CN102212080A - Reaction device for preparing methyl chlorosilane and reaction system comprising same - Google Patents
Reaction device for preparing methyl chlorosilane and reaction system comprising same Download PDFInfo
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- CN102212080A CN102212080A CN2010101466693A CN201010146669A CN102212080A CN 102212080 A CN102212080 A CN 102212080A CN 2010101466693 A CN2010101466693 A CN 2010101466693A CN 201010146669 A CN201010146669 A CN 201010146669A CN 102212080 A CN102212080 A CN 102212080A
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 114
- YGZSVWMBUCGDCV-UHFFFAOYSA-N chloro(methyl)silane Chemical compound C[SiH2]Cl YGZSVWMBUCGDCV-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000002002 slurry Substances 0.000 claims abstract description 134
- 239000007788 liquid Substances 0.000 claims description 38
- 239000002994 raw material Substances 0.000 claims description 37
- 238000004891 communication Methods 0.000 claims description 11
- 238000004064 recycling Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 5
- FBBDOOHMGLLEGJ-UHFFFAOYSA-N methane;hydrochloride Chemical compound C.Cl FBBDOOHMGLLEGJ-UHFFFAOYSA-N 0.000 abstract description 26
- 239000003054 catalyst Substances 0.000 abstract description 9
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 2
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- 238000007086 side reaction Methods 0.000 abstract description 2
- 239000000377 silicon dioxide Substances 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 54
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 28
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 24
- 238000000034 method Methods 0.000 description 23
- 239000000047 product Substances 0.000 description 17
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- 239000003921 oil Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000002699 waste material Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 238000012546 transfer Methods 0.000 description 10
- 238000009826 distribution Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000006227 byproduct Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 230000002194 synthesizing effect Effects 0.000 description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229940057995 liquid paraffin Drugs 0.000 description 4
- 239000002480 mineral oil Substances 0.000 description 4
- 235000010446 mineral oil Nutrition 0.000 description 4
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 4
- 229920003216 poly(methylphenylsiloxane) Polymers 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 150000004760 silicates Chemical class 0.000 description 4
- 229920002545 silicone oil Polymers 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 206010037660 Pyrexia Diseases 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005243 fluidization Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000013021 overheating Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000011863 silicon-based powder Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000010959 commercial synthesis reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 239000005055 methyl trichlorosilane Substances 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011856 silicon-based particle Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
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Abstract
The invention relates to the field of preparation of methyl chlorosilane, in particular to a reaction device for preparing methyl chlorosilane and a reaction system comprising the same. The reaction device for preparing methyl chlorosilane comprises a cylindrical slurry bed reactor, wherein an inert medium is filled in the slurry bed reactor; a contact mass prepared from a catalyst and silica power suspends in the inert medium; and a built-in heat exchanger is arranged in the slurry bed reactor. In the reactor for preparing methyl chlorosilane, the cylindrical slurry bed reactor, the built-in heat exchanger of the reactor and/or an outer inert medium circulation device externally provided with a heat exchange device are adopted firstly; by adopting the cylindrical slurry bed reactor, the residence time of methane chloride in the reactor is prolonged, and the circulation amount of methane chloride is reduced; and by adopting the built-in heat exchanger and an external heat exchanger in the reactor, heat released by the reaction can be removed easily the temperature of a catalyst bed is easy to control, side reactions are reduced, and the selectivity of dimethyl dichlorosilane is increased.
Description
Technical Field
The invention relates to the field of preparation of methyl chlorosilane, in particular to a reaction device for preparing methyl chlorosilane and a reaction system comprising the same.
Background
The organic silicon has the double properties of inorganic materials and organic materials, has the excellent characteristics of high and low temperature resistance, electric insulation, weather resistance, corrosion resistance, no toxicity, no odor and the like, and is widely applied to the fields of electronics, automobiles, petroleum, chemical engineering, buildings, aerospace and the like. In many sophisticated fields, silicone materials have irreplaceable special effects. Methylchlorosilane is the most important and most used organosilicon monomer for preparing organosilicon materials, is the foundation and pillar of the whole organosilicon industry, and the research on the production technology and process thereof is a very important subject in the chemical industry, wherein the direct method for directly synthesizing methylchlorosilane from monochloromethane and silicon powder under the action of a copper catalyst has become a hotspot of research.
In the reaction for synthesizing methylchlorosilane by the "direct method", dimethyldichlorosilane has a wide application range and a large amount of use, and thus is a main target product of the reaction. Since the reaction is a violent exothermic reaction, if the reactor is locally overheated, the formation of by-products such as methyltrichlorosilane and the like can be caused, but under proper catalyst and operation conditions, the selectivity of the dimethyldichlorosilane can be greatly improved. Therefore, in order to maximize the production efficiency and the operational continuity of the direct process reactor, the design of the exothermic heat removal mode of reaction in the reactor is the core content of the process technology.
