4, heating-up temperature is 600℃；
In the step (2), heating-up temperature is 1250-1300 DEG C.
Further, the microchannel hybrid heater is placed in electrically heated heater；
Wherein, the heater sets lagging facility and temperature automatically controlled facility；
The microchannel hybrid heater include micro-channel mixer unit and heater element, micro-channel mixer unit and Heater element is in arranged for interval；The micro-channel mixer unit includes the micro-channel mixer substrate no less than 1；It is described micro- Channel mixer substrate includes the microchannel no less than 1；The width of the microchannel is 10-500 microns, and depth is 10-300 Micron；
The micro passage reaction is placed in electrically heated heater；
Wherein, the heater sets lagging facility and temperature automatically controlled facility；
The micro passage reaction includes micro passage reaction unit and heater element, micro passage reaction unit and heating Device is in arranged for interval；The micro passage reaction unit includes the micro passage reaction substrate no less than 1；The microchannel Reactor substrate includes the microchannel no less than 1；The width of the microchannel is 10-500 microns, and depth is that 10-300 is micro- Rice.
Further, in the microchannel hybrid heater, the micro-channel mixer unit includes 10-100 pieces Micro-channel mixer substrate；The width of the microchannel is 200 microns, and depth is 100 microns；The microchannel hybrid heater Material be sapphire, carborundum, ceramics and corrosion resisting alloy in one kind；
In the micro passage reaction, the micro passage reaction unit includes the micro passage reaction base of 10-100 pieces Piece；The width of the microchannel is 200 microns, and depth is 100 microns；The material of the micro passage reaction is sapphire, carbon One kind in SiClx, ceramics and corrosion resisting alloy.
Further, in the microchannel hybrid heater, the micro-channel mixer unit includes 20 micro- logical Road blender substrate；The material of the microchannel hybrid heater is sapphire；
The micro passage reaction unit includes the micro passage reaction substrate of 20；The material of the micro passage reaction For sapphire.
Compared with prior art, the present invention is advantageous in that：
1st, a kind of hydrogenation of silicon tetrachloride technique of the present invention and trichlorosilane prepare high-purity silicon technology, with macro work work Skill is combined, and micro- chemical process has：Rapid mixing (reaction), reaction temperature homogenization, high efficiency temperature control, mitigation reaction temperature Degree, the accurate control of reaction, the advantage for suppressing side reaction, can improve the peace of reaction speed, the rate of producing into, selectivity, production technology Quan Xing, also has the advantages that to save resource, energy-saving and environmental protection, these advantages are all that existing hydrogenation of silicon tetrachloride technique is incomparable 's.
2nd, a kind of hydrogenation of silicon tetrachloride technique of the present invention and trichlorosilane prepare high-purity silicon technology, utilize macro work The characteristics of micro-channel mixer, micro passage reaction, percussion flow chemical reaction is carried out in micron-sized channel-type reactor；By Very small in space reactor, material is highly uniform by collisional mixing, haptoreaction completely, and from traditional work can be solved Skill reacts the not low technical barrier of thorough, reaction efficiency.
Brief description of the drawings
Fig. 1 is the arrangement schematic diagram of micro-channel mixer unit and heater element in microchannel, is 1. heat-insulation layer in figure, 2. it is heater element, is 3. micro-channel mixer unit；
Fig. 2 is the arrangement schematic diagram of micro passage reaction unit and heater element in microchannel, is 1. heat-insulation layer in figure, 2. it is heater element, is 4. micro passage reaction unit；
Fig. 3 is microchannel schematic diagram, in figure, is 5. microchannel, is 6. salient point；
Fig. 4 is a kind of process chart of hydrogenation of silicon tetrachloride technique described in embodiment 1-4；
Fig. 5 is a kind of process chart of hydrogenation of silicon tetrachloride technique described in embodiment 5-8；
Fig. 6 prepares the process chart of high-purity silicon technology for a kind of trichlorosilane described in embodiment 9-12.
Embodiment
High-purity silicon technology is prepared in order to which a kind of hydrogenation of silicon tetrachloride technique of the invention and trichlorosilane is expanded on further, is reached It is expected that goal of the invention, below in conjunction with preferred embodiment, to according to a kind of hydrogenation of silicon tetrachloride technique and trichlorine proposed by the present invention Hydrogen silicon prepares high-purity silicon technology, its embodiment, structure, feature and its effect, describes in detail as after.In the description below In, what different " embodiment " or " embodiment " referred to is not necessarily same embodiment.In addition, the spy in one or more embodiments Determining feature, structure or feature can be combined by any suitable form.
Before elaborating a kind of hydrogenation of silicon tetrachloride technique of the invention and trichlorosilane prepares high-purity silicon technology, having must Related process and material for being referred in the present invention etc. are described further, to reach more preferable effect.
Micro- Chemical Engineering Technology is the cutting edge technology risen at the beginning of the nineties in last century.The technology can promote process intensification and chemical industry system System miniaturization, improves the energy, the level of resources utilization, reaches energy-saving purpose, improves the security of process.The technology is recognized To be the revolutionary technology of 21 century chemical industry, successful exploitation and the application of micro- Chemical Engineering Technology will be produced to chemical field Significant impact.
Entirely different with traditional batch reactor production technology, micro- Chemical Engineering Technology is in the reaction of micron-sized channel-type Percussion flow chemical reaction is carried out in device.Because space reactor is very small, material is highly uniform by collisional mixing, and contact is anti- Should be complete, and react the technical barrier such as not thorough and explosive from traditional handicraft can be solved.
Macro work technology characteristics：Rapid mixing (reaction), reaction temperature homogenization, new product development, high efficiency temperature control System, relax reaction temperature, improve existing process, the accurate control of reaction, suppress side reaction, improve reaction speed, improve the rate of producing into, Improve selectivity, the security for improving production technology, particle diameter control, saving resource, energy-saving and environmental protection.
The core of micro- Chemical Engineering Technology is micro passage reaction.Compared with traditional chemical process, micro- Chemical Engineering Technology is most important It is reactor and fast reaction process conditions that research and development are suitable for micro- reaction system.At present, the research work of micro- Chemical Engineering Technology It is concentrated mainly on following three aspect：One is the update of traditional Chemical Engineering Technology, is concentrated mainly on petrochemical industry, medicine, agriculture The fields such as medicine, dyestuff, fire (fried) medicine, mainly including sulfonation, directly nitrification, fluorination, oxidation, peroxidating, amidatioon, diazotising etc. All kinds of strongly exothermic and inflammable and explosive gas-liquid and liquid-liquid course of reaction.Two be the research work in national security field, mainly It is related to chemical laser miniaturization, nuclear fuel efficient process, safety in production of special material etc..Three be the necks such as nano material synthesis Domain, particularly can be changed into image-stone oiling by the batch (-type)s such as fine chemistry industry, medication chemistry, less efficient synthesis technique Controllable continuous technique as work, allows reaction to be shortened to tens seconds from a few houres.
