CN114213445A - Method for returning organic silicon contact to bed - Google Patents
Method for returning organic silicon contact to bed Download PDFInfo
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- CN114213445A CN114213445A CN202111476986.6A CN202111476986A CN114213445A CN 114213445 A CN114213445 A CN 114213445A CN 202111476986 A CN202111476986 A CN 202111476986A CN 114213445 A CN114213445 A CN 114213445A
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- Prior art keywords
- contact
- fine powder
- fluidized bed
- activation
- bed reactor
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 37
- 239000010703 silicon Substances 0.000 title abstract description 17
- 229910052710 silicon Inorganic materials 0.000 title abstract description 17
- 230000004913 activation Effects 0.000 claims abstract description 78
- 239000000843 powder Substances 0.000 claims abstract description 72
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims abstract description 66
- YGZSVWMBUCGDCV-UHFFFAOYSA-N chloro(methyl)silane Chemical compound C[SiH2]Cl YGZSVWMBUCGDCV-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000012535 impurity Substances 0.000 claims abstract description 45
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 41
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000003054 catalyst Substances 0.000 claims abstract description 39
- 239000010949 copper Substances 0.000 claims abstract description 39
- 229910052802 copper Inorganic materials 0.000 claims abstract description 39
- 239000011863 silicon-based powder Substances 0.000 claims abstract description 38
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 229940050176 methyl chloride Drugs 0.000 claims abstract description 29
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 20
- 230000009471 action Effects 0.000 claims abstract description 18
- 230000008569 process Effects 0.000 claims abstract description 14
- 238000004064 recycling Methods 0.000 claims abstract description 14
- 239000007789 gas Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 238000000926 separation method Methods 0.000 claims description 36
- 239000002245 particle Substances 0.000 claims description 31
- 239000003921 oil Substances 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 13
- 239000012043 crude product Substances 0.000 claims description 9
- 239000002699 waste material Substances 0.000 claims description 8
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 7
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 7
- 229940112669 cuprous oxide Drugs 0.000 claims description 7
- 238000005070 sampling Methods 0.000 claims description 6
- 238000012360 testing method Methods 0.000 claims description 6
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 3
- 229940045803 cuprous chloride Drugs 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- 238000011084 recovery Methods 0.000 claims description 2
- 229910001873 dinitrogen Inorganic materials 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 8
- 238000001994 activation Methods 0.000 description 66
- 238000004519 manufacturing process Methods 0.000 description 15
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 7
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 3
- 238000012423 maintenance Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- WCCJDBZJUYKDBF-UHFFFAOYSA-N copper silicon Chemical compound [Si].[Cu] WCCJDBZJUYKDBF-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/12—Organo silicon halides
- C07F7/16—Preparation thereof from silicon and halogenated hydrocarbons direct synthesis
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/20—Purification, separation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The application provides a method for returning an organic silicon contact body to a bed, which comprises the following steps: mixing silicon powder and a copper catalyst in a contact tank to form a first contact, inputting the first contact into a fluidized bed reactor, simultaneously introducing methyl chloride gas into the fluidized bed reactor, reacting the silicon powder and the methyl chloride under the action of the copper catalyst to generate a crude methyl chlorosilane, separating the crude methyl chlorosilane through a cyclone separator, introducing the obtained methyl chlorosilane into an impurity removal process, directly conveying a second contact separated by a primary cyclone separator into the fluidized bed reactor for reaction, conveying a third contact and a fourth contact separated by secondary and tertiary cyclone separators into a fine powder activation bed for activation, introducing nitrogen into the fine powder activation bed, removing carbon impurities from the third contact and the fourth contact through the nitrogen, collecting the third contact and the fourth contact in the fine powder tank, and conveying the third contact and the fourth contact into the fluidized bed reactor for recycling. The method removes carbon on the surface of the contact, improves the reaction activity and the utilization rate of the silicon powder, and simultaneously improves the yield of the methyl chlorosilane.