Currently, the direct commercial synthesis of methylchlorosilanes is essentially a fluidized bed reactor based process technology. The fluidized bed reaction process with raw material gas as the contact fluidizing medium can disperse the contact uniformly, improve the heat transfer efficiency and facilitate the removal of reaction heat. However, the fluidized bed has a dead angle of fluidization, the utilization rate of raw materials is low, local overheating and burning are caused, the raw material methane chloride is decomposed, some byproducts are generated, and the particle size of a contact body is smaller and smaller along with the progress of reaction, so that the contact body is easily carried out of the reactor by gas flow to become a waste contact body. Patent CN2372052 discloses a synthetic methyl chlorosilane's fluidized bed, can destroy the big bubble, reduces the silica flour and takes out, prevents the deposition caking, local overheat fever etc. this patent mainly is through optimizing combination internals, sets up a vertical sleeve pipe by the barrel center, and the tube bank heat exchanger that the vertical sleeve pipe that its periphery set up two-layer annular arrangement constitutes to with the radial and vertical fixed of exerting on it with slip mount, fixed plate and tube sheet, a synthetic methyl chlorosilane's fluidized bed that designs. Patent CN2923012 is characterized in that a plurality of synthesis gas outlets are arranged on the side surface of a cylinder body at the lower part of a heat-conducting oil distributor, a plurality of feed back charging openings are arranged on the side surface of a cone at the upper part of the gas distributor, the number of the synthesis gas outlets is 2-4, the included angle is 180-90 degrees, and the number of the feed back charging openings is 1-4, so that the improvement can reduce fluidization dead angles. Patent CN1382690 provides a method for reacting fine silicon particles with monochloromethane in a fluidized bed and continuously and directly synthesizing methylchlorosilane. In the method, gaseous silane, other gaseous reactants, unreacted methane chloride and a product stream containing silicon dust are discharged from a fluidized bed, wherein at least part of the dust forms a suspension with the substances in the liquid silane, other liquid reactants and mixtures thereof, and is fed into the fluidized bed for circulation. In order to prolong the retention time of a contact in a reactor, patent CN101537329 discloses a fluidized bed reactor, and specifically, a gas guiding device is additionally arranged between a bottom distribution plate and a cylinder of the fluidized bed reactor, the device comprises a gas distribution pipe, a guiding pipe and a gas distribution flange, the gas distribution pipe is composed of at least 2 sections of bent pipes, the lower ends of the bent pipes are connected with the guiding pipe, the middle part of the outer end of each section of bent pipe is connected with a gas inlet, and the other end of the guiding pipe is connected with the gas distribution flange. After the diversion device is added, part of raw material gas can be diverted and enter the fluidized bed tangentially, tangential speed is added to the gas in the fluidized bed on the basis of the original upward axial speed by tangential gas inlet, so that the gas and entrained raw material particles spirally rise, and the contact time of the reaction materials is prolonged by the formed rotating flow field.
Although the current fluidized bed process is absolutely superior in industrial production of methyl chlorosilane, certain patents still improve and innovate the methyl chlorosilane every year, the fluidized bed reactor is designed to be more and more complex, is more and more difficult to operate, has higher and more cost, and cannot fundamentally solve the problems that the fluidized bed has a fluidized dead angle and causes local overheating and fever, and a contact body has smaller and smaller particle size and is easily carried out of the reactor by gas flow along with the reaction.
The direct process of synthesizing methyl chlorosilane in slurry bed process includes suspending the contact in one kind of thermally stable liquid inert medium with high boiling point, raising the temperature and introducing gaseous methane chloride for reaction to obtain methyl chlorosilane. The slurry bed process can make the contact bodies dispersed uniformly and improve the heat transfer efficiency obviously, is beneficial to the removal of reaction heat, and is easy to solve the problem that the fluidized bed is difficult to solve by taking the slurry bed as the main characteristic. Patent US7153991 reports a method for preparing nano-copper catalyst precursors and nano-assistants for synthesizing methylchlorosilane using a slurry bed direct process, the slurry bed reactor used in the reaction process is provided with a stirrer. Patent US5728858 discloses a slurry bed process for organosiloxane monomer synthesis, the slurry bed reactor of the process having a stirring paddle, alkyl alcohol being gasified and then entering the slurry bed from the bottom of the reactor together with hydrogen, the product and unreacted light components being removed from the top of the reactor in gaseous form, and after condensation separation, the unreacted light components being recycled. The above patents all use a non-long cylinder type slurry bed with a stirrer, which makes the residence time of gaseous monochloromethane in the reactor shorter, and increases the circulation amount of monochloromethane, but the stirrer has a poor material mixing effect on the long cylinder type slurry bed reactor. Because the direct method for synthesizing methyl chlorosilane is a strong exothermic process, the reaction exothermic of the slurry bed process technology is balanced by the removal and heat absorption of unreacted raw material gas and gasified products without adopting a heat exchanger for heat exchange, the heat extraction mode is moderate, the strength is difficult to control, the flexibility is poor, the heat exchanger is further adopted for exchanging for the reuse of extracted heat, and the economy and the universality are not realized.