There is no powerful manufacturing industry, just without country and national prosperity.The manufacturing industry with international competitiveness is made, is China lifting overall national strength, safeguard national security, building world power only way.On May 18th, 2015, State Council is formal Issue《Made in China 2025》Planning, is that China implements the strategic first 10 years programme of action of manufacturing power.German Industrial 4.0 It is the product of global the 4th industrial revolution, its core is also Lean Manufacturing, intelligent plant, efficiency and safety to improving production Property, the quality of product and its stability are significant.Micro- Chemical Engineering Technology in appearance only more than 20 years, is allowed with the glamour that it is exclusive We are full of reverie to following Chemical Manufacture.Using the technology that can be directly amplified, security is efficient, course of reaction is easily-controllable, change Become chemical industry some links, image of certain reaction pollution weight, high energy consumption and security difference, allow the strong of chemical process Change, be miniaturized and greenization, greatly improve the resource and efficiency of energy utilization of Chemical Manufacture, be entirely possible realization.China It is research and development, the big producer of customization of chemicals.The bright outlook of micro- Chemical Engineering Technology caused universities and colleges of China, research institution and The great attention of relevant enterprise, but need scientific and technological circle and business circles to be continually striving to setting a prairie fire, also from single spark is lighted." 13 " Period, we, which need to intensify our effort, captures micro-reacting tcchnology difficult point, first has to strengthen Optimal Structure Designing and the elder generation of micro- reaction system Enter manufacturing technology, system intelligent control technology and microreactor corrosion-and blocking-prevention plug technology etc..Secondly, traditional chemical industry skill is strengthened The update (including traditional consersion unit be difficult to new course of reaction exploitation) of art, concern sulfonation, nitrification, chlorination, Oxidation, peroxidating, amidatioon, rearrangement reaction, emphasis reacted for the strongly exothermic and inflammable and explosive gas-liquid of typical case, liquid-liquid Industrialization research is carried out in journey, and nano material controllable preparation etc..Again, emphasis to carry out for fine chemistry industry, field of medicaments Applied D emonstration is studied, in fine chemistry industry, rubber chemicals and nano material and the neck such as the new process based on micro-reacting tcchnology Domain obtains further break through.Complete above-mentioned task, it is necessary to strengthen microchemical engineering and the Basic and applied basic research of technology, Microchemical engineering and the crucial general character problem in science of technical field are solved, so could be that China's chemical industry is manufacturing be lifted energetically Make significant contribution！
HIGH-PURITY SILICON can obtain high-purity crystallized silicon through smelting.HIGH-PURITY SILICON is the system of semiconductor, integrated circuit, photovoltaic cell Make material.
Aluminum oxide, also known as there is alundum (Al2O3), corundum, alumina, alumina, and chemical formula is Al2O3, it is a kind of change of high rigidity Compound, fusing point is 2054 DEG C, and boiling point is 2980 DEG C, is ionic crystals ionizable at high temperature, as analytical reagent, You Jirong The dehydration of agent, adsorbent, organic reaction catalyst, grinding agent, polishing agent, raw material, the refractory material for smelting aluminium.
Sapphire (Al2O3) white stone is also known as, it is the crystalline material that hardness is only second to diamond in the world.In its structure Oxygen atom is arranged in the way of approaching HCP (hexagonal closed packed), and wherein the octahedral coordination between oxygen atom is about The space for having 2/3 is filled by aluminium atom, thus makes it have intensity, hardness high (Mohs' hardness 9), (fusing point reaches high temperature resistant 2050 DEG C), abrasion-resistant, corrosion resistance it is strong, chemical property is stable, general water insoluble, not acid corrosion, only at high temperature (more than 3000 DEG C) could be hydrofluoric acid (HF), phosphoric acid (H2PO4) and fusing caustic potash (KOH) corroded；And with same nitrogen Change the series of characteristics such as the good semi-conducting material combination matching such as gallium, translucidus energy, electrical insulation capability be excellent.
Carborundum (SiC) is with quartz sand, petroleum coke (or coal tar), wood chip (being needed plus salt during production green silicon carbide) Formed Deng raw material by resistance furnace pyrolytic semlting.There is also rare mineral, Mo Sangshi in the Nature for carborundum.Carborundum is also known as Moissanite.In the non-oxidized substance high-tech refractory raw material such as contemporary C, N, B, carborundum is most widely used, most economical one kind, It is properly termed as corundum or fire sand.The main application fields of silicon carbide wafer have LED solid state lightings and high-frequency device.The material Material have is higher by the good characteristics such as forbidden band, drift velocity, breakdown voltage, thermal conductivity, the high temperature resistant of traditional silicon several times, high temperature, The electronic application field and space flight, military project, nuclear energy etc. such as high pressure, high frequency, high-power, photoelectricity, radioresistance, microwave extreme environment should With there is irreplaceable advantage.
Corrosion resisting alloy, metals against corrosion material, for non-metal anti-corrosion material, metals against corrosion material is main There are ferrous alloy (corrosion-resistant stainless steel), nickel-base alloy (Ni-Cr alloy, Ni-Cr-Mo alloys, Ni-Cu alloys etc.), activity gold Category.
After above-mentioned related raw material has been understood, below in conjunction with specific embodiments, to a kind of silicon tetrachloride of the invention Hydrogenation process and trichlorosilane prepare high-purity silicon technology and are further described in detail：
A kind of hydrogenation of silicon tetrachloride technique, its reaction principle is：3SiCl4+3H2=3SiHCl3+ 3HCl (high temperature+catalysis Agent), process chart and embodiment 1-4 with reference to shown in Fig. 4 are done further to a kind of hydrogenation of silicon tetrachloride technique of the invention It is discussed in detail.
Embodiment 1.
(1) silicon tetrachloride gas and hydrogen are pressed 0.2：1 mol ratio is heated and mixed into microchannel hybrid heater, Heating-up temperature is 700 DEG C, the mixed gas after must heating.Microchannel hybrid heater is placed in electrically heated heater；Its In, heater sets lagging facility and temperature automatically controlled facility.Microchannel hybrid heater includes several micro-channel mixer lists First and several heater elements, micro-channel mixer unit and heater element are in arranged for interval, as shown in Figure 1；Micro-channel mixer Unit includes the micro-channel mixer substrate of 10, to ensure that heat is quickly transmitted；Micro-channel mixer substrate includes many In the microchannel of 1；The width of microchannel be 500 microns, depth be 300 microns, microchannel upper and lower part preferably do as Shown in Fig. 3, surface area can be increased to improve mixing efficiency, heat conduction efficiency.The material of the microchannel hybrid heater For ceramics.
(2) mixed gas after heating is sent into micro passage reaction by insulation, corrosion resistant pipeline, heated and in oxidation Reacted under the catalysis of aluminium, heating-up temperature is 1300 DEG C, after reaction terminates, obtains reacted mixed gas.Micro passage reaction is put In electrically heated heater；Wherein, heater sets lagging facility and temperature automatically controlled facility.Micro passage reaction includes Several micro passage reaction units and several heater elements, micro passage reaction unit and heater element are in arranged for interval, such as Fig. 2 It is shown；Micro passage reaction unit includes the micro passage reaction substrate of 10, to ensure that heat is quickly transmitted；Microchannel plate Device substrate is answered to include the microchannel no less than 1；The width of microchannel is 500 microns, and depth is 300 microns of (width of microchannel Degree is not less than depth), it is that microchannel upper and lower part is preferably done as shown in figure 3, surface area can be increased to improve mixing effect Rate, heat conduction efficiency.The material of micro passage reaction is carborundum.
(3) by reacted mixed gas fast cooling to 320 DEG C, it is easy to suppress side reaction, enters back into recovery separation dress Put, each component is separated, obtain hydrogen, hydrogen chloride and chlorosilane gas；Hydrogen returns to step (1), and hydrogen chloride sends to conjunction Into trichlorosilane；Chlorosilane is sent to after rectifying separating-purifying, obtains silicon tetrachloride and trichlorosilane, and wherein silicon tetrachloride accounts for few portion Point, it is largely trichlorosilane, silicon tetrachloride returns to step (1), and trichlorosilane hydrogen reduction produces polysilicon for reduction.
The conversion ratio of silicon tetrachloride is 52% in embodiment (1).
A kind of hydrogenation of silicon tetrachloride technique described in the embodiment of the present invention, compared with traditional handicraft, four in hydrogenation process Chlorination silicon conversion can reach more than 50%, and tail gas out comprises only a small amount of hydrogen and silicon tetrachloride, substantial amounts of trichlorine Hydrogen silicon and hydrogen chloride, these tail gas are sent in retracting device, and each component is separated, and is recycled.The work Skill is combined with micro- chemical process, the characteristics of using macro work micro-channel mixer, micro passage reaction, in micron-sized channel-type Percussion flow chemical reaction is carried out in reactor；Because space reactor is very small, material is highly uniform by collisional mixing, connects Touch reaction complete, so as to improve the security of reaction speed, the rate of producing into, selectivity, production technology, money can also be saved Source, reduction energy consumption, environmental protection.