Description
Technical Field
The application relates to the technical field of organic silicon, in particular to a method for returning an organic silicon contact to a bed.
Background
Organic silicon is widely applied as a new chemical material due to a series of advantages of high and low temperature resistance, corrosion resistance and the like. Methylchlorosilanes are the most important monomers for the preparation of silicone polymers, with dimethyldichlorosilane being used in amounts of up to about 90% of methylchlorosilanes.
In the production process of organic silicon, silicon powder and chloromethane are used as production raw materials, and copper is used as a catalyst to promote the synthesis of organic silicon monomers such as dimethyl dichlorosilane. In the reaction of producing dimethyldichlorosilane, silicon powder and copper catalyst are mixed to form active contact, and along with the prolonging of reaction time, the deposit on the surface of the contact is more and more, mainly because carbon-containing impurities are accumulated in the reaction process to pollute the silicon copper contact, the activity of the contact is reduced, and the synthesis rate of dimethyldichlorosilane is reduced.
In the prior art, the contact body is separated by the cyclone separator and then directly returns to the bed to participate in the reaction, carbon deposition on the surface of the contact body cannot be effectively removed, so that the activity of the contact body is reduced, the reactor needs to be stopped and overhauled when impurities reach a certain degree, a new contact body can be added to start a new reaction period after the reactor is cleaned, the production efficiency of methyl chlorosilane is greatly influenced by the process, the production period is further shortened, and the production cost of enterprises is improved. When the contact body pollution is relatively serious, the contact body can not be returned to the bed for use, so that the utilization rate of the silicon powder is reduced, and the production efficiency of the methyl chlorosilane is also reduced.
Disclosure of Invention
The application provides a method for an organic silicon contact body returning process, which is used for solving the problems of carbon deposition on the surface of the organic silicon contact body and reduction of activation performance.
The application provides a method for returning an organic silicon contact body to a bed, which comprises the following steps:
s1: mixing silicon powder and a copper catalyst in a contact tank to form a first contact, inputting the first contact into a fluidized bed reactor, and introducing methyl chloride gas into the fluidized bed reactor to react the silicon powder and the methyl chloride under the action of the copper catalyst to generate a crude product of methyl chlorosilane.
S2: and (3) sequentially inputting the crude methyl chlorosilane into a first-stage cyclone separator, a second-stage cyclone separator and a third-stage cyclone separator for separation, and sequentially separating to obtain a second contact, a third contact, a fourth contact, methyl chlorosilane and methyl chloride, wherein the methyl chlorosilane and the methyl chloride enter the next impurity removal process.
S3: and directly conveying the second contact body obtained by separation of the primary cyclone separator to a fluidized bed reactor for reaction, and conveying the third contact body obtained by separation of the secondary cyclone separator and the fourth contact body obtained by separation of the tertiary cyclone separator to a fine powder activation bed for activation.
S4: and introducing nitrogen into the fine powder activation bed to activate the third contact and the fourth contact, collecting the activated third contact and the activated fourth contact in a fine powder tank, and conveying the third contact and the activated fourth contact to the fluidized bed reactor for recycling.
Optionally, the copper-based catalyst is one or more of cuprous oxide and cuprous chloride.
Optionally, the mass fraction of the copper-based catalyst in the first contact is 4-7%.
Optionally, the temperature in the fluidized bed reactor is 280-310 ℃, and the pressure is 0.28-0.31 MPa.
Optionally, the fine powder activation bed is heated by heat conduction oil in the jacket, the temperature of the heat conduction oil is 240-260 ℃, the temperature in the fine powder activation bed is 100-120 ℃, and the pressure is 0.1-0.2 MPa.
Optionally, the third contact obtained by separation with the secondary cyclone separator and the fourth contact obtained by separation with the tertiary cyclone separator are transported to a fine powder activation bed for activation, including:
and (3) sampling and testing the particle sizes of the third contact and the fourth contact, and if the particle sizes of the third contact and the fourth contact are more than or equal to 30 micrometers, conveying the third contact and the fourth contact to a fine powder activation bed for activation.