Disclosure of Invention
Therefore, the invention aims to provide a reaction device for preparing methyl chlorosilane.
Another object of the present invention is to provide a system for preparing methylchlorosilanes comprising the above reaction apparatus.
The reaction device for preparing the methyl chlorosilane comprises a long-cylinder type slurry reactor 1, wherein the long-cylinder type slurry reactor 1 comprises a raw material gas distributor 2 and a slurry bed reactor 3 from bottom to top, an inert medium is filled in the slurry bed reactor 3, a contact body formed by a catalyst and silicon powder is suspended in the inert medium, a built-in heat exchanger 6 is arranged in the slurry bed reactor 3, the built-in heat exchanger can stably control the reaction temperature, and the exothermic reaction is converted into superheated steam for recycling.
Preferably, the reaction apparatus for producing methylchlorosilanes according to the invention may comprise a feed heat exchanger 7, said feed heat exchanger 7 being in communication with the bottom of said long-barrel type slurry reactor 1. The raw materials of the methane chloride and the nitrogen directly enter the long-cylinder slurry bed reactor after heat exchange and temperature rise of reaction products or without heat exchange, and the bottom of a slurry bed layer formed by the inert medium and the contact body ascends after being uniformly distributed by the gas distribution plate so as to meet the requirements of full contact between the methane chloride and the surface of the contact body and uniform reaction temperature of the bed layer. In order to ensure the constant temperature of the reaction bed layer, the heat generated in the reaction is taken by a heat exchanger 6 arranged in the reactor, and the heat exchange medium can be industrial boiler feed water, or heat conduction oil or other media for heat exchange. When boiler water supply heat exchange is adopted, superheated steam can be directly by-produced. If heat transfer oil is adopted for heat exchange, superheated steam can be generated as a byproduct by cooling the heat transfer oil with water, and the superheated steam generated by the two methods can be used for external supply or self-use. The reaction temperature of the slurry bed reactor is 200-400 ℃, the reaction pressure is 0.1-1.0 MPa, and the space velocity of the monochloro methane is 1000-15000 h-1The space velocity of nitrogen is 0-15000 h-1. The inert medium is one or more of silicone oil such as methyl silicone oil and phenyl silicone oil, silicate compounds, liquid paraffin, mineral oil, aromatic hydrocarbon and derivatives thereof, molten salt and other solvents, and the heat exchange medium is water or heat conduction oil.
The reaction device for preparing methyl chlorosilane can also comprise a long cylindrical slurry reactor 1, a medium circulation metering pump 4 and an external heat exchanger 5, wherein the long cylindrical slurry reactor 1 comprises a raw material gas distributor 2 and a slurry bed reactor 3 from bottom to top, and an inert medium is filled in the slurry bed reactor 3; one end of the medium circulation metering pump 4 is communicated with the upper part of the side wall of the slurry bed reactor 3, the other end of the medium circulation metering pump is communicated with the external heat exchanger 5, the other end of the external heat exchanger 5 is communicated with the lower part of the side wall of the slurry bed reactor 3, and under the action of the medium circulation metering pump 4, inert media are transferred from the upper part of the slurry bed reactor 3 to the lower part of the slurry bed reactor 3. The medium circulation metering pump 4 and the external heat exchanger 5 thus constitute an external circulation device for the inert medium. The inert medium is transferred from the upper part to the lower part of the reactor through a pump under the action of the external circulation device to strengthen the material mixing, the external heat exchanger 5 can stably control the reaction temperature and convert the reaction heat release into superheated steam for recycling. The catalyst and silicon powder form a contact suspended in an inert medium.