Embodiment 2.
(1) silicon tetrachloride gas and hydrogen are pressed 0.5：1 mol ratio is heated and mixed into microchannel hybrid heater, Heating-up temperature is 100 DEG C, the mixed gas after must heating.Microchannel hybrid heater is placed in electrically heated heater；Its In, heater sets lagging facility and temperature automatically controlled facility.Microchannel hybrid heater includes several micro-channel mixer lists First and several heater elements, micro-channel mixer unit and heater element are in arranged for interval, as shown in Figure 1；Micro-channel mixer Unit includes the micro-channel mixer substrate of 100, to ensure that heat is quickly transmitted；Micro-channel mixer substrate includes many In the microchannel of 1；The width of microchannel be 10 microns, depth be 10 microns, microchannel upper and lower part preferably do such as Fig. 3 It is shown, surface area can be increased to improve mixing efficiency, heat conduction efficiency.The material of the microchannel hybrid heater is carbon SiClx.
(2) mixed gas after heating is sent into micro passage reaction by insulation, corrosion resistant pipeline, heated and in oxidation Reacted under the catalysis of aluminium, heating-up temperature is 700 DEG C, after reaction terminates, obtains reacted mixed gas.Micro passage reaction is placed in In electrically heated heater；Wherein, heater sets lagging facility and temperature automatically controlled facility.Micro passage reaction includes number Individual micro passage reaction unit and several heater elements, micro passage reaction unit and heater element are in arranged for interval, such as Fig. 2 institutes Show；Micro passage reaction unit includes the micro passage reaction substrate of 100, to ensure that heat is quickly transmitted；Microchannel plate Device substrate is answered to include the microchannel of 1000；The width of microchannel is 10 microns, and depth is 10 microns, and (width of microchannel is not small In depth), it is that microchannel upper and lower part is preferably done to be passed as shown in figure 3, surface area increased to improve mixing efficiency, heat Lead efficiency.
The material of micro passage reaction is ceramics.
(3) by reacted mixed gas fast cooling to 350 DEG C, it is easy to suppress side reaction, enters back into recovery separation dress Put, each component is separated, obtain hydrogen, hydrogen chloride and chlorosilane gas；Hydrogen returns to step (1), and hydrogen chloride sends to conjunction Into trichlorosilane；Chlorosilane is sent to after rectifying separating-purifying, obtains silicon tetrachloride and trichlorosilane, and wherein silicon tetrachloride accounts for few portion Point, it is largely trichlorosilane, silicon tetrachloride returns to step (1), and trichlorosilane hydrogen reduction produces polysilicon for reduction.
The conversion ratio of silicon tetrachloride is 61% in embodiment (2).
A kind of hydrogenation of silicon tetrachloride technique described in the embodiment of the present invention, compared with traditional handicraft, four in hydrogenation process Chlorination silicon conversion can reach more than 50%, and tail gas out comprises only a small amount of hydrogen and silicon tetrachloride, substantial amounts of trichlorine Hydrogen silicon and hydrogen chloride, these tail gas are sent in retracting device, and each component is separated, and is recycled.The work Skill is combined with micro- chemical process, the characteristics of using macro work micro-channel mixer, micro passage reaction, in micron-sized channel-type Percussion flow chemical reaction is carried out in reactor；Because space reactor is very small, material is highly uniform by collisional mixing, connects Touch reaction complete, so as to improve the security of reaction speed, the rate of producing into, selectivity, production technology, money can also be saved Source, reduction energy consumption, environmental protection.
Embodiment 3.
(1) silicon tetrachloride gas and hydrogen are pressed 1：3 mol ratio is heated and mixed into microchannel hybrid heater, plus Hot temperature is 600 DEG C, the mixed gas after must heating.Microchannel hybrid heater is placed in electrically heated heater；Wherein, Heater sets lagging facility and temperature automatically controlled facility.Microchannel hybrid heater include several micro-channel mixer units and Several heater elements, micro-channel mixer unit and heater element are in arranged for interval, as shown in Figure 1；Micro-channel mixer unit Including the micro-channel mixer substrate of 20, to ensure that heat is quickly transmitted；Micro-channel mixer substrate includes being no less than 1 Microchannel；The width of microchannel be 200 microns, depth be 100 microns, microchannel upper and lower part preferably do such as Fig. 3 institutes Show, surface area can be increased to improve mixing efficiency, heat conduction efficiency.The material of the microchannel hybrid heater is blue precious Stone.
(2) mixed gas after heating is sent into micro passage reaction by insulation, corrosion resistant pipeline, heated and in oxidation Reacted under the catalysis of aluminium, heating-up temperature is 1200 DEG C, after reaction terminates, obtains reacted mixed gas.Micro passage reaction is put In electrically heated heater；Wherein, heater sets lagging facility and temperature automatically controlled facility.Micro passage reaction includes Several micro passage reaction units and several heater elements, micro passage reaction unit and heater element are in arranged for interval, such as Fig. 2 It is shown；Micro passage reaction unit includes the micro passage reaction substrate of 20, to ensure that heat is quickly transmitted；Microchannel plate Device substrate is answered to include the microchannel no less than 1；The width of microchannel is 200 microns, and depth is 100 microns of (width of microchannel Degree is not less than depth), it is that microchannel upper and lower part is preferably done as shown in figure 3, surface area can be increased to improve mixing effect Rate, heat conduction efficiency.
The material of micro passage reaction is sapphire.
(3) by reacted mixed gas fast cooling to 300 DEG C, it is easy to suppress side reaction, enters back into recovery separation dress Put, each component is separated, obtain hydrogen, hydrogen chloride and chlorosilane gas；Hydrogen returns to step (1), and hydrogen chloride sends to conjunction Into trichlorosilane；Chlorosilane is sent to after rectifying separating-purifying, obtains silicon tetrachloride and trichlorosilane, and wherein silicon tetrachloride accounts for few portion Point, it is largely trichlorosilane, silicon tetrachloride returns to step (1), and trichlorosilane hydrogen reduction produces polysilicon for reduction.
The conversion ratio of silicon tetrachloride is 82% in embodiment (3).
A kind of hydrogenation of silicon tetrachloride technique described in the embodiment of the present invention, compared with traditional handicraft, four in hydrogenation process Chlorination silicon conversion can reach more than 80%, and tail gas out comprises only a small amount of hydrogen and silicon tetrachloride, substantial amounts of trichlorine Hydrogen silicon and hydrogen chloride, these tail gas are sent in retracting device, and each component is separated, and is recycled.The work Skill is combined with micro- chemical process, the characteristics of using macro work micro-channel mixer, micro passage reaction, in micron-sized channel-type Percussion flow chemical reaction is carried out in reactor；Because space reactor is very small, material is highly uniform by collisional mixing, connects Touch reaction complete, so as to improve the security of reaction speed, the rate of producing into, selectivity, production technology, money can also be saved Source, reduction energy consumption, environmental protection.
Embodiment 4.
(1) silicon tetrachloride gas and hydrogen are pressed 0.4：1 mol ratio is heated and mixed into microchannel hybrid heater, Heating-up temperature is 500 DEG C, after reaction terminates, the mixed gas after must heating.Microchannel hybrid heater is placed in electrically heated add In thermal；Wherein, heater sets lagging facility and temperature automatically controlled facility.Microchannel hybrid heater includes several micro- logical Road mixer unit and several heater elements, micro-channel mixer unit and heater element are in arranged for interval, as shown in Figure 1；It is micro- Channel mixer unit includes the micro-channel mixer substrate of 40, to ensure that heat is quickly transmitted；Micro-channel mixer base Piece includes the microchannel no less than 1；The width of microchannel is 400 microns, and depth is 150 microns, microchannel upper and lower part It is preferred that do as shown in figure 3, surface area can be increased to improve mixing efficiency, heat conduction efficiency.The microchannel mixing adds The material of hot device is corrosion resisting alloy.
