CN105314637B - Halogen silicon polymer cracking prepares the method and device of halosilanes - Google Patents
Halogen silicon polymer cracking prepares the method and device of halosilanes Download PDFInfo
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- CN105314637B CN105314637B CN201510407316.7A CN201510407316A CN105314637B CN 105314637 B CN105314637 B CN 105314637B CN 201510407316 A CN201510407316 A CN 201510407316A CN 105314637 B CN105314637 B CN 105314637B
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Abstract
The step of the invention discloses the method and devices that a kind of halogen silicon polymer cracking prepares halosilanes, including halogen silicon polymer is passed through in cracking reactor, are cracked to form halosilanes under the action of catalyst and decomposition agent.According to the method for the present invention, without using auxiliary fuel, generation without waste residue, reduce discharge of wastewater, greatly improve the circulation of tail gas utilization rate of improved Siemens production of polysilicon, accomplish environmental-friendly, while halosilanes raw material needed for converting production of polysilicon for halogen silicon polymer, reduces production of polysilicon cost.
Description
Technical field
The present invention relates to the preparation technical field of high purity polycrystalline silicon, in particular to the halogen silicon generated in production of polysilicon polymerize
Object cracking prepares the method and device of halosilanes.
Background technique
Whole world production of polysilicon prevailing technology uses improved Siemens polysilicon production process, improved Siemens at present
It is, using high temperature reduction technique, in high-purity hydrogen atmosphere, trichlorosilane reduction to be deposited on silicon core using trichlorosilane as raw material
Above form polysilicon.In reduction reaction tail gas can comprising a large amount of unreacted trichlorosilanes, dichlorosilane, silicon tetrachloride,
Hydrogen and partial oxidation hydrogen, and the tail gas recycle process for entering rear end is handled.In addition, the technique is inevitable in process of production
Meeting generate chlorine silicon polymer (for polysilane, boiling point be high, and viscosity is big, and molecular formula is [SiHxCly]n), especially after scale amplification
Problem is more prominent.The method of common processing high-boiling components includes elution Hydrolyze method, but alkali lye consumption amount can be brought big, environmental pollution
Seriously, the problems such as production of polysilicon is at high cost.If effectively cannot directly recycle, a large amount of material waste will be caused, together
When it is extremely unfriendly to environment, cannot achieve the closed cycle of production of polysilicon truly.
In the prior art, CN200810017017.2, which is disclosed, a kind of prepares methylchlorosilane using organosilicon high-boiling product
2500Kg organosilicon high-boiling product and 62.5Kg catalyst are added in the cracking still with material filling type fractionating column by method.With steam plus
Heat is warming up to 115 DEG C, is passed through 25Nm from cracking still bottom3The hydrogen chloride gas (continuous) of/h reacts under normal pressure.Start reaction 1.2
Hour, high-boiling components 200Kg/h is continuously added into cracking still, and add catalyst 0.3Kg/h simultaneously, successive reaction 41 hours,
The mix monomer condensed out is continuously collected from condenser.For the conversion ratio of its high-boiling components up to 93.7%, catalyst is that mass ratio is 1:
1 tri-n-butylamine and N, the mixture of accelerine.
CN201110455830.X discloses a kind of using N, accelerine, tri-n-butylamine and N, N- diethyl formyl
Amine mixing be used as catalyst, 120-140 DEG C in reaction kettle by organosilicon high-boiling product and the hydrogen chloride of heating carry out catalysis split
The technical solution of solution.In addition, there are also such as CN200410094960.5 to disclose one kind organosilicon height at a temperature of 400-900 DEG C
Boil the technical solution that object and the hydrogen chloride Pintsch process under no catalysts conditions generate monomeric silanes.But skill is prepared in polysilicon
Art field is rarely reported by the technology that chlorine silicon polymer cracking prepares chlorosilane.
Summary of the invention
The object of the present invention is to provide a kind of methods that the cracking of halogen silicon polymer prepares halosilanes, and halogen silicon polymer is converted
For halosilanes raw material needed for production of polysilicon, and the generation without waste residue, reduce discharge of wastewater, makes improved Siemens polycrystalline
The circulation of tail gas utilization rate of silicon production greatly improves, and has accomplished environmental-friendly, while reducing production of polysilicon cost.
It is a further object of the present invention to provide the devices that a kind of halogen silicon polymer cracking prepares halosilanes, may be implemented above-mentioned
Technique.
To achieve the above object and technical effect, The technical solution adopted by the invention is as follows:
A kind of method that the cracking of halogen silicon polymer prepares halosilanes, comprising the following steps:
1) cracking reaction step: halogen silicon polymer, catalyst and decomposition agent are passed through in cracking reactor, 25~250
DEG C, cracking reaction occurs at preferably 100~250 DEG C of temperature and 0.05~0.5Mpa pressure condition and generates halosilanes；
2) gas-liquid separation step: the product of step 1) is preheated to 40~250 DEG C by preheater, preferably 100~250 DEG C into
Enter gas-liquid separator, control 0.05~0.3Mpa of pressure, is separated into the on-condensible gas at top and the liquid of bottom；
3) catalyst separating step: the liquid of step 2 separation enters catalyst separator, will at the top of catalyst separator
The halosilanes that reaction generates, which are collected, enters subsequent processing, and bottom obtains mixture；
4) process catalyst regeneration step: the mixture that step 3) bottom obtains is sent into catalyst regenerator and is regenerated；
5) circulation step: mixing by the catalyst that step 4) regenerates with raw catelyst, send to step 1) reactor
It recycles；
Wherein, the halogen in the halogen silicon polymer is selected from F, Cl, Br or I, preferably Cl；
The catalyst is nitrogenous compound, selected from one or more of nitro, nitrous base class, nitrile or amine；
The decomposition agent is by hydrogen halides, H2, halosilanes are mixed in a certain ratio.