Preferably, the reaction apparatus for preparing methylchlorosilane described above may include a raw material heat exchanger 7, and the raw material heat exchanger 7 is communicated with the bottom of the long-tube type slurry reactor 1. The raw materials of the methane chloride and the nitrogen directly enter the long-cylinder slurry bed reactor after heat exchange and temperature rise of reaction products or without heat exchange, and the bottom of a slurry bed layer formed by the inert medium and the contact body ascends after being uniformly distributed by the gas distribution plate so as to meet the requirements of full contact between the methane chloride and the surface of the contact body and uniform reaction temperature of the bed layer. In order to ensure the constant temperature of the reaction bed layer, the heat generated in the reaction is taken by an inert medium external circulation device with an external heat exchange device 5, and the heat exchange medium can be industrial boiler water supply, heat conduction oil or other media for heat exchange. When boiler water supply heat exchange is adopted, superheated steam can be directly by-produced. If heat transfer oil is adopted for heat exchange, superheated steam can be generated as a byproduct by cooling the heat transfer oil with water, and the superheated steam generated by the two methods can be used for external supply or self-use.
Preferably, according to the reaction device of the present invention, in the system of the inert medium external circulation device with the heat exchange device, a liquid-solid separator 8 may be provided, wherein one end of the solid-liquid separator 8 is communicated with the upper part of the sidewall of the slurry bed reactor 3, and the other end is communicated with the medium circulation metering pump 4. The spent contact and/or spent inert medium may be separated from the reaction system as needed for the reaction, while fresh inert medium and contact are replenished.
When the reaction device is used for preparing methyl chlorosilane, the reaction temperature of the long-cylinder type slurry reactor 1 is 200-400 ℃, the reaction pressure is 0.1-1.0 MPa, and the space velocity of the methane chloride is 1000-15000 h-1The space velocity of nitrogen is 0-15000 h-1. The inert medium is one or more of silicone oil such as methyl silicone oil and phenyl silicone oil, silicate compounds, liquid paraffin, mineral oil, aromatic hydrocarbon and derivatives thereof, molten salt and other solvents, and the heat exchange medium is water or heat conduction oil.
The reaction device for preparing methyl chlorosilane provided by the invention can comprise a long cylinder type slurry reactor 1, a medium circulation metering pump 4 and an external heat exchanger 5, wherein the long cylinder type slurry reactor 1 comprises a raw material gas distributor 2 and a slurry bed reactor 3 from bottom to top, an inert medium is filled in the slurry bed reactor 3, and an internal heat exchanger 6 is arranged in the slurry bed reactor 3; one end of the medium circulation metering pump 4 is communicated with the upper part of the side wall of the slurry bed reactor 3, the other end of the medium circulation metering pump is communicated with the external heat exchanger 5, the other end of the external heat exchanger 5 is communicated with the lower part of the side wall of the slurry bed reactor 3, and under the action of the medium circulation metering pump 4, inert media are transferred from the upper part of the slurry bed reactor 3 to the lower part of the slurry bed reactor 3.
According to the reaction device for preparing methyl chlorosilane, inert media are transferred from the upper part to the lower part of the reactor through the pump under the action of the external circulation device (the media circulation metering pump 4) to strengthen material mixing, the internal heat exchanger 6 and the external heat exchanger 5 of the slurry bed can stably control the reaction temperature, and the exothermic reaction is converted into superheated steam for recycling.
Preferably, the reaction apparatus for preparing methylchlorosilane according to the present invention may comprise a raw material heat exchanger 7, and the raw material heat exchanger 7 is in communication with the bottom of the long-tube type slurry reactor 1. The catalyst and silicon powder form a contact body suspended in an inert medium, the raw materials of methane chloride and nitrogen directly enter the long-cylinder slurry bed reactor 3 through heat exchange and temperature rise of reaction products or without heat exchange, and the raw materials of methane chloride and nitrogen are uniformly distributed through a gas distribution plate and then ascend from the bottom of a slurry bed layer formed by the inert medium and the contact body so as to meet the requirements of full contact of the methane chloride and the surface of the contact body and uniform reaction temperature of the bed layer. In order to ensure the constant temperature of the reaction bed layer, the heat generated in the reaction is taken by a heat exchanger 6 arranged in the reactor and an inert medium external circulation device with an external heat exchanger 5, and the heat exchange medium can be industrial boiler water supply, or heat conduction oil or other media for heat exchange. When boiler water supply heat exchange is adopted, superheated steam can be directly by-produced. If heat transfer oil is adopted for heat exchange, superheated steam can be generated as a byproduct by cooling the heat transfer oil with water, and the superheated steam generated by the two methods can be used for external supply or self-use.
Preferably, the reaction device for preparing methyl chlorosilane according to the invention is provided with a liquid-solid separator 8 in a system of an inert medium external circulation device with a heat exchange device, and can separate waste contact bodies or waste inert medium from the reaction system according to the reaction requirement and simultaneously replenish fresh inert medium and contact bodies. The reaction temperature of the slurry bed reactor is 200-400 ℃, the reaction pressure is 0.1-1.0 MPa, and the space velocity of the monochloro methane is 1000-15000 h-1The space velocity of nitrogen is 0-15000 h-1. The inert medium is one or more of silicone oil such as methyl silicone oil and phenyl silicone oil, silicate compounds, liquid paraffin, mineral oil, aromatic hydrocarbon and derivatives thereof, molten salt and other solvents, and the heat exchange medium is water or heat conduction oil.
