CN111068602A - Device and method for producing phenylchlorosilane - Google Patents
Device and method for producing phenylchlorosilane Download PDFInfo
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- CN111068602A CN111068602A CN201911327697.2A CN201911327697A CN111068602A CN 111068602 A CN111068602 A CN 111068602A CN 201911327697 A CN201911327697 A CN 201911327697A CN 111068602 A CN111068602 A CN 111068602A
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F33/00—Other mixers; Mixing plants; Combinations of mixers
- B01F33/40—Mixers using gas or liquid agitation, e.g. with air supply tubes
- B01F33/402—Mixers using gas or liquid agitation, e.g. with air supply tubes comprising supplementary stirring elements
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- 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
Abstract
The invention provides a device and a method for producing phenylchlorosilane, wherein the reaction device is a vertical reaction device and comprises the following steps: furnace body, solid feed inlet, gaseous feed inlet, discharge gate, furnace body top-down is provided with agitating unit including expanding district, low temperature reaction district, high temperature reaction district and in the furnace body, agitating unit runs through the rotation axis expand district, low temperature reaction district and high temperature reaction district, and agitating unit is at least be provided with the stirring paddle leaf on the rotation axis in the high temperature reaction district be provided with the spiral belt structure on the rotation axis in the low temperature reaction district. The median cross-sectional area of the expanded region is greater than the median cross-sectional area of the low temperature reaction region and/or the high temperature reaction region.
Description
Technical Field
The invention belongs to the field of chemical raw material production equipment, particularly relates to a device for producing phenyl chlorosilane, and particularly relates to a vertical synthesis device for producing phenyl chlorosilane by a direct method and a production method based on the device.
Background
Phenylchlorosilanes generally refer to phenyltrichlorosilane, diphenyldichlorosilane, methylphenyldichlorosilane in larger amounts, and other triphenylchlorosilanes in smaller amounts. The phenyl organosilicon polymer material prepared by the method comprises phenyl organosilicon resin, methyl phenyl silicone oil and phenyl silicone rubber. Due to the existence of phenyl groups, the high and low temperature resistance, the high refractive index, the flame retardance and the radiation resistance of the high-performance high-molecular material are all superior to those of methyl organic silicon high-molecular materials. The phenyl organosilicon polymer material is widely applied to the fields of electronics, daily chemicals, buildings, medical treatment, national defense, military industry and the like. Compared with million tons of annual output on the domestic methyl organic silicon, the annual output of phenyl organic silicon in China is less than ten thousand tons at present, and the development and the application of downstream phenyl-containing organic silicon materials are restricted.
At present, for the production of phenylchlorosilane, three methods are available, namely a Grignard method, a direct method and a gas phase condensation method.
The Grignard method comprises the steps of firstly preparing a phenyl Grignard agent from chlorobenzene and magnesium chips in a solvent, and then reacting the phenyl Grignard agent with silicon tetrachloride or methyltrichlorosilane to prepare phenylchlorosilane, wherein the preparation method has the defects that the reaction temperature is higher than the boiling point of the solvent in the preparation process of the Grignard agent, the initiation is difficult, a large amount of solvent is required to be used, the initiation is difficult to control, and the flushing or explosion is easy to cause; the amount of the magnesium salt as a byproduct is large, and the filtration is difficult; the solvent recovery treatment is complicated; the production efficiency is low, and the industrial large-scale production is basically difficult to carry out; meanwhile, the side reaction is more, and the yield is lower.
Therefore, the thermal condensation method and the direct method are widely adopted at present for industrially producing phenylchlorosilane.
The method for producing phenylchlorosilane by using a gas phase condensation method comprises the step of reacting chlorobenzene with trichlorosilane or methyldichlorosilane at about 650 ℃ under the pressure of 0.2-0.8 MPa to produce phenyltrichlorosilane or methylphenyldichlorosilane, so that the problem of large demand of phenyltrichlorosilane is solved, and the product cost is greatly reduced.
Citation 1 describes a method for producing phenylchlorosilane by a thermal condensation method, in which chlorobenzene and trichlorosilane or methyldichlorosilane are used as raw materials, an initiator such as chloroform is used for carrying out a condensation reaction in a high-temperature furnace tube at about 600 ℃, the proportion of the raw materials, the preheating temperature, the residence time, the reaction temperature and the pressure of the furnace tube are controlled to achieve a satisfactory conversion rate, phenyltrichlorosilane and methylphenyldichlorosilane can be obtained, the product yield can reach 40%, and byproducts such as benzene, hydrogen chloride, silicon tetrachloride and methyltrichlorosilane are obtained. The reactor can be used for reference of ethylene cracking furnaces in the petrochemical industry.
Citation 2 discloses a reactor for producing phenylchlorosilane by thermal condensation, wherein reaction heat can be better utilized by adding a sleeve, but equipment is too complex, expensive in manufacturing cost, easy to maintain and difficult to find damage and leakage, and certain potential safety hazards exist. The overlong sleeve makes the temperature of the preheated raw material unstable, increases the possibility of cracking reaction, causes the increase of carbon deposition to block a pipeline, greatly influences the heat transfer effect of the furnace tube due to the excessive carbon deposition, needs to be frequently removed, and shortens the reaction period and the service life of the furnace tube.