In a preferred embodiment, further include 6) pre-treatment step: halogen silicon polymer is passed through into pretreatment of raw material
Device is handled, and halogen silicon polymer clear liquid is obtained, and the clear liquid is sent into step 1) and carries out cracking reaction.
In a preferred embodiment, further include 7) catalyst preparation step: by catalyst and halosilanes intermixture
It is mixed in a certain ratio preparation, it is 5%~60% that wherein catalyst, which accounts for the mass ratio of intermixture, and mixing temperature control is 30~100
℃。
Wherein, the catalyst circulation amount and halogen silicon polymer expect that clearly recycling mass ratio is 0.5 ~ 2.
Wherein, hydrogen halides molar content 3%~90% in the decomposition agent, H2Molar content 5%~90%, halosilanes mole contain
Amount 5 ~ 20%.
Wherein, the halogen silicon polymer and decomposition agent mass ratio are 1:0.13 ~ 0.15.
Wherein, the catalyst is nitrile and fatty amines mixed catalyst.
Wherein, the nitrile catalyst is selected from one of aliphatic nitrile or dintrile or mixing, aromatic series nitrile or two
One of nitrile or mixing.
Wherein, the Arneel SD is selected from the straight chain that carbon atom number is 3 ~ 20 or the Arneel SD with branch.
Wherein, the amines catalyst is selected from one of fatty amine or diamines or mixing.
Wherein, the fatty amine is selected from the straight chain that carbon atom number is 3 ~ 20 or the fatty amine with branch.
Another aspect of the present invention, a kind of aforementioned halogen silicon polymer cracking prepare the device of halosilanes method, including raw material
Preprocessor, catalyst preparation device, cracking reactor, gas-liquid separator, catalyst separator, catalyst regenerator, the original
Material preprocessor and the catalyst preparation device are connected with the cracking reactor respectively as charging, and the cracking reactor goes out
Material part is connected with the gas-liquid separator, and the gas-liquid separator is connected with the catalyst separator, the catalyst point
It is connected from device with the catalyst regenerator, the catalyst regenerator is connected with the catalyst preparation device.
Halogen silicon polymer cracking according to the present invention prepares the method and device of halosilanes, by special catalyst and splits
Halogen silicon polymer is cracked into halosilanes, cracking reaction fever, without using auxiliary fuel by solution agent system；Elution is not used to hydrolyze
Technique, the generation of no waste residue, reduces discharge of wastewater, makes the circulation of tail gas utilization rate of improved Siemens production of polysilicon significantly
It improves, has accomplished environmental-friendly, while halosilanes raw material needed for converting production of polysilicon for halogen silicon polymer, reduced more
Crystal silicon production cost.
Detailed description of the invention
Fig. 1 is the schematic device that halogen silicon polymer cracking of the present invention prepares halosilanes.
Wherein, 1 is raw material preprocessor, 2 cracking reactors, 3 preheaters, 4 gas-liquid separators, 5 catalyst separators, 6
Catalyst regenerator, 7 catalyst preparation devices, 8 pumps, 9 chlorine silicon polymers, 10 decomposition agents, 11 intermixtures, 12 catalyst, 13 are not coagulated
Gas, 14 chlorosilanes.
Specific embodiment
Detailed description of the preferred embodiments below, still, it is necessary to explanation, protection of the invention
Range is not limited to these specific embodiments, specifically proportion and response parameter and object involved in specific embodiment
Material selection is to enumerate in this embodiment to illustrate the invention, is not any limitation of the invention.
In a specific embodiment, a kind of method that the cracking of halogen silicon polymer prepares halosilanes, including following step
Rapid: 1) cracking reaction step: halogen silicon polymer, catalyst and decomposition agent are passed through in cracking reactor, in 25~250 DEG C of temperature
Halosilanes are generated with cracking reaction occurs under 0.05~0.5Mpa pressure condition；2) gas-liquid separation step: the product warp of step 1)
It crosses preheater and is preheated to 40~250 DEG C into gas-liquid separator, control 0.05~0.3Mpa of pressure, be separated into the fixed gas at top
The liquid of body and bottom；3) catalyst separating step: the liquid of step 2 separation enters catalyst separator, catalyst separator
The halosilanes that top generates reaction, which are collected, enters subsequent processing, and bottom obtains mixture；4) process catalyst regeneration step: step 3)
The mixture that bottom obtains is sent into catalyst regenerator and is regenerated；5) circulation step: the catalysis regenerated by step 4)
Agent is mixed with raw catelyst, is sent to step 1) reactor cycles and is utilized.