(2) mixed gas after heating is sent into micro passage reaction by insulation, corrosion resistant pipeline, heated and in oxidation Reacted under the catalysis of aluminium, heating-up temperature is 1250 DEG C, obtains reacted mixed gas.Micro passage reaction is placed in electrically heated add In thermal；Wherein, heater sets lagging facility and temperature automatically controlled facility.Micro passage reaction includes several microchannel plates Device unit and several heater elements are answered, micro passage reaction unit and heater element are in arranged for interval, as shown in Figure 2；Microchannel Reactor unit includes the micro passage reaction substrate of 30, to ensure that heat is quickly transmitted；Micro passage reaction substrate bag Include the microchannel no less than 1；The width of microchannel is 250 microns, and depth is 180 microns, and (width of microchannel is not less than deep Degree), it is that microchannel upper and lower part is preferably done as shown in figure 3, surface area can be increased to improve mixing efficiency, heat transfer effect Rate.The material of micro passage reaction is corrosion resisting alloy.
(3) by reacted mixed gas fast cooling to 250 DEG C, it is easy to suppress side reaction, enters back into recovery separation dress Put, each component is separated, obtain hydrogen, hydrogen chloride and chlorosilane gas；Hydrogen returns to step (1), and hydrogen chloride sends to conjunction Into trichlorosilane；Chlorosilane is sent to after rectifying separating-purifying, obtains silicon tetrachloride and trichlorosilane, and wherein silicon tetrachloride accounts for few portion Point, it is largely trichlorosilane, silicon tetrachloride returns to step (1), and trichlorosilane hydrogen reduction produces polysilicon for reduction.
The conversion ratio of silicon tetrachloride is 72% in embodiment (4).
A kind of hydrogenation of silicon tetrachloride technique described in the embodiment of the present invention, compared with traditional handicraft, four in hydrogenation process Chlorination silicon conversion can reach more than 50%, and tail gas out comprises only a small amount of hydrogen and silicon tetrachloride, substantial amounts of trichlorine Hydrogen silicon and hydrogen chloride, these tail gas are sent in retracting device, and each component is separated, and is recycled.The work Skill is combined with micro- chemical process, the characteristics of using macro work micro-channel mixer, micro passage reaction, in micron-sized channel-type Percussion flow chemical reaction is carried out in reactor；Because space reactor is very small, material is highly uniform by collisional mixing, connects Touch reaction complete, so as to improve the security of reaction speed, the rate of producing into, selectivity, production technology, money can also be saved Source, reduction energy consumption, environmental protection.
A kind of hydrogenation of silicon tetrachloride technique, its reaction principle is：SiCl4+2H2=Si+4HCl (high temperature+catalyst), with reference to Process chart and embodiment 5-8 shown in Fig. 5, further Jie in detail is to a kind of hydrogenation of silicon tetrachloride technique of the invention Continue.
Embodiment 5.
(1) silicon tetrachloride gas and hydrogen are pressed 0.1：1 mol ratio is heated and mixed into microchannel hybrid heater, Heating-up temperature is 800 DEG C, the mixed gas after must heating.Microchannel hybrid heater is placed in electrically heated heater；Its In, heater sets lagging facility and temperature automatically controlled facility.Microchannel hybrid heater includes several micro-channel mixer lists First and several heater elements, micro-channel mixer unit and heater element are in arranged for interval, as shown in Figure 1；Micro-channel mixer Unit includes the micro-channel mixer substrate of 100, to ensure that heat is quickly transmitted；Micro-channel mixer substrate includes many In the microchannel of 1；The width of microchannel is 10 microns, and depth is 10 microns (width of microchannel is not less than depth), micro- logical It is that road upper and lower part is preferably done as shown in figure 3, surface area can be increased to improve mixing efficiency, heat conduction efficiency.It is micro- logical The material of road hybrid heater is ceramics.
(2) mixed gas after heating is sent into micro passage reaction by insulation, corrosion resistant pipeline, heated and in oxidation Reacted under the catalysis of aluminium, heating-up temperature is 1400 DEG C, after reaction terminates, obtains reacted mixture；By reacted mixing Thing is cooled to 250 DEG C, is easy to suppress side reaction, then is separated by solid and gas, obtains the mixed gas after HIGH-PURITY SILICON and cooling.Microchannel Reactor is placed in electrically heated heater；Wherein, heater sets lagging facility and temperature automatically controlled facility.Microchannel plate Device is answered to include several micro passage reaction units and several heater elements, micro passage reaction unit and heater element are in interval cloth Put, as shown in Figure 2；Micro passage reaction unit includes the micro passage reaction substrate of 100, to ensure that heat is quickly passed Pass；Micro passage reaction substrate includes the microchannel no less than 1；The width of microchannel is 10 microns, and depth is 10 microns (micro- The width of passage is not less than depth), it is that microchannel upper and lower part is preferably done as shown in figure 3, surface area can be increased to carry High mixing efficiency, heat conduction efficiency.The material of micro passage reaction is ceramics.
(3) cool down after mixed gas enter reclaim separator, each component is separated, obtain hydrogen, hydrogen chloride and Chlorosilane gas；HIGH-PURITY SILICON product is sold, and hydrogen returns to step (1), and hydrogen chloride sends to synthesizing trichlorosilane；Chlorosilane is sent to After rectifying separating-purifying, silicon tetrachloride and trichlorosilane are obtained, silicon tetrachloride returns to step (1), and trichlorosilane is used for hydrogen also Original produces polysilicon.
The conversion ratio of silicon tetrachloride is 65% in embodiment (5).
A kind of hydrogenation of silicon tetrachloride technique described in the embodiment of the present invention, compared with traditional handicraft, four in hydrogenation process Chlorination silicon conversion can reach more than 50%, and tail gas out comprises only a small amount of hydrogen and silicon tetrachloride, substantial amounts of chlorination Hydrogen and HIGH-PURITY SILICON, these tail gas are sent in retracting device, and each component is separated, recycled；And the work Skill direct hydrogenation produces HIGH-PURITY SILICON, and high conversion rate, comprehensive energy consumption is low, and production process is not by secondary pollution.Also the technique with it is micro- Chemical process is combined, the characteristics of using macro work micro-channel mixer, micro passage reaction, in micron-sized channel-type reactor Interior progress percussion flow chemical reaction；Because space reactor is very small, material is highly uniform by collisional mixing, haptoreaction Completely, so as to improve the security of reaction speed, the rate of producing into, selectivity, production technology, resource, reduction can also be saved Energy consumption, environmental protection.
Embodiment 6.
(1) silicon tetrachloride gas and hydrogen are pressed 0.3：1 mol ratio is heated and mixed into microchannel hybrid heater, Heating-up temperature is 100 DEG C, the mixed gas after must heating.Microchannel hybrid heater is placed in electrically heated heater；Its In, heater sets lagging facility and temperature automatically controlled facility.Microchannel hybrid heater includes several micro-channel mixer lists First and several heater elements, micro-channel mixer unit and heater element are in arranged for interval, as shown in Figure 1；Micro-channel mixer Unit includes the micro-channel mixer substrate of 10, to ensure that heat is quickly transmitted；Micro-channel mixer substrate includes many In the microchannel of 1；The width of microchannel is 500 microns, and depth is 300 microns (width of microchannel is not less than depth), micro- It is that channel upper and bottom are preferably done as shown in figure 3, surface area can be increased to improve mixing efficiency, heat conduction efficiency.It is micro- The material of passage hybrid heater is carborundum.
(2) mixed gas after heating is sent into micro passage reaction by insulation, corrosion resistant pipeline, heated and in oxidation Reacted under the catalysis of aluminium, heating-up temperature is 700 DEG C, after reaction terminates, obtains reacted mixture；By reacted mixture 350 DEG C are cooled to, is easy to suppress side reaction, then is separated by solid and gas, the mixed gas after HIGH-PURITY SILICON and cooling is obtained.Microchannel plate Device is answered to be placed in electrically heated heater；Wherein, heater sets lagging facility and temperature automatically controlled facility.Microchannel plate should Device includes several micro passage reaction units and several heater elements, and micro passage reaction unit and heater element are in interval cloth Put, as shown in Figure 2；Micro passage reaction unit includes the micro passage reaction substrate of 10, to ensure that heat is quickly transmitted； Micro passage reaction substrate includes the microchannel no less than 1；The width of microchannel is 500 microns, and depth is 300 microns (micro- The width of passage is not less than depth), it is that microchannel upper and lower part is preferably done as shown in figure 3, surface area can be increased to carry High mixing efficiency, heat conduction efficiency.The material of micro passage reaction is carborundum.