Optionally, if the particle size of the third contact and the fourth contact is smaller than 30 μm, the third contact and the fourth contact are used as waste contacts and subjected to directional conversion treatment by the contact tank.
Optionally, the contact tank is further configured to send the contact that has not been reacted in the fluidized bed reactor to the contact tank when the fluidized bed reactor is stopped for maintenance or is stopped in case of a fault emergency, and send the contact of the contact tank to the fluidized bed reactor for reaction when the system resumes production and is started again.
Optionally, the flow rate of nitrogen in the fine powder activation bed is 1000Nm3/h。
Optionally, a filtering system is arranged behind the fine powder activation bed, and the filtering system collects the carbon impurities on the surfaces of the third contact and the fourth contact and then burns the carbon impurities.
According to the method for the organic silicon contact body returning process, methyl chlorosilane and a contact body synthesized in a fluidized bed reactor are separated through a cyclone separator, the obtained contact body is conveyed to a fine powder activation bed for impurity removal, and after carbon impurities deposited on the surface of the contact body are blown off through nitrogen, the contact body is conveyed into the fluidized bed reactor again for recycling, so that the purpose of impurity removal on the surface of the contact body is achieved, the utilization rate of silicon powder is improved, the production efficiency of the methyl chlorosilane is improved, and the production cost is reduced.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present application, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a flow chart of a method of silicone contact set-back provided herein.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application are clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present application, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
Fig. 1 is a flow chart of a method of silicone contact bed recovery provided herein, which may include, as shown in fig. 1:
s1: and (2) stirring and mixing the silicon powder and the copper catalyst in a contact tank to form a first contact, inputting the first contact into a fluidized bed reactor, and simultaneously introducing methyl chloride gas into the fluidized bed reactor to react the silicon powder and the methyl chloride under the action of the copper catalyst to generate a crude product of methyl chlorosilane.
Specifically, silicon powder and a copper catalyst are mixed in a contact tank to form a first contact with reaction activity, the first contact is input into a fluidized bed reactor, methyl chloride gas is introduced into the fluidized bed reactor, the silicon powder and the methyl chloride react under the action of the copper catalyst, the first contact which is uniformly mixed in advance in the contact tank can increase the contact area of the silicon powder and the methyl chloride, and the copper catalyst can better promote the reaction of the silicon powder and the methyl chloride to generate a crude methyl chlorosilane.
S2: and (3) sequentially inputting the crude methyl chlorosilane into a first-stage cyclone separator, a second-stage cyclone separator and a third-stage cyclone separator for separation, and sequentially separating to obtain a second contact, a third contact, a fourth contact and methyl chlorosilane, wherein the methyl chlorosilane enters the next impurity removal process.
Specifically, the gas methyl chlorosilane crude product synthesized by the fluidized bed reactor is sequentially input into a first-stage cyclone separator, a second-stage cyclone separator and a third-stage cyclone separator for separation, the gas methyl chlorosilane crude product at the outlet of the fluidized bed reactor comprises methyl chlorosilane and methyl chloride generated by reaction and a contact body brought out along with gas, gas-solid separation is carried out under the action of the cyclone separators, and the methyl chlorosilane and the methyl chloride obtained by separation are input into the next impurity removal process.
S3: and directly conveying the second contact body obtained by separation of the primary cyclone separator to a fluidized bed reactor for reaction, and conveying the third contact body obtained by separation of the secondary cyclone separator and the fourth contact body obtained by separation of the tertiary cyclone separator to a fine powder activation bed for activation.
Specifically, the second contact body obtained by separation of the primary cyclone separator is directly conveyed to the fluidized bed reactor for recycling, the contact body obtained by separation of the primary cyclone separator is more in amount, the particle size of the contact body is larger, the contact body has reaction activity and can directly participate in reaction, and then the third contact body obtained by separation of the secondary cyclone separator and the fourth contact body obtained by separation of the tertiary cyclone separator are conveyed to the fine powder activation bed for activation.