In a specific embodiment, a kind of method that the cracking of halogen silicon polymer prepares halosilanes, including following step
Rapid: 1) cracking reaction step: halogen silicon polymer, catalyst and decomposition agent are passed through in cracking reactor, in 100~250 DEG C of temperature
Cracking reaction occurs under degree and 0.05~0.5Mpa pressure condition and generates halosilanes；2) gas-liquid separation step: the product of step 1)
100~250 DEG C are preheated to by preheater and enters gas-liquid separator, controls 0.05~0.3Mpa of pressure, are separated into top not
The liquid of solidifying gas and bottom；3) catalyst separating step: the liquid of step 2 separation enters catalyst separator, catalyst point
It is collected from the halosilanes for generating reaction at the top of device and enters subsequent processing, bottom obtains mixture；4) process catalyst regeneration step: step
The mixture that rapid 3) bottom obtains is sent into catalyst regenerator and is regenerated；5) it circulation step: is regenerated by step 4)
Catalyst is mixed with raw catelyst, is sent to step 1) reactor cycles and is utilized.
It in a preferred embodiment, further include pretreatment and the catalyst preformulation step of raw material, i.e., a kind of halogen
The method that silicon polymer cracking prepares halosilanes, comprising the following steps: 1) pre-treatment step: halogen silicon polymer is pre- by raw material
Processor is handled, and halogen silicon polymer clear liquid is obtained, and the clear liquid is sent into step 3) and carries out cracking reaction；2) catalyst preparation
Step: being mixed in a certain ratio preparation for catalyst and halosilanes intermixture, and it is 5% that wherein catalyst, which accounts for the mass ratio of intermixture,
~60%, mixing temperature control is 30~100 DEG C；3) cracking reaction step: halogen silicon polymer, catalyst and decomposition agent are passed through
In cracking reactor, cracking reaction occurs at 25~250 DEG C of temperature and 0.05~0.5Mpa pressure condition and generates halosilanes；4)
Gas-liquid separation step: the product of step 3) is preheated to 40~250 DEG C by preheater and enters gas-liquid separator, controls pressure 0.05
~0.3Mpa is separated into the on-condensible gas at top and the liquid of bottom；5) catalyst separating step: step 4) separation liquid into
Enter catalyst separator, the halosilanes for reaction being generated at the top of catalyst separator, which are collected, enters subsequent processing, and bottom is mixed
Close object；6) process catalyst regeneration step: the mixture that step 5) bottom obtains is sent into catalyst regenerator and is regenerated；7) it recycles
Step: mixing by the catalyst that step 6) regenerates with raw catelyst, send to step 3) reactor cycles and utilizes.
It further include pretreatment and the catalyst preformulation step of raw material, i.e. one kind in a further preferred embodiment
The method that halogen silicon polymer cracking prepares halosilanes, comprising the following steps: 1) pre-treatment step: halogen silicon polymer is passed through into raw material
Preprocessor is handled, and halogen silicon polymer clear liquid is obtained, and the clear liquid is sent into step 3) and carries out cracking reaction；2) catalyst is matched
Step processed: being mixed in a certain ratio preparation for catalyst and halosilanes intermixture, and wherein catalyst accounts for the mass ratio of intermixture and is
5%~60%, mixing temperature control is 30~100 DEG C；3) cracking reaction step: halogen silicon polymer, catalyst and decomposition agent are led to
Enter in cracking reactor, cracking reaction occurs at 100~250 DEG C of temperature and 0.05~0.5Mpa pressure condition and generates halogen silicon
Alkane；4) gas-liquid separation step: the product of step 3) is preheated to 100~250 DEG C by preheater and enters gas-liquid separator, control pressure
0.05~0.3Mpa of power is separated into the on-condensible gas at top and the liquid of bottom；5) catalyst separating step: step 4) separation
Liquid enters catalyst separator, and the halosilanes for generating reaction at the top of catalyst separator, which are collected, enters subsequent processing, bottom
Obtain mixture；6) process catalyst regeneration step: the mixture that step 5) bottom obtains is sent into catalyst regenerator and is regenerated；
7) circulation step: mixing by the catalyst that step 6) regenerates with raw catelyst, send to step 3) reactor cycles and utilizes.
In the present invention, the halogen silicon polymer is, for example, that silicon-fluorine polymer object, chlorine silicon polymer, bromine silicon polymer, iodine silicon are poly-
Object object, preferably chlorine silicon polymer are closed, molecular formula is [SiHxCly]n, such as Si2Cl6、Si2HCl5、Si3H4Cl6Deng, but it is unlimited
In this.Methods and apparatus of the present invention is described in further detail by taking chlorine silicon polymer as an example below, is similarly applicable to other halogen
The situation of element, this is not limited the present invention in any way.