Therefore, the invention also provides a system for preparing methyl chlorosilane, which comprises the reaction device for preparing methyl chlorosilane, heat exchangers 9 and 10, gas- liquid separators 11 and 12 and a medium recycling metering pump 13;
wherein,
the reaction device can comprise a long cylindrical slurry reactor 1, the interior of the reactor comprises a raw material gas distributor 2 and a slurry bed reactor 3 from bottom to top, an inert medium is filled in the slurry bed reactor 3, a built-in heat exchanger 6 is arranged in the slurry bed reactor 3,
or, the reaction device comprises a long-cylinder type slurry reactor 1, a medium circulation metering pump 4 and an external heat exchanger 5, an inert medium is filled in the slurry bed reactor 3, one end of the medium circulation metering pump 4 is communicated with the upper part of the side wall of the slurry bed reactor 3, the other end of the medium circulation metering pump is communicated with the external heat exchanger 5, the other end of the external heat exchanger 5 is communicated with the lower part of the side wall of the slurry bed reactor 3, and under the action of the medium circulation metering pump 4, the inert medium is transferred from the upper part of the slurry bed reactor 3 to the lower part of the slurry bed reactor 3,
or, the reaction device comprises a long cylindrical slurry reactor 1, a medium circulation metering pump 4 and an external heat exchanger 5, an inert medium is filled in the slurry reactor 3, an internal heat exchanger 6 is arranged in the slurry reactor 3, one end of the medium circulation metering pump 4 is communicated with the upper part of the side wall of the slurry reactor 3, the other end of the medium circulation metering pump is communicated with the external heat exchanger 5, the other end of the external heat exchanger 5 is communicated with the lower part of the side wall of the slurry reactor 3, and under the action of the medium circulation metering pump 4, the inert medium is transferred from the upper part of the slurry reactor 3 to the lower part of the slurry reactor 3,
the top of long tube type slurry reactor 1 with the top intercommunication of condenser 9, the top of vapour and liquid separator 11 respectively with the bottom of heat exchanger 9 with the top intercommunication of condenser 10, the bottom of vapour and liquid separator 11 with the one end intercommunication of medium retrieval and utilization measuring pump 13, the other end of medium retrieval and utilization measuring pump 13 and another relative lateral wall lower part intercommunication of slurry bed reactor 3, the top of vapour and liquid separator 12 respectively with the bottom of condenser 10 with the bottom intercommunication of long tube type slurry reactor 1.
Preferably, the reaction device for preparing methyl chlorosilane according to the invention is provided with a liquid-solid separator 8 in a system of an inert medium external circulation device with a heat exchange device, and can separate waste contact bodies or waste inert medium from the reaction system according to the reaction requirement and simultaneously replenish fresh inert medium and contact bodies.
The reaction temperature of the slurry bed reactor 3 is 200-400 ℃, the reaction pressure is 0.1-1.0 MPa, and the space velocity of the methane chloride is 1000-15000 h-1The space velocity of nitrogen is 0-15000 h-1. Through the reaction system, after unreacted methane chloride and products are removed from the upper end of the slurry bed reactor in a gaseous state, the methane chloride and the products are cooled for the first time (a condenser 9), the gas outlet temperature is controlled to be 120-200 ℃, some entrained inert media are separated out and recycled through a medium recycling metering pump 13, after the methane chloride and the products are cooled for the second time through a condenser 10, the gas outlet temperature is controlled to be 10-30 ℃, the obtained liquid products are conveyed to a product refining unit, and the obtained unreacted methane chloride gas is conveyed to the long-cylinder type slurry bed reactor 1 for recycling. The inert medium is one or more of silicone oil such as methyl silicone oil and phenyl silicone oil, silicate compounds, liquid paraffin, mineral oil, aromatic hydrocarbon and derivatives thereof, molten salt and other solvents, and the heat exchange medium is water or heat conduction oil.
The invention has the advantages that:
1. the reactor for preparing the methyl chlorosilane firstly adopts a long-cylinder slurry bed reactor, an inner heat exchanger and/or an inert medium outer circulating device with a heat exchange device are/is arranged outside the reactor, the long-cylinder slurry bed increases the retention time of the methane chloride in the reactor, reduces the circulating amount of the methane chloride, and both an internal heat exchanger and an external heat exchanger in the reactor can ensure that the reaction heat release is easy to move out and the temperature of a catalyst bed layer is easy to control, thereby being beneficial to reducing the occurrence of side reaction and improving the selectivity of the dimethyl dichlorosilane.