S4: and introducing nitrogen into the fine powder activation bed to activate the third contact and the fourth contact, collecting the activated third contact and the activated fourth contact in a fine powder tank, and conveying the third contact and the activated fourth contact to the fluidized bed reactor for recycling.
Specifically, nitrogen is introduced into a fine powder activation bed to remove impurities on the surfaces of a third contact and a fourth contact, the nitrogen has a certain flow velocity in the fine powder activation bed, so that the contacts have a fluid-like flowing state in the fine powder activation bed, and silicon powder particles have certain hardness, the contact particles collide and rub with each other under the action of airflow, carbon impurities deposited on the surfaces of the contacts fall off from the surfaces of the contacts, the activated contacts are obtained, the carbon impurities on the surfaces of the contacts are carbon generated by thermal decomposition of a small amount of carbon contained in the silicon powder and methyl chloride, and then the activated third contact and the activated fourth contact are collected in a fine powder tank and conveyed to a fluidized bed reactor for recycling.
Optionally, the copper-based catalyst is one or more of cuprous oxide and cuprous chloride.
Wherein, the copper catalyst has higher activity and can promote the reaction of the silicon powder and the chloromethane.
Optionally, the mass fraction of the copper-based catalyst in the first contact is 4-7%.
When the silicon powder and the copper catalyst are mixed, the mass fraction of the copper catalyst in the contact body is 4-7%, the activity of the copper catalyst is high, and the reaction can be promoted only by a small amount.
Optionally, the temperature in the fluidized bed reactor is 280-310 ℃, and the pressure is 0.28-0.31 MPa.
Wherein, the temperature in the fluidized bed reactor is controlled at the temperature of 280-310 ℃, the reaction rate of the main product dimethyldichlorosilane can be increased by increasing the temperature in the temperature range, but the reaction rate is decreased by continuously increasing the temperature, so that the generation of the main product dimethyldichlorosilane is facilitated by controlling the temperature at the temperature of 280-310 ℃. Proper pressurization in the fluidized bed reactor can lead to higher yield of the main product dimethyldichlorosilane, but the over-high pressure has less influence on the generated product and increases the production cost.
Optionally, a jacket is arranged outside the fine powder activation bed, the fine powder activation bed is heated by heat conduction oil in the jacket, the temperature of the heat conduction oil is 240-260 ℃, the temperature in the fine powder activation bed is 100-120 ℃, and the pressure is 0.1-0.2 MPa. The contact activation process is 4-8 hours, and the yield of the methyl chlorosilane can be improved by 2-3 percent after the contact is activated and returned to the bed.
The third contact and the fourth contact are input into the fine powder activation bed, a jacket is arranged outside the fine powder activation bed, heat conduction oil is introduced into the jacket, the temperature of the heat conduction oil is controlled to be 240-fold-260 ℃, the fine powder activation bed is heated by taking the heat conduction oil as a heat transfer medium, the temperature in the fine powder activation bed is kept to be 100-fold-120 ℃, and meanwhile, the pressure is controlled to be 0.1-0.2MPa, so that carbon impurities on the surface of the contact can fall off from the surface of the contact.
Optionally, the third contact obtained by separation with the secondary cyclone separator and the fourth contact obtained by separation with the tertiary cyclone separator are transported to a fine powder activation bed for activation, including:
and (3) sampling and testing the particle sizes of the third contact and the fourth contact, and if the particle sizes of the third contact and the fourth contact are more than or equal to 30 micrometers, conveying the third contact and the fourth contact to a fine powder activation bed for activation.
Specifically, when the particle diameters of the third contact and the fourth contact are greater than or equal to 30 μm, silicon powder reacting with methyl chloride exists in the contacts, and the area of the silicon powder capable of participating in the reaction is reduced because the surfaces of the third contact and the fourth contact are covered by deposited carbon impurities, so that the carbon impurities on the surfaces of the third contact and the fourth contact need to be removed, the silicon powder with reaction activity is exposed, and the utilization rate of the silicon powder is improved.