As shown in Figure 1, chlorine silicon polymer 9 is through raw material preprocessor 1, treated that clear liquid enters cracking reactor 2, cracking
Agent 10 enters cracking reactor 2, intermixture 11 and catalyst 12 enter after 7 preformulation of catalyst preparation device with regenerated catalyst
Cracking reactor 2 is squeezed by pump after mixing.Chlorine silicon polymer, catalyst and decomposition agent 25~250 DEG C of temperature and 0.05~
Under 0.5Mpa pressure condition, preferably 100~250 DEG C, 0.1~0.4Mpa；More preferably it is preheated to 150~200 DEG C, 0.2~
Under the conditions of 0.3Mpa, cracking reaction occurring in cracking 2 and generates the products such as chlorosilane, product is preheated to 40 by preheater 3~
250 DEG C enter gas-liquid separator 4, are preferably preheated to 100~250 DEG C, are more preferably preheated to 150~200 DEG C, control gas-liquid separation
The pressure of device 4 is 0.05~0.3Mpa, and under preferably 0.1~0.2Mpa pressure, pyrolysis product is separated into the on-condensible gas at top
13 and bottom liquid；The liquid of bottom separation enters catalyst separator 5, passes through the centrifugation of catalyst separator, top
Portion obtains the chlorosilane 11 that reaction generates and is collected into subsequent processing, and bottom obtains mixture；The mixing that bottom obtains
Object is sent into catalyst regenerator 6 and carries out catalyst regeneration；It regenerates obtained catalyst to mix with raw catelyst, send to cracking reaction
The reaction was continued for device 2, recycles；Or the obtained catalyst of regeneration enter catalyst preparation device 7 together with fresh catalyst into
After row is prepared, it is driven into (not shown) in cracking reactor 2.Pass through this process cycles, chlorine silicon polymer cracking production chlorine
This reaction mass of silane is turned waste into wealth by the reasonable utilization of material, reduces the production cost of polysilicon；Pass through simultaneously
The cracking of chlorine silicon polymer, the collection processing of chlorosilane, catalyst regeneration cycle, the generation of no waste residue, reduce waste water row
It puts, greatly improves the circulation of tail gas utilization rate of improved Siemens production of polysilicon, accomplished environmental-friendly.
In feed pretreatment step, chlorine silicon polymer obtains clear liquid by raw material preprocessor, and it is anti-that clear liquid enters cracking
Device is answered to participate in reaction.The pre-treatment step for example can be centrifuge separation, filtering, sedimentation etc., but not limited to this, as long as energy
Realize that the method being separated by solid-liquid separation or equipment may be applicable to the present invention.
The decomposition agent is directly entered cracking reactor, and the decomposition agent is by hydrogen halides, H2, halosilanes mix by a certain percentage
It closes.Halogen in decomposition agent is also selected from F, Cl, Br or I, preferably Cl or Br；Such as it is mixed by hydrogen chloride, hydrogen, chlorosilane
It closes.Hydrogen halides is, for example, hydrogen chloride or hydrogen bromide；Halosilanes are, for example, trichlorosilane, silicon tetrachloride, dichlorosilane, three
Any one of bromine hydrogen silicon, silicon bromide or dibromo dihydro silicon or mixing.By taking hydrogen chloride and chlorosilane as an example, wherein described to split
Solve hydrogen chloride molar content 3%~90% in agent, H2Molar content 5%~90%, chlorosilane molar content 5 ~ 20%；Preferably chlorination
Hydrogen molar content 10%~80%, H2Molar content 10%~80%, chlorosilane molar content 10 ~ 15%.The use of decomposition agent in the present invention
Amount is passed through according to the stoichiometric of chlorine silicon polymer cracking reaction, such as by halogen silicon polymer and decomposition agent mass ratio is 1:
0.13 ~ 0.15 is passed through, but not limited to this, it can be suitable according to the treating capacity of chlorine silicon polymer according to specific reactor for treatment ability
When the dosage of adjustment decomposition agent, usually guarantees decomposition agent halogen silicon polymer and decomposition agent mass ratio is 1:0.13 ~ 0.15.Institute
Chlorine silicon polymer cracking scission of link can be played an active part in by stating the hydrogen chloride in decomposition agent, hydrogen, chlorosilane, help to improve the polymerization of chlorine silicon
Object is cracked to form the conversion ratio of chlorosilane.