(3) mixed gas after cooling down, which enters, reclaims separator, and each component is separated, hydrogen, hydrogen chloride, chlorine is obtained Silane gas；HIGH-PURITY SILICON product is sold, and hydrogen returns to step (1), and hydrogen chloride sends to synthesizing trichlorosilane；Chlorosilane is sent to essence Evaporate after separating-purifying, obtain silicon tetrachloride and trichlorosilane, silicon tetrachloride returns to step (1), and trichlorosilane is used for hydrogen reduction Produce polysilicon.
The conversion ratio of silicon tetrachloride is 51% in embodiment (6).
A kind of hydrogenation of silicon tetrachloride technique described in the embodiment of the present invention, compared with traditional handicraft, four in hydrogenation process Chlorination silicon conversion can reach more than 50%, and tail gas out comprises only a small amount of hydrogen and silicon tetrachloride, substantial amounts of chlorination Hydrogen and HIGH-PURITY SILICON, these tail gas are sent in retracting device, and each component is separated, recycled；And the work Skill direct hydrogenation produces HIGH-PURITY SILICON, and high conversion rate, comprehensive energy consumption is low, and production process is not by secondary pollution.Also the technique with it is micro- Chemical process is combined, the characteristics of using macro work micro-channel mixer, micro passage reaction, in micron-sized channel-type reactor Interior progress percussion flow chemical reaction；Because space reactor is very small, material is highly uniform by collisional mixing, haptoreaction Completely, so as to improve the security of reaction speed, the rate of producing into, selectivity, production technology, resource, reduction can also be saved Energy consumption, environmental protection.
Embodiment 7.
(1) silicon tetrachloride gas and hydrogen are pressed 1：6 mol ratio is heated and mixed into microchannel hybrid heater, plus Hot temperature is 600 DEG C, the mixed gas after must heating.Microchannel hybrid heater is placed in electrically heated heater；Wherein, Heater sets lagging facility and temperature automatically controlled facility.Microchannel hybrid heater include several micro-channel mixer units and Several heater elements, micro-channel mixer unit and heater element are in arranged for interval, as shown in Figure 1；Micro-channel mixer unit Including the micro-channel mixer substrate of 20, to ensure that heat is quickly transmitted；Micro-channel mixer substrate includes being no less than 1 Microchannel；The width of microchannel is 200 microns, and depth is on 100 microns (width of microchannel is not less than depth), microchannel It is that portion and bottom are preferably done as shown in figure 3, surface area can be increased to improve mixing efficiency, heat conduction efficiency.Mix microchannel The material for closing heater is sapphire.
(2) mixed gas after heating is sent into micro passage reaction by insulation, corrosion resistant pipeline, heated and in oxidation Reacted under the catalysis of aluminium, heating-up temperature is 1360 DEG C, after reaction terminates, obtains reacted mixture；By reacted mixing Thing is cooled to 300 DEG C, is easy to suppress side reaction, then is separated by solid and gas, obtains the mixed gas after HIGH-PURITY SILICON and cooling.Microchannel Reactor is placed in electrically heated heater；Wherein, heater sets lagging facility and temperature automatically controlled facility.Microchannel plate Device is answered to include several micro passage reaction units and several heater elements, micro passage reaction unit and heater element are in interval cloth Put, as shown in Figure 2；Micro passage reaction unit includes the micro passage reaction substrate of 20 pieces, to ensure that heat is quickly passed Pass；Micro passage reaction substrate includes the microchannel no less than 1；The width of microchannel is 200 microns, and depth is 100 microns (width of microchannel be not less than depth), it is that microchannel upper and lower part is preferably done as shown in figure 3, can increase surface area so as to Improve mixing efficiency, heat conduction efficiency.The material of micro passage reaction is sapphire.
(3) mixed gas after cooling down, which enters, reclaims separator, and each component is separated, hydrogen, hydrogen chloride, chlorine is obtained Silane gas；HIGH-PURITY SILICON product is sold, and hydrogen returns to step (1), and hydrogen chloride sends to synthesizing trichlorosilane；Chlorosilane is sent to essence Evaporate after separating-purifying, obtain silicon tetrachloride and trichlorosilane, silicon tetrachloride returns to step (1), and trichlorosilane is used for hydrogen reduction Produce polysilicon.
The conversion ratio of silicon tetrachloride is 83% in embodiment (7).
A kind of hydrogenation of silicon tetrachloride technique described in the embodiment of the present invention, compared with traditional handicraft, four in hydrogenation process Chlorination silicon conversion can reach more than 80%, and tail gas out comprises only a small amount of hydrogen and silicon tetrachloride, substantial amounts of chlorination Hydrogen and HIGH-PURITY SILICON, these tail gas are sent in retracting device, and each component is separated, recycled；And the work Skill direct hydrogenation produces HIGH-PURITY SILICON, and high conversion rate, comprehensive energy consumption is low, and production process is not by secondary pollution.Also the technique with it is micro- Chemical process is combined, the characteristics of using macro work micro-channel mixer, micro passage reaction, in micron-sized channel-type reactor Interior progress percussion flow chemical reaction；Because space reactor is very small, material is highly uniform by collisional mixing, haptoreaction Completely, so as to improve the security of reaction speed, the rate of producing into, selectivity, production technology, resource, reduction can also be saved Energy consumption, environmental protection.
Embodiment 8.
(1) silicon tetrachloride gas and hydrogen are pressed 0.2：1 mol ratio is heated and mixed into microchannel hybrid heater, Heating-up temperature is 500 DEG C, the mixed gas after must heating.Microchannel hybrid heater is placed in electrically heated heater；Its In, heater sets lagging facility and temperature automatically controlled facility.Microchannel hybrid heater includes several micro-channel mixer lists First and several heater elements, micro-channel mixer unit and heater element are in arranged for interval, as shown in Figure 1；Micro-channel mixer Unit includes the micro-channel mixer substrate of 30, to ensure that heat is quickly transmitted；Micro-channel mixer substrate includes many In the microchannel of 1；The width of microchannel is 440 microns, and depth is 250 microns (width of microchannel is not less than depth), micro- It is that channel upper and bottom are preferably done as shown in figure 3, surface area can be increased to improve mixing efficiency, heat conduction efficiency.It is micro- The material of passage hybrid heater is corrosion resisting alloy.
(2) mixed gas after heating is sent into micro passage reaction by insulation, corrosion resistant pipeline, heated and in oxidation Reacted under the catalysis of aluminium, heating-up temperature is 1380 DEG C, after reaction terminates, obtains reacted mixture；By reacted mixing Thing is cooled to 280 DEG C, is easy to suppress side reaction, then is separated by solid and gas, obtains the mixed gas after HIGH-PURITY SILICON and cooling.Microchannel Reactor is placed in electrically heated heater；Wherein, heater sets lagging facility and temperature automatically controlled facility.Microchannel plate Device is answered to include several micro passage reaction units and several heater elements, micro passage reaction unit and heater element are in interval cloth Put, as shown in Figure 2；Micro passage reaction unit includes the micro passage reaction substrate of 35, to ensure that heat is quickly transmitted； Micro passage reaction substrate includes the microchannel no less than 1；The width of microchannel is 250 microns, and depth is 150 microns (micro- The width of passage is not less than depth), it is that microchannel upper and lower part is preferably done as shown in figure 3, surface area can be increased to carry High mixing efficiency, heat conduction efficiency.The material of micro passage reaction is corrosion resisting alloy.