Optionally, if the particle size of the third contact and the fourth contact is smaller than 30 μm, the third contact and the fourth contact are used as waste contacts and subjected to directional conversion treatment by the contact tank.
Specifically, if the particle sizes of the third contact and the fourth contact are smaller than 30 μm, the ultrafine silicon powder increases the aggregation force among the particles, the dispersibility is poor, the heat dissipation of the system is adversely affected or the entrainment amount along with the air flow is increased, and the contact particles contain more impurities which affect the reaction between the silicon powder and the methyl chloride and are not beneficial to the reaction, so that the third contact and the fourth contact are used as waste contacts to be subjected to directional conversion treatment through the contact tank.
Optionally, the contact tank is further used for feeding the contacts in the fluidized bed reactor into the contact tank when the fluidized bed reactor is stopped.
Specifically, the contact tank is also used for sending the unreacted contacts in the fluidized bed reactor into the contact tank when the fluidized bed reactor is stopped for maintenance or the system needs emergency stop when meeting faults, and sending the contacts in the contact tank into the fluidized bed reactor to participate in reaction when the system recovers a normal production cycle.
Optionally, the flow rate of nitrogen in the fine powder activation bed is 1000Nm3/h。
Specifically, the nitrogen in the fine powder activation bed has a certain flow velocity, so that the contact body has a fluid-like flow state in the fine powder activation bed, and in the flow state, carbon impurities on the surface of the contact body can be removed.
Optionally, a filtering system is arranged behind the fine powder activation bed, and the filtering system collects the removed carbon impurities on the surfaces of the third contact and the fourth contact and then burns the carbon impurities.
Specifically, the third contact and the fourth contact which are subjected to impurity removal by the fine powder activation bed are recycled, the removed carbon impurities are filtered and collected by a filtering system arranged behind the fine powder activation bed, and then the collected carbon impurities are incinerated, so that the pollution to the environment is reduced compared with direct discharge.
The technical solution of the present application is illustrated in detail by the following specific examples.
Example 1
A method for returning an organic silicon contact body to a bed comprises the following steps:
1) mixing silicon powder and a copper catalyst in a contact tank to form a first contact, wherein the mass percentage of the copper catalyst in the contact is 4% and the copper catalyst is cuprous oxide during mixing. And inputting the first contact into a fluidized bed reactor, and simultaneously introducing methyl chloride gas into the fluidized bed reactor to enable silicon powder and methyl chloride to react under the action of a copper catalyst to generate a crude product of methyl chlorosilane, wherein the temperature in the fluidized bed reactor is 280 ℃, and the pressure in the fluidized bed reactor is 0.28 MPa.
2) And (2) sequentially inputting the crude methyl chlorosilane synthesized in the fluidized bed reactor into a primary cyclone separator, a secondary cyclone separator and a tertiary cyclone separator for separation, performing gas-solid separation under the action of the cyclone separators, sequentially separating to obtain a second contact, a third contact, a fourth contact, methyl chlorosilane and methyl chloride, and feeding the methyl chlorosilane and the methyl chloride obtained by separation into the next impurity removal process.
3) And (3) directly conveying the second contact body separated by the primary cyclone separator to a fluidized bed reactor for recycling, then sampling and testing the particle sizes of the third contact body and the fourth contact body separated by the secondary cyclone separator and the tertiary cyclone separator, conveying the third contact body and the fourth contact body to a fine powder activation bed for activation if the particle sizes of the third contact body and the fourth contact body are more than or equal to 30 microns, and taking the third contact body and the fourth contact body as waste contact bodies to be subjected to directional conversion treatment by a contact body tank if the particle sizes of the third contact body and the fourth contact body are less than 30 microns.