In catalyst preparation step, catalyst and halosilanes intermixture are mixed in a certain ratio preparation, wherein being catalyzed
The mass ratio that agent accounts for intermixture is 5%~60%, and mixing temperature control is 30~100 DEG C；The preferably catalyst matter that accounts for intermixture
For amount than being 10%~50%, mixing temperature control is 40~90 DEG C；More preferably catalyst account for intermixture mass ratio be 20%~
40%, mixing temperature control is 50~80 DEG C, but is not limited to, as long as falling into the mass ratio or temperature value within the scope of aforementioned value
Point should all be within protection scope of the present invention.Wherein halosilanes are preferably chlorosilane, bromo-silicane, such as trichlorosilane, tetrachloro
SiClx, dichlorosilane, tribromo hydrogen silicon, silicon bromide or dibromo dihydro silicon etc. are any one or more of, more preferably tetrabromo
SiClx.The halosilanes intermixture is this or these halosilanes mixtures, and mixed proportion does not have any restrictions,
It realizes technical effect of the invention, is used for example, by using the chlorosilane of recycling as the intermixture.The catalyst is nitrogen
Object is closed, selected from one or more of nitro, nitrous base class, nitrile or amine.Preferably, the catalyst is nitrile and fat
Amine mixed catalyst.Wherein, the nitrile catalyst is selected from one of aliphatic nitrile or dintrile or mixing, aromatic nitrile
One of class or dintrile or mixing.The Arneel SD is selected from the straight chain that carbon atom number is 3 ~ 20 or the Arneel SD with branch,
Such as selected from carbon atom number be 8 ~ 20 straight chain or with the Arneel SD of branch；Or selected from 5 ~ 8 straight chain or with branch
Arneel SD；Or more carbon atom numbers straight chain or Arneel SD with branch.The amines catalyst is selected from fatty amine or two
One of amine or mixing.The fatty amine is selected from the straight chain that carbon atom number is 3 ~ 20 or the fatty amine with branch, such as selects
From carbon atom number be 4 ~ 10 straight chain or with the fatty amine of branch；Such as selected from carbon atom number be 5 ~ 8 straight chain or with branch
The fatty amine of chain；Or more carbon atom numbers straight chain or fatty amine with branch.Such as nitro class catalyst can be nitre
Base octane, nitrobenzene etc.；Nitrous base class catalyst can be dinitrosobenzene, nitrosophenol etc.；Nitrile catalyst can be with
For cyanophenyl, positive caprylic nitrile, p-chlorobenzyl cyanide, dimethylaminopropionitrile, malononitrile etc.；Amines catalyst can be for triethanolamine, three just
Octylame, hexamethylene diamine etc., but not limited to this.In a particular embodiment, such as catalyst is nitrooctane and triethanolamine
Hybrid catalyst system；In another example being the hybrid catalyst system of dinitrosobenzene and nitrobenzene；It is also, for example, nitrobenzene and three
Hybrid catalyst system of n-octyl amine, etc., but not limited to this, it can appoint in nitro, nitrous base class, nitrile or amine
It is one or more of.In the present invention, the mixed catalyst has concerted catalysis effect.In special catalyst body of the invention
Under system and decomposition agent system, chlorine silicon polymer conversion per pass is up to 95% or more.In addition, the catalyst of prior art report is deposited
The problem of polluting to waste disposal system and to contamination of products, catalyst system of the invention is completely avoided common catalyzed
Systemic contamination caused by agent (n,N-Dimethylaniline and/or tri-n-butylamine etc.) discharge, while avoiding typical catalyst pair
The case where chlorosilane contamination of products, occurs.
In the present invention, prepared fresh catalyst and the catalyst of regeneration cycle are mixed into cracking reactor and join
With cracking reaction；Or the catalyst of regeneration cycle also enter catalyst preparation device carry out preparing together with fresh catalyst it is laggard
Enter cracking reactor.The dosage and chlorine silicon polymer of catalyst expect that clearly recycling mass ratio is 0.5 ~ 2, i.e., every 1 ton of chlorine silicon polymerization
Object is expected clearly, and 0.5 ~ 2 ton of catalyst is added and carries out cracking reaction, the dosage of the catalyst includes fresh catalyst and regeneration cycle
Catalyst total amount.The dosage and chlorine silicon polymer of the catalyst expect that clearly recycling mass ratio is preferably 0.8 ~ 1.5.
In cracking reaction step, chlorine silicon polymer, catalyst and decomposition agent are in cracking reactor in 25~250 DEG C of temperature
Under 0.05~0.5Mpa pressure condition, preferably 100~250 DEG C, 0.1~0.4Mpa；150~200 DEG C more preferably are preheated to,
Under the conditions of 0.2~0.3Mpa, cracking reaction occurs and generates chlorosilane.Cracking reaction is exothermic reaction, passes through the reaction heat of itself
Energy needed for can provide reactor is heated without using auxiliary fuel.The preheated device of reaction product is preheated to 40~250 DEG C
Enter gas-liquid separator afterwards, controls pressure of the gas and liquid separator in 0.05~0.3Mpa, be preferably preheated to 100~250 DEG C, more preferably
150~200 DEG C are preheated to, the pressure of control gas-liquid separator 4 is preferably 0.1~0.2Mpa, and cleavage reaction product is separated into
The on-condensible gas at top and the liquid of bottom.
In catalyst separating step, isolated bottom liquid enters catalyst separator, and the catalyst separator is for example
For flash tank, plate distillation column etc., but not limited to this.Controlling column bottom temperature is 80~150 DEG C, and pressure is 0.05~0.5Mpa,
It is preferred that column bottom temperature is 100~130 DEG C, pressure is 0.1~0.3Mpa, and isolated reaction generates at the top of catalyst separator
Chlorosilane, including dichlorosilane, trichlorosilane and silicon tetrachloride etc. collect chlorosilane and enter subsequent processing, such as rectifying
Purification etc.；Mixture that bottom is separated, including catalyst, part chlorosilane, metal chloride etc..
In process catalyst regeneration step, the mixture that catalyst separation tower bottom obtains enters catalyst regenerator, passes through water
Solution, distillation or the catalyst recovery process such as dry are by catalyst regeneration, such as after heat drying is regenerated to 200 ~ 300 DEG C
Catalyst.Catalyst after regeneration enters catalyst preparation device and carries out catalyst preformulation or mixed with prepared fresh catalyst
Enter cracking reactor after conjunction to be recycled.