(3) mixed gas after cooling down, which enters, reclaims separator, and each component is separated, hydrogen, hydrogen chloride, chlorine is obtained Silane gas；HIGH-PURITY SILICON product is sold, and hydrogen returns to step (1), and hydrogen chloride sends to synthesizing trichlorosilane；Chlorosilane is sent to essence Evaporate after separating-purifying, obtain silicon tetrachloride and trichlorosilane, silicon tetrachloride returns to step (1), and trichlorosilane is used for hydrogen reduction Produce polysilicon.
The conversion ratio of silicon tetrachloride is 74% in embodiment (8).
A kind of hydrogenation of silicon tetrachloride technique described in the embodiment of the present invention, compared with traditional handicraft, four in hydrogenation process Chlorination silicon conversion can reach more than 50%, and tail gas out comprises only a small amount of hydrogen and silicon tetrachloride, substantial amounts of chlorination Hydrogen and HIGH-PURITY SILICON, these tail gas are sent in retracting device, and each component is separated, recycled；And the work Skill direct hydrogenation produces HIGH-PURITY SILICON, and high conversion rate, comprehensive energy consumption is low, and production process is not by secondary pollution.Also the technique with it is micro- Chemical process is combined, the characteristics of using macro work micro-channel mixer, micro passage reaction, in micron-sized channel-type reactor Interior progress percussion flow chemical reaction；Because space reactor is very small, material is highly uniform by collisional mixing, haptoreaction Completely, so as to improve the security of reaction speed, the rate of producing into, selectivity, production technology, resource, reduction can also be saved Energy consumption, environmental protection.
A kind of trichlorosilane prepares high-purity silicon technology, and its reaction principle is：SiHCl3+H2=Si+3HCl (catalyst+height Temperature), process chart and embodiment 9-12 with reference to shown in Fig. 6 prepare high-purity silicon technology to a kind of trichlorosilane of the invention and done Further it is discussed in detail.
Embodiment 9.
(1) trichlorosilane gas and hydrogen are pressed 0.2：1 mol ratio is heated and mixed into microchannel hybrid heater, Heating-up temperature is 800 DEG C, the mixed gas after must heating.Microchannel hybrid heater is placed in electrically heated heater；Its In, heater sets lagging facility and temperature automatically controlled facility.Microchannel hybrid heater includes several micro-channel mixer lists First and several heater elements, micro-channel mixer unit and heater element are in arranged for interval, as shown in Figure 1；Micro-channel mixer Unit includes the micro-channel mixer substrate of 10, to ensure that heat is quickly transmitted；Micro-channel mixer substrate includes many In the microchannel of 1；The width of microchannel is 500 microns, and depth is 300 microns (width of microchannel is not less than depth), micro- It is that channel upper and bottom are preferably done as shown in figure 3, surface area can be increased to improve mixing efficiency, heat conduction efficiency.Institute The material for stating microchannel hybrid heater is corrosion resisting alloy.
(2) mixed gas after heating is sent into micro passage reaction by insulation, corrosion resistant pipeline, is heated to 1300 DEG C, and reacted under the catalysis of aluminum oxide, after reaction terminates, obtain reacted mixture.Micro passage reaction is placed in electrical heating Heater in；Wherein, heater sets lagging facility and temperature automatically controlled facility.Micro passage reaction includes several micro- logical Road reactor unit and several heater elements, micro passage reaction unit and heater element are in arranged for interval, as shown in Figure 2；It is micro- Channel reactor unit includes the micro passage reaction substrate of 100, to ensure that heat is quickly transmitted；Micro passage reaction base Piece includes the microchannel no less than 1；The width of microchannel is 10 microns, and depth is 10 microns, and (width of microchannel is not less than Depth), it is that microchannel upper and lower part is preferably done as shown in figure 3, surface area can be increased to improve mixing efficiency, heat transfer Efficiency.The material of micro passage reaction is corrosion resisting alloy.
(3) reacted mixture is cooled to 250 DEG C, is easy to suppress side reaction, then separated by solid and gas, obtain HIGH-PURITY SILICON With the mixed gas after cooling；Mixed gas after cooling, which enters, reclaims separator, and each component is separated, obtain hydrogen, Hydrogen chloride and chlorosilane gas；HIGH-PURITY SILICON product is sold, and hydrogen returns to step (1), and hydrogen chloride sends to synthesizing trichlorosilane；Chlorine Silane is sent to after rectifying separating-purifying, obtains trichlorosilane and silicon tetrachloride, and trichlorosilane returns to step (1).
The conversion ratio of trichlorosilane is 56% in embodiment (9).
A kind of trichlorosilane described in the embodiment of the present invention prepares high-purity silicon technology, compared with traditional handicraft, hydrogenation process In trichlorosilane conversion ratio can reach more than 50%, out tail gas comprise only a small amount of hydrogen and trichlorosilane, largely Hydrogen chloride and HIGH-PURITY SILICON, these tail gas are sent in retracting device, each component are separated, recycled；And And the process synthesis energy consumption is low, production process is not by secondary pollution.Also the technique is combined with micro- chemical process, utilizes macro work The characteristics of micro-channel mixer, micro passage reaction, percussion flow chemical reaction is carried out in micron-sized channel-type reactor；By Very small in space reactor, material is highly uniform by collisional mixing, and haptoreaction is completely, fast so as to improve reaction Spend, the security of the rate of producing into, selectivity, production technology, can also save resource, reduction energy consumption, environmental protection.
Embodiment 10.
(1) trichlorosilane gas and hydrogen are pressed 0.5：1 mol ratio is heated and mixed into microchannel hybrid heater, Heating-up temperature is 100 DEG C, the mixed gas after must heating.Microchannel hybrid heater is placed in electrically heated heater；Its In, heater sets lagging facility and temperature automatically controlled facility.Microchannel hybrid heater includes several micro-channel mixer lists First and several heater elements, micro-channel mixer unit and heater element are in arranged for interval, as shown in Figure 1；Micro-channel mixer Unit includes the micro-channel mixer substrate of 100, to ensure that heat is quickly transmitted；Micro-channel mixer substrate includes many In the microchannel of 1；The width of microchannel is 10 microns, and depth is 10 microns (width of microchannel is not less than depth), micro- logical It is that road upper and lower part is preferably done as shown in figure 3, surface area can be increased to improve mixing efficiency, heat conduction efficiency.It is micro- logical The material of road hybrid heater is ceramics.
(2) mixed gas after heating is sent into micro passage reaction by insulation, corrosion resistant pipeline, is heated to 1000 DEG C, and reacted under the catalysis of aluminum oxide, after reaction terminates, obtain reacted mixture.Micro passage reaction is placed in electrical heating Heater in；Wherein, heater sets lagging facility and temperature automatically controlled facility.Micro passage reaction includes several micro- logical Road reactor unit and several heater elements, micro passage reaction unit and heater element are in arranged for interval, as shown in Figure 2；It is micro- Channel reactor unit includes the micro passage reaction substrate of 10, to ensure that heat is quickly transmitted；Micro passage reaction base Piece includes the microchannel no less than 1；The width of microchannel is 500 microns, and depth is 300 microns, and (width of microchannel is not small In depth), it is that microchannel upper and lower part is preferably done to be passed as shown in figure 3, surface area increased to improve mixing efficiency, heat Lead efficiency.The material of micro passage reaction is ceramics.
(3) reacted mixture is cooled to 350 DEG C, is easy to suppress side reaction, then separated by solid and gas, obtain HIGH-PURITY SILICON With the mixed gas after cooling；Mixed gas after cooling, which enters, reclaims separator, and each component is separated, obtain hydrogen, Hydrogen chloride and chlorosilane gas；HIGH-PURITY SILICON product is sold, and hydrogen returns to step (1), and hydrogen chloride sends to synthesizing trichlorosilane；Chlorine Silane is sent to after rectifying separating-purifying, obtains trichlorosilane and silicon tetrachloride, and trichlorosilane returns to step (1).