4) Introducing nitrogen into the fine powder activation bed to remove impurities, wherein the nitrogen has a certain flow velocity in the fine powder activation bed, the silicon powder particles have a certain hardness, under the action of air flow, the contact particles collide and rub with each other,and (3) enabling the carbon impurities deposited on the surface of the contact body to fall off from the surface of the contact body, and obtaining the activated contact body. The flow rate of nitrogen in the fine powder activation bed is 1000Nm3And h, arranging a jacket outside the fine powder activation bed, and heating the fine powder activation bed through heat conduction oil in the jacket, wherein the temperature of the heat conduction oil is 240 ℃, the temperature in the fine powder activation bed is 100 ℃, and the pressure is 0.1 MPa. And a filtering system is arranged behind the fine powder activation bed, and the filtering system collects the carbon impurities on the surface of the blown contact body and then burns the carbon impurities.
5) And collecting the activated contact bodies in a fine powder tank and conveying the contact bodies to the fluidized bed reactor for recycling.
Example 2
A method for returning an organic silicon contact body to a bed comprises the following steps:
1) mixing silicon powder and a copper catalyst in a contact tank to form a first contact, wherein the mass percentage of the copper catalyst in the contact is 5% and the copper catalyst is cuprous oxide during mixing. And inputting the first contact into a fluidized bed reactor, and simultaneously introducing methyl chloride gas into the fluidized bed reactor to enable silicon powder and methyl chloride to react under the action of a copper catalyst to generate a crude product of methyl chlorosilane, wherein the temperature in the fluidized bed reactor is 295 ℃, and the pressure in the fluidized bed reactor is 0.29 MPa.
2) And (2) sequentially inputting the crude methyl chlorosilane synthesized in the fluidized bed reactor into a primary cyclone separator, a secondary cyclone separator and a tertiary cyclone separator for separation, performing gas-solid separation under the action of the cyclone separators, sequentially separating to obtain a second contact, a third contact, a fourth contact, methyl chlorosilane and methyl chloride, and feeding the methyl chlorosilane and the methyl chloride obtained by separation into the next impurity removal process.
3) And (3) directly conveying the second contact body separated by the primary cyclone separator to a fluidized bed reactor for recycling, then sampling and testing the particle sizes of the third contact body and the fourth contact body separated by the secondary cyclone separator and the tertiary cyclone separator, conveying the third contact body and the fourth contact body to a fine powder activation bed for activation if the particle sizes of the third contact body and the fourth contact body are more than or equal to 30 microns, and taking the third contact body and the fourth contact body as waste contact bodies to be subjected to directional conversion treatment by a contact body tank if the particle sizes of the third contact body and the fourth contact body are less than 30 microns.
4) And introducing nitrogen into the fine powder activation bed to remove impurities, wherein the nitrogen has a certain flow velocity in the fine powder activation bed, and the silicon powder particles have certain hardness, and under the action of air flow, the contact body particles collide and rub with each other, so that carbon impurities deposited on the surface of the contact body fall off from the surface of the contact body, and the activated contact body is obtained. The flow rate of nitrogen in the fine powder activation bed is 1000Nm3And h, arranging a jacket outside the fine powder activation bed, and heating the fine powder activation bed through heat conduction oil in the jacket, wherein the temperature of the heat conduction oil is 250 ℃, the temperature in the fine powder activation bed is 112 ℃, and the pressure is 0.15 MPa. And a filtering system is arranged behind the fine powder activation bed, and the filtering system collects the carbon impurities on the surface of the blown contact body and then burns the carbon impurities.
5) And collecting the activated contact bodies in a fine powder tank and conveying the contact bodies to the fluidized bed reactor for recycling.
Example 3
A method for returning an organic silicon contact body to a bed comprises the following steps:
1) mixing silicon powder and a copper catalyst in a contact tank to form a first contact, wherein the mass percentage of the copper catalyst in the contact is 7% and the copper catalyst is cuprous oxide during mixing. And inputting the first contact into a fluidized bed reactor, and simultaneously introducing methyl chloride gas into the fluidized bed reactor to enable the silicon powder and the methyl chloride to react under the action of a copper catalyst to generate a crude product of the methyl chlorosilane, wherein the temperature in the fluidized bed reactor is 310 ℃, and the pressure in the fluidized bed reactor is 0.31 MPa.