2. The external circulation device with the inert medium replaces a built-in stirrer to strengthen the material mixing of the long-cylinder type slurry bed reactor, and solves the problems that the stirrer is not beneficial to the material mixing of the long-cylinder type slurry bed reactor, the built-in heat exchanger is not beneficial to the installation of the stirrer and the like.
3. In the system of the inert medium external circulation device, a liquid-solid separator is arranged, so that waste contact bodies and/or waste inert mediums can be separated from the reaction system in time according to the reaction requirement, and simultaneously, fresh inert mediums and slurry of the contact bodies are supplemented.
4. A single-stage or multi-stage heat exchanger is arranged in an internal heat exchange system and an external heat exchange system of the slurry bed reactor, heat released in the reaction for preparing the methyl chlorosilane is used for producing superheated steam to be enriched and recovered, and the heat generated by the reaction is easier to recycle.
5. The long-barrel type slurry bed reactor with the built-in heat exchanger and the built-out heat exchanger can stably control the temperature of a catalyst bed layer in the reaction process, and is also suitable for other gas-solid reactions which are characterized by exothermic reactions.
Drawings
Fig. 1 is a system for preparing methylchlorosilanes according to example 1 of the present invention.
Fig. 2 is a system for preparing methylchlorosilanes according to example 2 of the present invention.
Fig. 3 is a system for preparing methylchlorosilanes according to example 3 of the present invention.
Description of the drawings:
1: long barrel type slurry reactor 2: raw material gas distributor
3: slurry bed reactor 4: medium circulation metering pump
5: the external heat exchanger 6: built-in heat exchanger
7: raw material heat exchanger 8: liquid-solid separator
9: the condenser 10: condenser
11: the gas-liquid separator 12: gas-liquid separator
13: metering pump for recycling medium
Detailed Description
The specific implementation steps of the process of the present invention are further illustrated by the accompanying fig. 1, fig. 2 and fig. 3.
Example 1
As shown in figure 1, the temperature of the raw material gas, namely the chloromethane and nitrogen, is firstly raised to 250 ℃ by a raw material heat exchanger 7 before entering the reactor, then the raw material gas enters a slurry bed reactor 3 filled with inert media through a raw material gas distributor 2, the reaction is carried out at the reaction temperature of 300 ℃ and the reaction pressure of 0.3MPa, and the reaction space velocity of the raw material gas, namely the chloromethane, is adjusted to 8000h-1The space velocity of nitrogen is 10000h-1. In order to ensure the constant temperature of the bed layer of the reactor, the heat released by the reaction is timely taken out by the built-in heat exchanger 6 of the fluidized bed reactor, and superheated steam with the pressure of more than 1.5MPa is by-produced. The product after the reaction in the slurry bed reactor 3 and the unreacted methane chloride are removed from the upper end of the slurry bed reactor 3 in a gaseous state, cooled by the condenser 9 for one time, passed through the gas-liquid separator 11, the gas outlet temperature is controlled at 160 ℃, the liquid is an entrained inert medium, and recycled by the metering pump 13. The gas from the gas-liquid separator 11 is cooled for the second time by the condenser 10, then passes through the gas-liquid separator 12, the gas outlet temperature is controlled to be 20 ℃, the gas is unreacted methane chloride, the gas is recycled by the recycled raw material heat exchanger 7, the liquid is also a product, and the liquid is conveyed to a product refining unit, so that the selectivity of the obtained dimethyldichlorosilane reaches 84%.
Example 2
As shown in FIG. 2, theThe feed gas, namely the chloromethane and the nitrogen, is heated to 250 ℃ by a feed heat exchanger 7 before entering the reactor, then enters a slurry bed reactor 3 filled with inert media through a feed gas distributor 2, the reaction is carried out at the reaction temperature of 300 ℃ and the reaction pressure of 0.3MPa, and the reaction space velocity of the feed gas, namely the chloromethane, is adjusted to 8000h-1The space velocity of nitrogen is 10000h-1. In order to ensure the constant temperature of the bed layer of the reactor, the heat released by the reaction is timely taken out by an external heat exchanger 5 of the fluidized bed reactor, and superheated steam with the pressure of more than 1.5MPa is byproduct. The material mixing is enhanced by adjusting the medium circulation metering pump 4 to transfer the inert medium from the upper part of the reactor to the lower part of the reactor through the pump under the action of the external circulation device. In the system of the inert medium external circulation device with the heat exchange device, the liquid-solid separator 8 is arranged, so that waste contact bodies or waste inert media can be separated from the reaction system according to the reaction requirement, and simultaneously fresh inert media and slurry of the contact bodies are supplemented. The product after the reaction in the slurry bed reactor 3 and the unreacted methane chloride are removed from the upper end of the slurry bed reactor 3 in a gaseous state, cooled by the condenser 9 for one time, passed through the gas-liquid separator 11, the gas outlet temperature is controlled at 160 ℃, the liquid is an entrained inert medium, and recycled by the metering pump 13. The gas from the gas-liquid separator 11 is cooled for the second time by the condenser 10, then passes through the gas-liquid separator 12, the gas outlet temperature is controlled to be 20 ℃, the gas is unreacted methane chloride, the gas is recycled by the recycled raw material heat exchanger 7, the liquid is also a product, and the liquid is conveyed to a product refining unit, so that the selectivity of the obtained dimethyldichlorosilane reaches 89%.