Another aspect of the present invention, provides the device that halogen silicon polymer cracking of the present invention prepares halosilanes, including raw material is pre-
Processor 1, catalyst preparation device 7, cracking reactor 2, gas-liquid separator 4, catalyst separator 5, catalyst regenerator 6, institute
It states raw material preprocessor 1 and the catalyst preparation device 7 to be connected with the cracking reactor 2 respectively as charging, the cracking
2 discharging portion of reactor is connected with the gas-liquid separator 4, and the gas-liquid separator 4 is connected with the catalyst separator 5,
The catalyst separator 5 is connected with the catalyst regenerator 6, the catalyst regenerator 6 and the catalyst preparation device 7
Or cracking reactor 2 is connected.Wherein, preheater 3, gas-liquid are connected among the cracking reactor 2 and the gas-liquid separator 4
It is connected with pump 8 between separator 4 and catalyst separator 5, pump is connected between catalyst separator 5 and catalyst regenerator 6
8, pump 8 is connected between catalyst regenerator 6 and cracking reactor 2 and between catalyst preparation device 7 and cracking reactor 2,
The smooth charging of each device is realized by pump 8.In addition, can be also equipped with according to the actual situation on each process pipe valve, pressure gauge,
Thermometer etc., this is the common knowledge of this field.
Halogen silicon polymer cracking through the invention prepares the device of halosilanes, and the halogen silicon of production of polysilicon by-product is polymerize
Object is cracked to form halosilanes, and catalyst makes the circulation of tail gas of improved Siemens production of polysilicon by recycling utilization
Utilization rate greatly improves, and has accomplished environmental-friendly.
Below by more specific embodiment further illustration technique and effect of the invention, but this is to the present invention
Constitute any restrictions.
Embodiment 1
Catalyst dinitrosobenzene and nitrobenzene and trichlorosilane are hybridly prepared into mixed catalytic under the conditions of 55 DEG C of temperature
Agent is simultaneously passed through cracking reactor, and the mass ratio that catalyst accounts for trichlorosilane is 25%, mixed catalyst and production of polysilicon by-product
The mass ratio of chlorine silicon polymer is 1.25, hydrogen chloride molar content 70% in decomposition agent, H2Molar content 20%, chlorosilane mole contains
Amount 10% is passed through cracking reactor by the flow of 70 kilograms/h, and chlorine silicon polymer reacts under mixed catalyst effect with decomposition agent
It generates chlorosilane and obtains chlorosilane by separation regeneration step above-mentioned, and calculate chlorine silicon polymer conversion per pass and reach
85% or more.
Embodiment 2
Catalyst hexamethylene diamine and dichlorosilane and silicon tetrachloride are hybridly prepared into mixed catalytic under the conditions of 80 DEG C of temperature
Agent is simultaneously passed through cracking reactor, and it is 50% that catalyst, which accounts for dichlorosilane and the mass ratio of silicon tetrachloride, mixed catalyst and polycrystalline
The mass ratio that silicon produces the chlorine silicon polymer of by-product is 1.8, hydrogen chloride molar content 65% in decomposition agent, H2Molar content 30%,
Chlorosilane (silicon tetrachloride) molar content 5% is passed through cracking reactor by the flow of 70 kilograms/h, and chlorine silicon polymer is urged in mixing
Generation chlorosilane is reacted under agent effect with decomposition agent and obtains chlorosilane by separation regeneration step above-mentioned, and calculates chlorine
Silicon polymer conversion per pass is up to 95% or more.
Embodiment 3
Catalyst nitrooctane and nitrosophenol are hybridly prepared into mix with silicon bromide under the conditions of 30 DEG C of temperature urges
Agent is simultaneously passed through cracking reactor, and the mass ratio that catalyst accounts for silicon bromide is 5%, mixed catalyst and production of polysilicon by-product
The mass ratio of chlorine silicon polymer be 0.75, hydrogen bromide molar content 90% in decomposition agent, H2Molar content 5%, silicon bromide rubs
Your content 5% is passed through cracking reactor by the flow of 50 kilograms/h, chlorine silicon polymer in the case where mixed catalyst is acted on decomposition agent
Reaction generates chlorosilane and obtains chlorosilane by separation regeneration step above-mentioned, and calculates chlorine silicon polymer conversion per pass
Up to 95% or more.
Embodiment 4
Catalyst hexamethylene diamine and positive caprylic nitrile and silicon bromide are hybridly prepared into mixed catalyst simultaneously under the conditions of 70 DEG C of temperature
It is passed through cracking reactor, the mass ratio that catalyst accounts for silicon tetrachloride is 35%, the chlorine silicon of mixed catalyst and production of polysilicon by-product
The mass ratio of polymer is 1.5, hydrogen bromide molar content 50% in decomposition agent, H2Molar content 37%, bromo-silicane molar content 13%
(tribromo hydrogen silicon accounts for 6%, silicon bromide and accounts for 7%) is passed through cracking reactor by the flow of 80 kilograms/h, and chlorine silicon polymer is urged in mixing
Generation chlorosilane is reacted under agent effect with decomposition agent and obtains chlorosilane by separation regeneration step above-mentioned, and calculates chlorine
Silicon polymer conversion per pass is up to 87% or more.