2) And (2) sequentially inputting the crude methyl chlorosilane synthesized in the fluidized bed reactor into a primary cyclone separator, a secondary cyclone separator and a tertiary cyclone separator for separation, performing gas-solid separation under the action of the cyclone separators, sequentially separating to obtain a second contact, a third contact, a fourth contact, methyl chlorosilane and methyl chloride, and feeding the methyl chlorosilane and the methyl chloride obtained by separation into the next impurity removal process.
3) And (3) directly conveying the second contact body separated by the primary cyclone separator to a fluidized bed reactor for recycling, then sampling and testing the particle sizes of the third contact body and the fourth contact body separated by the secondary cyclone separator and the tertiary cyclone separator, conveying the third contact body and the fourth contact body to a fine powder activation bed for activation if the particle sizes of the third contact body and the fourth contact body are more than or equal to 30 microns, and taking the third contact body and the fourth contact body as waste contact bodies to be subjected to directional conversion treatment by a contact body tank if the particle sizes of the third contact body and the fourth contact body are less than 30 microns.
4) And introducing nitrogen into the fine powder activation bed to remove impurities, wherein the nitrogen has a certain flow velocity in the fine powder activation bed, and the silicon powder particles have certain hardness, and under the action of air flow, the contact body particles collide and rub with each other, so that carbon impurities deposited on the surface of the contact body fall off from the surface of the contact body, and the activated contact body is obtained. The flow rate of nitrogen in the fine powder activation bed is 1000Nm3And h, arranging a jacket outside the fine powder activation bed, and heating the fine powder activation bed through heat conduction oil in the jacket, wherein the temperature of the heat conduction oil is 250 ℃, the temperature in the fine powder activation bed is 120 ℃, and the pressure is 0.2 MPa. And a filtering system is arranged behind the fine powder activation bed, and the filtering system collects the carbon impurities on the surface of the blown contact body and then burns the carbon impurities.
5) And collecting the activated contact bodies in a fine powder tank and conveying the contact bodies to the fluidized bed reactor for recycling.
Comparative example 1
A method for returning an organic silicon contact body to a bed comprises the following steps:
1) mixing silicon powder and a copper catalyst in a contact tank to form a first contact, wherein the mass percentage of the copper catalyst in the contact is 7% and the copper catalyst is cuprous oxide during mixing. And inputting the first contact into a fluidized bed reactor, and simultaneously introducing methyl chloride gas into the fluidized bed reactor to enable the silicon powder and the methyl chloride to react under the action of a copper catalyst to generate a crude product of the methyl chlorosilane, wherein the temperature in the fluidized bed reactor is 310 ℃, and the pressure in the fluidized bed reactor is 0.31 MPa.
2) Inputting the crude methylchlorosilane synthesized in the fluidized bed reactor into a primary cyclone separator, a secondary cyclone separator and a tertiary cyclone separator in sequence for separation, separating in sequence to obtain a second contact, a third contact, a fourth contact, methylchlorosilane and chloromethane, carrying out gas-solid separation under the action of the cyclone separator, and feeding the separated methylchlorosilane and chloromethane into the next impurity removal process.
3) And directly conveying the second contact body, the third contact body and the fourth contact body which are obtained by separation through the cyclone separator to the fluidized bed reactor for recycling.
Experimental example 1
A comparison of the above-described protocols in examples 1-3 with the protocol in comparative example 1 was calculated and the results are shown in table one.
Watch 1
Through the comparison of the schemes of the above embodiments, the application has the following beneficial effects:
(1) the application realizes the purpose of activating the surface of the organic silicon contact body and returning to the bed, and compared with the prior art (comparative example 1), the yield of the methyl chlorosilane product is higher.