The conversion ratio of trichlorosilane is 66% in embodiment (10).
A kind of trichlorosilane described in the embodiment of the present invention prepares high-purity silicon technology, compared with traditional handicraft, hydrogenation process In trichlorosilane conversion ratio can reach more than 50%, out tail gas comprise only a small amount of hydrogen and trichlorosilane, largely Hydrogen chloride and HIGH-PURITY SILICON, these tail gas are sent in retracting device, each component are separated, recycled；And And the process synthesis energy consumption is low, production process is not by secondary pollution.Also the technique is combined with micro- chemical process, utilizes macro work The characteristics of micro-channel mixer, micro passage reaction, percussion flow chemical reaction is carried out in micron-sized channel-type reactor；By Very small in space reactor, material is highly uniform by collisional mixing, and haptoreaction is completely, fast so as to improve reaction Spend, the security of the rate of producing into, selectivity, production technology, can also save resource, reduction energy consumption, environmental protection.
Embodiment 11.
(1) trichlorosilane gas and hydrogen are pressed 1：3 mol ratio is heated and mixed into microchannel hybrid heater, plus Hot temperature is 600 DEG C, the mixed gas after must heating.Microchannel hybrid heater is placed in electrically heated heater；Wherein, Heater sets lagging facility and temperature automatically controlled facility.Microchannel hybrid heater include several micro-channel mixer units and Several heater elements, micro-channel mixer unit and heater element are in arranged for interval, as shown in Figure 1；Micro-channel mixer unit Including the micro-channel mixer substrate of 20, to ensure that heat is quickly transmitted；Micro-channel mixer substrate includes being no less than 1 Microchannel；The width of microchannel is 200 microns, and depth is on 100 microns (width of microchannel is not less than depth), microchannel It is that portion and bottom are preferably done as shown in figure 3, surface area can be increased to improve mixing efficiency, heat conduction efficiency.Mix microchannel The material for closing heater is sapphire.
(2) mixed gas after heating is sent into micro passage reaction by insulation, corrosion resistant pipeline, is heated to 1250 DEG C, and reacted under the catalysis of aluminum oxide, after reaction terminates, obtain reacted mixture.Micro passage reaction is placed in electrical heating Heater in；Wherein, heater sets lagging facility and temperature automatically controlled facility.Micro passage reaction includes several micro- logical Road reactor unit and several heater elements, micro passage reaction unit and heater element are in arranged for interval, as shown in Figure 2；It is micro- Channel reactor unit includes the micro passage reaction substrate of 20 pieces, to ensure that heat is quickly transmitted；Micro passage reaction Substrate includes the microchannel no less than 1；The width of microchannel is 200 microns, and depth is 100 microns, and (width of microchannel is not Less than depth), it is that microchannel upper and lower part is preferably done as shown in figure 3, surface area can be increased to improve mixing efficiency, heat Conduction efficiency.The material of micro passage reaction is sapphire.
(3) reacted mixture is cooled to 300 DEG C, is easy to suppress side reaction, then separated by solid and gas, obtain HIGH-PURITY SILICON With the mixed gas after cooling；Mixed gas after cooling, which enters, reclaims separator, and each component is separated, obtain hydrogen, Hydrogen chloride and chlorosilane gas；HIGH-PURITY SILICON product is sold, and hydrogen returns to step (1), and hydrogen chloride sends to synthesizing trichlorosilane；Chlorine Silane is sent to after rectifying separating-purifying, obtains trichlorosilane and silicon tetrachloride, and trichlorosilane returns to step (1).
The conversion ratio of trichlorosilane is 81% in embodiment (11).
A kind of trichlorosilane described in the embodiment of the present invention prepares high-purity silicon technology, compared with traditional handicraft, hydrogenation process In trichlorosilane conversion ratio can reach more than 80%, out tail gas comprise only a small amount of hydrogen and trichlorosilane, largely Hydrogen chloride and HIGH-PURITY SILICON, these tail gas are sent in retracting device, each component are separated, recycled；And And the process synthesis energy consumption is low, production process is not by secondary pollution.Also the technique is combined with micro- chemical process, utilizes macro work The characteristics of micro-channel mixer, micro passage reaction, percussion flow chemical reaction is carried out in micron-sized channel-type reactor；By Very small in space reactor, material is highly uniform by collisional mixing, and haptoreaction is completely, fast so as to improve reaction Spend, the security of the rate of producing into, selectivity, production technology, can also save resource, reduction energy consumption, environmental protection.
Embodiment 12.
(1) trichlorosilane gas and hydrogen are pressed 1：4 mol ratio is heated and mixed into microchannel hybrid heater, plus Hot temperature is 500 DEG C, the mixed gas after must heating.Microchannel hybrid heater is placed in electrically heated heater；Wherein, Heater sets lagging facility and temperature automatically controlled facility.Microchannel hybrid heater include several micro-channel mixer units and Several heater elements, micro-channel mixer unit and heater element are in arranged for interval, as shown in Figure 1；Micro-channel mixer unit Including the micro-channel mixer substrate of 25, to ensure that heat is quickly transmitted；Micro-channel mixer substrate includes being no less than 1 Microchannel；The width of microchannel is 400 microns, and depth is on 130 microns (width of microchannel is not less than depth), microchannel It is that portion and bottom are preferably done as shown in figure 3, surface area can be increased to improve mixing efficiency, heat conduction efficiency.Mix microchannel The material for closing heater is carborundum.
(2) mixed gas after heating is sent into micro passage reaction by insulation, corrosion resistant pipeline, is heated to 1280 DEG C, and reacted under the catalysis of aluminum oxide, after reaction terminates, obtain reacted mixture.Micro passage reaction is placed in electrical heating Heater in；Wherein, heater sets lagging facility and temperature automatically controlled facility.Micro passage reaction includes several micro- logical Road reactor unit and several heater elements, micro passage reaction unit and heater element are in arranged for interval, as shown in Figure 2；It is micro- Channel reactor unit includes the micro passage reaction substrate of 35, to ensure that heat is quickly transmitted；Micro passage reaction base Piece includes the microchannel no less than 1；The width of microchannel is 280 microns, and depth is 160 microns, and (width of microchannel is not small In depth), it is that microchannel upper and lower part is preferably done to be passed as shown in figure 3, surface area increased to improve mixing efficiency, heat Lead efficiency.The material of micro passage reaction is carborundum.
(3) reacted mixture is cooled to 310 DEG C, is easy to suppress side reaction, then separated by solid and gas, obtain HIGH-PURITY SILICON With the mixed gas after cooling；Mixed gas after cooling, which enters, reclaims separator, and each component is separated, obtain hydrogen, Hydrogen chloride and chlorosilane gas；HIGH-PURITY SILICON product is sold, and hydrogen returns to step (1), and hydrogen chloride sends to synthesizing trichlorosilane；Chlorine Silane is sent to after rectifying separating-purifying, obtains trichlorosilane and silicon tetrachloride, and trichlorosilane returns to step (1).
The conversion ratio of trichlorosilane is 74% in embodiment (12).
A kind of trichlorosilane described in the embodiment of the present invention prepares high-purity silicon technology, compared with traditional handicraft, hydrogenation process In trichlorosilane conversion ratio can reach more than 50%, out tail gas comprise only a small amount of hydrogen and trichlorosilane, largely Hydrogen chloride and HIGH-PURITY SILICON, these tail gas are sent in retracting device, each component are separated, recycled；And And the process synthesis energy consumption is low, production process is not by secondary pollution.Also the technique is combined with micro- chemical process, utilizes macro work The characteristics of micro-channel mixer, micro passage reaction, percussion flow chemical reaction is carried out in micron-sized channel-type reactor；By Very small in space reactor, material is highly uniform by collisional mixing, and haptoreaction is completely, fast so as to improve reaction Spend, the security of the rate of producing into, selectivity, production technology, can also save resource, reduction energy consumption, environmental protection.