Embodiment 5
Catalyst hexamethylene diamine and cyanophenyl and ocratation are hybridly prepared into mixed catalyst under the conditions of 85 DEG C of temperature and lead to
Enter cracking reactor, the mass ratio that catalyst accounts for ocratation is 45%, and the chlorine silicon of mixed catalyst and production of polysilicon by-product is poly-
The mass ratio for closing object is 1.75, hydrogen fluoride molar content 20% in decomposition agent, H2Molar content 64%, chlorosilane molar content 16%
(dichlorosilane and silicon tetrachloride respectively account for 8%) is passed through cracking reactor by the flow of 90 kilograms/h, and chlorine silicon polymer is mixing
Generation chlorosilane, which is reacted, with decomposition agent under catalyst action obtains chlorosilane, and calculate by separation regeneration step above-mentioned
Chlorine silicon polymer conversion per pass is up to 96% or more.
Embodiment 6
Catalyst nitrobenzene and tri-n-octyl amine and dichlorosilane are hybridly prepared into mixed catalytic under the conditions of 100 DEG C of temperature
Agent is simultaneously passed through cracking reactor, and the mass ratio that catalyst accounts for dichlorosilane is 60%, mixed catalyst and production of polysilicon by-product
The mass ratio of chlorine silicon polymer be 2, hydrogen chloride molar content 3% in decomposition agent, H2Molar content 77%, chlorosilane (dichloro two
Hydrogen silicon) molar content 20%, it is passed through cracking reactor by the flow of 100 kilograms/h, chlorine silicon polymer is under mixed catalyst effect
Generation chlorosilane is reacted with decomposition agent and obtains chlorosilane by separation regeneration step above-mentioned, and calculates chlorine silicon polymer list
Journey conversion ratio is up to 80% or more.
Embodiment 7
Catalyst hexamethylene diamine and tri-n-octyl amine and silicon bromide are hybridly prepared into mixed catalyst under the conditions of 50 DEG C of temperature
And it is passed through cracking reactor, the mass ratio that catalyst accounts for dichlorosilane is 20%, mixed catalyst and production of polysilicon by-product
The mass ratio of chlorine silicon polymer is 1, hydrogen chloride molar content 80% in decomposition agent, H2Molar content 10%, chlorosilane (four chlorinations
Silicon) molar content 10%, be passed through cracking reactor by the flow of 100 kilograms/h, chlorine silicon polymer under mixed catalyst effect with
Decomposition agent reaction generates chlorosilane and obtains chlorosilane by separation regeneration step above-mentioned, and calculates chlorine silicon polymer one way
Conversion ratio is up to 95% or more.
Embodiment 8
Catalyst triethanolamine and hexamethylene diamine and dichlorosilane are hybridly prepared into mixed catalytic under the conditions of 70 DEG C of temperature
Agent is simultaneously passed through cracking reactor, and the mass ratio that catalyst accounts for dichlorosilane is 30%, mixed catalyst and production of polysilicon by-product
The mass ratio of chlorine silicon polymer be 1.6, hydrogen bromide molar content 60% in decomposition agent, H2Molar content 35%, bromo-silicane (tetrabromo
SiClx) molar content 5%, be passed through cracking reactor by the flow of 90 kilograms/h, chlorine silicon polymer under mixed catalyst effect with
Decomposition agent reaction generates chlorosilane and obtains chlorosilane by separation regeneration step above-mentioned, and calculates chlorine silicon polymer one way
Conversion ratio is up to 95% or more.
Embodiment 9
Catalyst dimethylaminopropionitrile and silicon bromide are hybridly prepared into mixed catalyst under the conditions of 60 DEG C of temperature and lead to
Enter cracking reactor, the mass ratio that catalyst accounts for silicon bromide is 40%, and the chlorine silicon of mixed catalyst and production of polysilicon by-product is poly-
The mass ratio for closing object is 0.8, hydrogen bromide molar content 80% in decomposition agent, H2Molar content 15%, bromo-silicane (silicon bromide) rub
Your content 5% is passed through cracking reactor by the flow of 80 kilograms/h, chlorine silicon polymer in the case where mixed catalyst is acted on decomposition agent
Reaction generates chlorosilane and obtains chlorosilane by separation regeneration step above-mentioned, and calculates chlorine silicon polymer conversion per pass
Up to 95% or more.
Embodiment 10
Catalyst nitrooctane and p-chlorobenzyl cyanide are hybridly prepared under the conditions of 40 DEG C of temperature with dichlorosilane to be mixed
Catalyst is simultaneously passed through cracking reactor, and the mass ratio that catalyst accounts for dichlorosilane is 15%, mixed catalyst and production of polysilicon
The mass ratio of the chlorine silicon polymer of by-product is 0.9, hydrogen bromide molar content 80% in decomposition agent, H2Molar content 13%, chlorosilane
3.5%) molar content 7%(silicon tetrachloride and dichlorosilane respectively account for, be passed through cracking reactor, chlorine silicon by the flow of 60 kilograms/h
Polymer reacts generation chlorosilane with decomposition agent under mixed catalyst effect and obtains chlorine by separation regeneration step above-mentioned
Silane, and chlorine silicon polymer conversion per pass is calculated up to 95% or more.
Although a specific embodiment of the invention has been described in detail above in conjunction with the embodiments, needs are indicated
, the scope of protection of the present invention is not limited by these specific embodiments, but is determined by claims.Ability
Field technique personnel can technical though according to the present invention various equivalent changes and suitably modified are carried out to above embodiment,
It, should all be within protection scope of the present invention when the spirit that generated function is still covered without departing from specification.