Example 3
As shown in figure 3, the temperature of the raw material gas, namely the chloromethane and the nitrogen, is firstly raised to 250 ℃ by a raw material heat exchanger 7 before entering the reactor, then the raw material gas enters a slurry bed reactor 3 filled with inert media through a raw material gas distributor 2, the reaction is carried out at the reaction temperature of 300 ℃ and the reaction pressure of 0.3MPa, and the reaction space velocity of the raw material gas, namely the chloromethane, is adjusted to 8000h-1The space velocity of nitrogen is 10000h-1. In order to ensure the constant temperature of the bed layer of the reactor, the heat released by the reaction is built-in from the fluidized bed reactorThe heat exchanger 6 and the external heat exchanger 5 take heat in time, and generate a byproduct of superheated steam with the pressure of more than 1.5 MPa. The material mixing is enhanced by adjusting the medium circulation metering pump 4 to transfer the inert medium from the upper part of the reactor to the lower part of the reactor through the pump under the action of the external circulation device. In the system of the inert medium external circulation device with the heat exchange device, the liquid-solid separator 8 is arranged, so that waste contact bodies or waste inert media can be separated from the reaction system according to the reaction requirement, and fresh inert media and contact bodies are supplemented. The product after the reaction in the slurry bed reactor 3 and the unreacted methane chloride are removed from the upper end of the slurry bed reactor 3 in a gaseous state, cooled by the condenser 9 for one time, passed through the gas-liquid separator 11, the gas outlet temperature is controlled at 160 ℃, the liquid is an entrained inert medium, and recycled by the metering pump 13. The gas from the gas-liquid separator 11 is cooled for the second time by the condenser 10, then passes through the gas-liquid separator 12, the gas outlet temperature is controlled to be 20 ℃, the gas is unreacted methane chloride, the gas is recycled by the recycled raw material heat exchanger 7, the liquid is also a product, and the liquid is conveyed to a product refining unit, so that the selectivity of the obtained dimethyldichlorosilane reaches 92%.
Claims (10)
1. The reaction device for preparing the methyl chlorosilane is characterized by comprising a long-cylinder slurry reactor (1), wherein the interior of the long-cylinder slurry reactor comprises a raw material gas distributor (2) and a slurry bed reactor (3) from bottom to top, an inert medium is filled in the slurry bed reactor (3), and a built-in heat exchanger (6) is arranged in the slurry bed reactor (3).
2. The reaction apparatus for the production of methylchlorosilanes as claimed in claim 1, further comprising a feedstock heat exchanger (7), said feedstock heat exchanger (7) being in communication with the bottom of said long-tube slurry reactor (1).
3. A reaction device for preparing methyl chlorosilane is characterized by comprising a long cylindrical slurry reactor (1), a medium circulation metering pump (4) and an external heat exchanger (5),
wherein,
the long-cylinder type slurry reactor (1) comprises a raw material gas distributor (2) and a slurry bed reactor (3) from bottom to top, and an inert medium is filled in the slurry bed reactor (3);
one end of the medium circulation metering pump (4) is communicated with the upper part of the side wall of the slurry bed reactor (3), the other end of the medium circulation metering pump is communicated with the external heat exchanger (5), the other end of the external heat exchanger (5) is communicated with the lower part of the side wall of the slurry bed reactor (3), and under the action of the medium circulation metering pump (4), inert media are transferred to the lower part of the slurry bed reactor (3) from the upper part of the slurry bed reactor (3) through the medium circulation metering pump (4).
4. The reaction device for preparing methylchlorosilane as claimed in claim 3, wherein said reaction device further comprises a solid-liquid separator (8), one end of said solid-liquid separator (8) being in communication with the upper portion of the side wall of said slurry bed reactor (3), and the other end being in communication with said external medium circulation metering pump (4).
5. The reaction apparatus for the production of methylchlorosilanes as claimed in claim 3, further comprising a feedstock heat exchanger (7), said feedstock heat exchanger (7) being in communication with the bottom of said long barrel type slurry reactor (1).