It is described above, only it is the preferred embodiment of the embodiment of the present invention, not makees any shape to the embodiment of the present invention Limitation in formula, according to the embodiment of the present invention technical spirit above example is made any simple modification, equivalent variations With modification, in the range of still falling within technical scheme of the embodiment of the present invention.

Claims (10)

1. a kind of hydrogenation of silicon tetrachloride technique, it is characterised in that comprise the following steps：
(1) silicon tetrachloride gas and hydrogen are pressed into 0.2-0.5：1 mol ratio is heated and mixed into microchannel hybrid heater, Heating-up temperature is 100-700 DEG C, the mixed gas after must heating；Mixed gas after heating is sent into micro passage reaction, plus Heat is simultaneously reacted under the catalysis of catalyst, and heating-up temperature is 700-1300 DEG C, obtains reacted mixed gas；Will be reacted Mixed gas is cooled to 250-350 DEG C, the mixed gas after must cooling down；The catalyst is aluminum oxide；
Or silicon tetrachloride gas and hydrogen are pressed into 0.1-0.3：1 mol ratio is heated and mixed into microchannel hybrid heater, Heating-up temperature is 100-800 DEG C, the mixed gas after must heating；Mixed gas after heating is sent into micro passage reaction, plus Heat is simultaneously reacted under the catalysis of catalyst, and heating-up temperature is 700-1400 DEG C, obtains reacted mixture；Will be reacted Mixture is cooled to after 250-350 DEG C, is separated by solid and gas, obtains the mixed gas after HIGH-PURITY SILICON and cooling；The catalyst is Aluminum oxide；
(2) mixed gas after cooling down, which enters, reclaims separator, and each component is separated, hydrogen, hydrogen chloride and chlorine silicon is obtained Alkane gas；Hydrogen returns to step (1), and chlorosilane is sent to after rectifying separating-purifying, obtains silicon tetrachloride and trichlorosilane, tetrachloro SiClx returns to step (1).
2. hydrogenation process according to claim 1, it is characterised in that wherein,
In the step (1), the mol ratio of silicon tetrachloride gas and hydrogen is 1：3, the mixed gas temperature after heating is 600 ℃；Reacted mixed gas temperature is 1200-1300 DEG C；
Or in the step (1), the mol ratio of silicon tetrachloride gas and hydrogen is 1：6, the mixed gas temperature after heating is 600 ℃；Reacted mixture temperature is 1360-1400 DEG C.
3. hydrogenation process according to claim 1, it is characterised in that wherein,
The microchannel hybrid heater is placed in electrically heated heater；
Wherein, the heater sets lagging facility and temperature automatically controlled facility；
The microchannel hybrid heater includes micro-channel mixer unit and heater element, micro-channel mixer unit and heating Device is in arranged for interval；The micro-channel mixer unit includes the micro-channel mixer substrate no less than 1；The microchannel Blender substrate includes the microchannel no less than 1；The width of the microchannel is 10-500 microns, and depth is that 10-300 is micro- Rice；
The micro passage reaction is placed in electrically heated heater；
Wherein, the heater sets lagging facility and temperature automatically controlled facility；
The micro passage reaction includes micro passage reaction unit and heater element, micro passage reaction unit and heater element In arranged for interval；The micro passage reaction unit includes the micro passage reaction substrate no less than 1；The microchannel plate should Device substrate includes the microchannel no less than 1；The width of the microchannel is 10-500 microns, and depth is 10-300 microns.
4. hydrogenation process according to claim 3, it is characterised in that wherein,
In the microchannel hybrid heater, the micro-channel mixer unit includes the micro-channel mixer base of 10-100 pieces Piece；The width of the microchannel is 200 microns, and depth is 100 microns；The material of the microchannel hybrid heater is blue precious One kind in stone, carborundum, ceramics and corrosion resisting alloy；
In the micro passage reaction, the micro passage reaction unit includes the micro passage reaction substrate of 10-100 pieces；Institute The width for stating microchannel is 200 microns, and depth is 100 microns；The material of the micro passage reaction be sapphire, carborundum, One kind in ceramics and corrosion resisting alloy.
5. hydrogenation process according to claim 4, it is characterised in that wherein,
In the microchannel hybrid heater, the micro-channel mixer unit includes the micro-channel mixer substrate of 20；Institute The material for stating microchannel hybrid heater is sapphire；
The micro passage reaction unit includes the micro passage reaction substrate of 20；The material of the micro passage reaction is indigo plant Jewel.
6. a kind of trichlorosilane prepares high-purity silicon technology, it is characterised in that comprise the following steps：
(1) trichlorosilane gas and hydrogen are heated and mixed into microchannel hybrid heater, heating-up temperature is 100-800 DEG C, the mixed gas after must heating；The mol ratio of the trichlorosilane gas and hydrogen is 0.2-0.5：1；
(2) mixed gas after heating is sent into micro passage reaction, is heated to 1000-1300 DEG C, and in the presence of catalyst Lower reaction, obtains reacted mixture；The catalyst is aluminum oxide；
(3) reacted mixture is cooled to after 250-350 DEG C, separated by solid and gas, obtain the mixing after HIGH-PURITY SILICON and cooling Gas；Mixed gas after cooling, which enters, reclaims separator, and each component is separated, hydrogen, hydrogen chloride and chlorosilane is obtained Gas；Hydrogen returns to step (1)；Chlorosilane is sent to after rectifying separating-purifying, obtains trichlorosilane and silicon tetrachloride, trichlorine hydrogen Silicon returns to step (1).
7. trichlorosilane according to claim 6 prepares high-purity silicon technology, it is characterised in that wherein,
In the step (1), the mol ratio of trichlorosilane gas and hydrogen is 1:3-4, heating-up temperature is 600 DEG C；
In the step (2), heating-up temperature is 1250-1300 DEG C.
8. trichlorosilane according to claim 6 prepares high-purity silicon technology, it is characterised in that wherein,
The microchannel hybrid heater is placed in electrically heated heater；
Wherein, the heater sets lagging facility and temperature automatically controlled facility；
The microchannel hybrid heater includes micro-channel mixer unit and heater element, micro-channel mixer unit and heating Device is in arranged for interval；The micro-channel mixer unit includes the micro-channel mixer substrate no less than 1；The microchannel Blender substrate includes the microchannel no less than 1；The width of the microchannel is 10-500 microns, and depth is that 10-300 is micro- Rice；
The micro passage reaction is placed in electrically heated heater；
Wherein, the heater sets lagging facility and temperature automatically controlled facility；
The micro passage reaction includes micro passage reaction unit and heater element, micro passage reaction unit and heater element In arranged for interval；The micro passage reaction unit includes the micro passage reaction substrate no less than 1；The microchannel plate should Device substrate includes the microchannel no less than 1；The width of the microchannel is 10-500 microns, and depth is 10-300 microns.
9. trichlorosilane according to claim 8 prepares high-purity silicon technology, it is characterised in that wherein,
In the microchannel hybrid heater, the micro-channel mixer unit includes the micro-channel mixer base of 10-100 pieces Piece；The width of the microchannel is 200 microns, and depth is 100 microns；The material of the microchannel hybrid heater is blue precious One kind in stone, carborundum, ceramics and corrosion resisting alloy；
In the micro passage reaction, the micro passage reaction unit includes the micro passage reaction substrate of 10-100 pieces；Institute The width for stating microchannel is 200 microns, and depth is 100 microns；The material of the micro passage reaction be sapphire, carborundum, One kind in ceramics and corrosion resisting alloy.
10. trichlorosilane according to claim 9 prepares high-purity silicon technology, it is characterised in that wherein,
In the microchannel hybrid heater, the micro-channel mixer unit includes the micro-channel mixer substrate of 20；Institute The material for stating microchannel hybrid heater is sapphire；
The micro passage reaction unit includes the micro passage reaction substrate of 20；The material of the micro passage reaction is indigo plant Jewel.
CN201710522320.7A 2017-06-30 2017-06-30 A kind of hydrogenation of silicon tetrachloride technique and trichlorosilane prepare high-purity silicon technology Pending CN107162003A (en)

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