Claims (10)
1. a kind of method that the cracking of halogen silicon polymer prepares halosilanes, comprising the following steps:
1) cracking reaction step: halogen silicon polymer, catalyst and decomposition agent are passed through in cracking reactor, in 25~250 DEG C of temperature
Cracking reaction occurs under degree and 0.05~0.5MP a pressure condition and generates halosilanes；
2) gas-liquid separation step: the product of step 1) is preheated to 40~250 DEG C by preheater and enters gas-liquid separator, control pressure
Power 0.05~0.3MP a is separated into the on-condensible gas at top and the liquid of bottom；
3) catalyst separating step: the liquid of step 2 separation enters catalyst separator, will reaction at the top of catalyst separator
The halosilanes of generation, which are collected, enters subsequent processing, and bottom obtains mixture；
4) process catalyst regeneration step: the mixture that step 3) bottom obtains is sent into catalyst regenerator and is regenerated；
5) circulation step: mixing by the catalyst that step 4) regenerates with raw catelyst, send to step 1) reactor cycles
It utilizes；
Wherein, the halogen in the halogen silicon polymer is selected from F, Cl, Br or I；
The catalyst is nitrogenous compound, selected from one or more of nitro, nitrous base class, nitrile or amine；
The decomposition agent is by hydrogen halides, H2, halosilanes are mixed in a certain ratio.
2. the method that halogen silicon polymer cracking according to claim 1 prepares halosilanes, it is characterised in that further include 6) pre-
Processing step: halogen silicon polymer is handled by raw material preprocessor, obtains halogen silicon polymer clear liquid, and the clear liquid is sent into
Step 1) carries out cracking reaction.
3. the method that halogen silicon polymer cracking according to claim 1 prepares halosilanes, it is characterised in that further include 7) urging
Agent preparation steps: being mixed in a certain ratio preparation for catalyst and halosilanes mixture, and wherein catalyst accounts for halosilanes mixing
The mass ratio of object is 5%~60%, and mixing temperature control is 30~100 DEG C.
4. the method that halogen silicon polymer cracking according to claim 2 prepares halosilanes, it is characterised in that the catalyst
Internal circulating load and halogen silicon polymer clear liquid dosage mass ratio are 0.5 ~ 2.
5. the method that halogen silicon polymer cracking according to claim 1 prepares halosilanes, it is characterised in that the decomposition agent
Middle hydrogen halides molar content 3%~90%, H2Molar content 5%~90%, halosilanes molar content 5 ~ 20%.
6. the method that halogen silicon polymer cracking according to claim 1 prepares halosilanes, it is characterised in that the halogen silicon is poly-
It closes object and decomposition agent mass ratio is 1:0.13 ~ 0.15.
7. the method that halogen silicon polymer cracking according to claim 1 prepares halosilanes, it is characterised in that the catalyst
For nitrile and fatty amines mixed catalyst.
8. the method that halogen silicon polymer cracking according to claim 1 prepares halosilanes, it is characterised in that the amine is urged
Agent is selected from one of fatty amine or diamines or mixing.
9. the method that halogen silicon polymer cracking according to claim 8 prepares halosilanes, it is characterised in that the fatty amine
Selected from carbon atom number be 3 ~ 20 straight chain or with the fatty amine of branch.
10. the method that -9 described in any item halogen silicon polymer cracking prepare halosilanes according to claim 1 prepares halosilanes
Device, including raw material preprocessor, catalyst preparation device, cracking reactor, gas-liquid separator, catalyst separator, catalyst
Regenerator, the raw material preprocessor and the catalyst preparation device are connected with the cracking reactor respectively as charging, institute
It states cracking reactor discharging portion to be connected with the gas-liquid separator, the gas-liquid separator and the catalyst separator phase
Even, the catalyst separator is connected with the catalyst regenerator, the catalyst regenerator and the catalyst preparation device
It is connected.
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| CN109384233B (en) * | 2018-12-13 | 2023-10-20 | 江苏中能硅业科技发展有限公司 | Method for treating silicon polymers |
| CN111659329B (en) * | 2019-03-07 | 2022-05-24 | 江西福特化工新材料有限公司 | Condensation reaction device |
| CN110627071B (en) * | 2019-11-12 | 2021-08-10 | 四川永祥新能源有限公司 | Polychlorosilane processing apparatus in polycrystalline silicon production |
| CN111921480A (en) * | 2020-09-01 | 2020-11-13 | 新疆协鑫新能源材料科技有限公司 | Device and process for regenerating high-boiling-point substance auxiliary agent |
| CN114573629A (en) * | 2020-11-30 | 2022-06-03 | 新疆硅基新材料创新中心有限公司 | Organic silicon monomer preparation method and system and polycrystalline silicon system |
| CN113603097B (en) * | 2021-08-18 | 2023-01-24 | 新疆协鑫新能源材料科技有限公司 | Device and process for on-line recovery of high-boiling cracking catalyst |
| CN115106045B (en) * | 2022-07-26 | 2024-03-29 | 乐山协鑫新能源科技有限公司 | High-boiling treatment system for slurry |
| CN116440516A (en) * | 2023-03-02 | 2023-07-18 | 江西蓝星星火有机硅有限公司 | Method and device for improving HCl conversion rate in cracking of organosilicon high-boiling-point mixture |
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