6. A reaction device for preparing methyl chlorosilane is characterized by comprising a long cylindrical slurry reactor (1), a medium circulation metering pump (4) and an external heat exchanger (5),
wherein,
the long-cylinder type slurry reactor (1) comprises a raw material gas distributor (2) and a slurry bed reactor (3) from bottom to top, a built-in heat exchanger (6) is arranged in the slurry bed reactor (3), and an inert medium is filled in the slurry bed reactor (3);
one end of the medium circulation metering pump (4) is communicated with the upper part of the side wall of the slurry bed reactor (3), the other end of the medium circulation metering pump is communicated with the external heat exchanger (5), the other end of the heat exchanger (5) is communicated with the lower part of the side wall of the slurry bed reactor (3), and under the action of the medium circulation metering pump (4), inert media are transferred from the upper part of the slurry bed reactor (3) to the lower part of the slurry bed reactor (3).
7. The reaction device for preparing methylchlorosilane as claimed in claim 6, wherein said reaction device further comprises a solid-liquid separator (8), one end of said solid-liquid separator (8) being in communication with the upper portion of the sidewall of said slurry bed reactor (3), and the other end being in communication with said medium circulation metering pump (4).
8. The reaction apparatus for the production of methylchlorosilanes according to claim 6, wherein said apparatus further comprises a feedstock heat exchanger (7), said feedstock heat exchanger (7) being in communication with the bottom of said long-tube slurry reactor (1).
9. A system for preparing methyl chlorosilane is characterized by comprising a reaction device for preparing methyl chlorosilane, condensers (9) and (10), gas-liquid separators (11) and (12) and a medium recycling metering pump (13);
wherein,
the reaction device comprises a long-tube type slurry reactor (1), a raw material gas distributor (2) and a slurry bed reactor (3) are arranged in the long-tube type slurry reactor from bottom to top, an inert medium is filled in the slurry bed reactor (3), a built-in heat exchanger (6) is arranged in the slurry bed reactor (3), and/or the reaction device further comprises a medium circulation metering pump (4) and an external heat exchanger (5), one end of the medium circulation metering pump (4) is communicated with the upper part of the side wall of the slurry bed reactor (3) through a solid-liquid separator (8), the other end of the medium circulation metering pump is communicated with the external heat exchanger (5), the other end of the external heat exchanger (5) is communicated with the lower part of the side wall of the slurry bed reactor (3), and under the action of the medium circulation metering pump (4), the inert medium is transferred from the upper part of the slurry bed reactor (3) to the lower part of the slurry bed reactor (3,
the top of long tube-type slurry reactor (1) with the top intercommunication of condenser (9), the top of vapour and liquid separator (11) respectively with the bottom of condenser (9) with the top intercommunication of condenser (10), the bottom of vapour and liquid separator (11) with the one end intercommunication of medium retrieval and utilization measuring pump (13), the other end of medium retrieval and utilization measuring pump (13) and another relative lateral wall lower part intercommunication of slurry bed reactor (3), the top of vapour and liquid separator (12) respectively with the bottom of heat exchanger (10) with the bottom intercommunication of long tube-type slurry reactor (1).
10. The system for preparing methylchlorosilanes according to claim 9, wherein said apparatus further comprises a feedstock heat exchanger (7), one end of said feedstock heat exchanger (7) being in communication with the bottom end of said long barrel type slurry reactor (1), the other end being in communication with the top of said gas-liquid separator (12).
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| CN2010101466693A CN102212080A (en) | 2010-04-12 | 2010-04-12 | Reaction device for preparing methyl chlorosilane and reaction system comprising same |
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| CN103172072A (en) * | 2011-12-20 | 2013-06-26 | 储晞 | Reactor and method for realizing synthesis of chlorosilane |
| CN105296956A (en) * | 2015-11-20 | 2016-02-03 | 沈阳黎明航空发动机(集团)有限责任公司 | Aluminizing process method for inner cavity and outer surface of cobalt-base alloy blade |
| CN106749380A (en) * | 2017-02-23 | 2017-05-31 | 镇江江南化工有限公司 | A kind of methyl chlorosilane monomer synthesizes circulating reaction system |
| CN109821483A (en) * | 2019-03-28 | 2019-05-31 | 合盛硅业股份有限公司 | The automatic continuous adding method of catalyst and device |
| CN113200834A (en) * | 2021-05-15 | 2021-08-03 | 公主岭市恒昌科技有限公司 | Method for preparing hydroxypivalaldehyde |
| CN114130328A (en) * | 2021-11-10 | 2022-03-04 | 北京中教金源科技有限公司 | Photo-thermal synergistic continuous phase catalytic system |
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