(2) The edulcoration reagent quantity of this application scheme is still less, compares in prior art (comparative example 1), and the contact is returned the bed and is improved the utilization ratio of silica flour, has reduced manufacturing cost.
(3) When the contact body is activated in the production process of the scheme, the waste contact body is discharged and treated, the production period is prolonged, the problem that frequent parking and maintenance are needed due to more impurities is solved, and the production efficiency is improved.
(4) The process is convenient to operate and easy to realize industrialization.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present application, and not for limiting the same; although the present application has been described in detail with reference to the foregoing embodiments, it will be understood by those skilled in the art; the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present application.
Claims (10)
1. A method of silicone contact recovery from a bed, comprising:
s1: mixing silicon powder and a copper catalyst in a contact tank to form a first contact, inputting the first contact into a fluidized bed reactor, and simultaneously introducing methyl chloride gas into the fluidized bed reactor to react the silicon powder and the methyl chloride under the action of the copper catalyst to generate a crude product of methyl chlorosilane;
s2: inputting the crude methyl chlorosilane into a first-stage cyclone separator, a second-stage cyclone separator and a third-stage cyclone separator in sequence for separation, and obtaining a second contact, a third contact, a fourth contact, methyl chlorosilane and methyl chloride through separation in sequence, wherein the methyl chlorosilane and the methyl chloride enter the next impurity removal process;
s3: directly conveying the second contact body obtained by separation of the primary cyclone separator to the fluidized bed reactor for reaction, and conveying the third contact body obtained by separation of the secondary cyclone separator and the fourth contact body obtained by separation of the tertiary cyclone separator to a fine powder activation bed for activation;
s4: and introducing nitrogen into the fine powder activation bed to activate the third contact and the fourth contact, collecting the activated third contact and the activated fourth contact in a fine powder tank, and conveying the activated third contact and the activated fourth contact to the fluidized bed reactor for recycling.
2. The method of claim 1, wherein the copper-based catalyst is one or more of cuprous oxide and cuprous chloride.
3. The method of claim 1 or 2, wherein the mass fraction of the copper-based catalyst in the first contact is 4-7%.
4. The method as claimed in claim 1, wherein the temperature in the fluidized bed reactor is 280-310 ℃ and the pressure is 0.28-0.31 MPa.
5. The method as claimed in claim 1, wherein the fine powder activation bed is heated by heat conducting oil in the jacket, the temperature of the heat conducting oil is 240-260 ℃, the temperature in the fine powder activation bed is 100-120 ℃, and the pressure is 0.1-0.2 MPa.
6. The method of claim 1, wherein the step of feeding the third contact separated by the secondary cyclone and the fourth contact separated by the tertiary cyclone to a fine powder activation bed for activation comprises:
and sampling and testing the particle sizes of the third contact and the fourth contact, and if the particle sizes of the third contact and the fourth contact are more than or equal to 30 micrometers, conveying the third contact and the fourth contact to a fine powder activation bed for activation.
7. The method of claim 6, further comprising:
and if the particle sizes of the third contact and the fourth contact are smaller than 30 mu m, performing directional conversion treatment on the third contact and the fourth contact serving as waste contacts through the contact tank.
8. The method of claim 1, wherein the contact tank is further configured to feed contacts within the fluidized bed reactor into the contact tank when the fluidized bed reactor is shut down.
9. The process of claim 1, wherein the flow rate of the nitrogen gas within the fine powder activation bed is 1000Nm3/h。
10. The method of claim 1, wherein the activated bed of fine powder is followed by a filtration system, and the filtration system collects the removed carbon impurities on the surfaces of the third and fourth contacts and then incinerates the collected carbon impurities.
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| CN114917845A (en) * | 2022-06-10 | 2022-08-19 | 合盛硅业股份有限公司 | Organic silicon monomer production method and system |
| CN115178189A (en) * | 2022-07-12 | 2022-10-14 | 合盛硅业股份有限公司 | Organic silicon monomer production system and method |
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