In general, the thermal condensation method can realize continuous industrial production, has fewer byproducts, is simple and easily available in raw materials, and has relatively low cost, but the thermal condensation method can only produce phenyltrichlorosilane and methylphenyldichlorosilane, and the direct method is generally adopted industrially to obtain widely used diphenyldichlorosilane.
Citation 3 describes a direct process for producing phenylchlorosilane, in which chlorobenzene reacts with silicon powder at about 500 ℃ in the presence of a copper-based catalyst to simultaneously obtain phenyltrichlorosilane and diphenyldichlorosilane, and the conversion rate and the yield of the target product diphenyldichlorosilane are improved by controlling the vaporization and reaction temperature of chlorobenzene, the selection of the catalyst, and the contact of gas-solid reaction and heat transfer effect. The direct method has the advantages of easily obtained raw materials, simple working procedures, no solvent, high space-time yield, simple, safe and reliable working procedures and easy realization of continuous large-scale production.
Because the direct method is a gas (chlorobenzene) solid (silicon powder and copper catalyst) reaction, the requirement of the heat transfer effect on the reactor is higher; the consumption of the copper catalyst is larger, and is usually more than 30 percent of silicon powder; the catalyst such as silicon powder, copper powder and the like has large abrasion on equipment and needs to be periodically replaced or alloy materials with high manufacturing cost are adopted; the ultrafine silica fume and the waste catalyst are mixed in the mixed coarse monomer, which brings harm to the subsequent rectification separation process, and the dust pollution is inevitable when the ultrafine silica fume and the waste catalyst are discharged out of the furnace body.
The current direct method for producing phenylchlorosilane usually adopts two forms of fluidized bed and stirred bed.
Citation 4 discloses a fluidized bed reactor, which comprises an upper end enclosure, a lower end enclosure, an expansion section and a reaction section, wherein a gas distributor with a conical structure is arranged at the bottom of the reaction section, so that the mixing effect of gas-solid reaction is enhanced. The transducer is additionally arranged, and the purpose is to solve the problem that the central temperature of the fluidized bed cannot reach the temperature required by the reaction, but the phenomenon that solid components are accumulated inside the fluidized bed to cause the reduction of the production efficiency still exists.
It can be seen that there is room and room in the art for further improvements in processes and apparatus for the production of phenylchlorosilanes using the direct process.
Cited documents:
cited document 1: CN 102443021A
Cited document 2: CN 102019155A
Cited document 3: CN 102936261A
Cited document 4: CN 102350274A
Disclosure of Invention
Problems to be solved by the invention
Based on long-term research on the existing method and device for producing phenylchlorosilane by the direct method, the inventor of the invention finds that the reaction device of the existing method for producing phenylchlorosilane by the direct method has the following problems in the running process:
in the gas-solid reaction, the mixing effect of chlorobenzene gas, silicon powder and a catalyst is very important. Because the specific gravity of the copper catalyst is usually larger in the existing production method due to the requirement of improving the production efficiency, the existing various fluidized beds only depend on the natural power transmission (input pressure, specific gravity, heat and other factors) of gas, and continuous feeding and continuous discharging are difficult.
In some cases, the unreacted silicon powder and the copper catalyst are inevitably partially carried out of the reactor under the winding belt of the product gas flow, so that great waste is caused.
In addition, the catalyst system of the direct method generally has 5 or more components, and for example, in the fluidized bed described in cited document 4, oxygen and water entrained in the introduced nitrogen gas inevitably affect the catalyst and reduce the activity.
In addition, in the direct method for producing phenylchlorosilane, the generated highly crosslinked phenyl organosilicon polymer has a high boiling point, is difficult to remove from a reactor, and is mixed with silicon powder and catalyst which are accumulated in a block shape at the lower end cone section part of the reactor, so that the gas distributor pipe is blocked, chlorobenzene steam cannot be introduced, and the reactor has to be temporarily stopped for cleaning.
Therefore, an object of the present invention is to provide a vertical reaction apparatus having a specific structure, which can uniformly distribute the temperature in the reaction apparatus during the production process, without reducing the reaction activity, and the synthesized gas product can be rapidly and smoothly discharged from the reaction apparatus without inclusion of excessive unreacted solid components, and even after a long period of production, the productivity reduction and the equipment wear caused by the deposition of solid materials inside the reaction apparatus will not occur.
Means for solving the problems
Through intensive research by the inventors of the present invention, it was found that the above technical problems can be solved by implementing the following technical solutions:
[1] the invention provides a reaction device for producing phenylchlorosilane, which is a vertical reaction device and comprises:
a furnace body, a solid raw material feeding port, a gas raw material feeding port and a discharging port,
the furnace body comprises an expansion area, a low-temperature reaction area and a high-temperature reaction area from top to bottom, a stirring device is arranged in the furnace body,
the stirring device penetrates through the expansion area, the low-temperature reaction area and the high-temperature reaction area through a rotating shaft, a plurality of stirring blades are arranged on the rotating shaft at least in the high-temperature reaction area, a spiral belt structure is arranged on the rotating shaft in the low-temperature reaction area,
the cross-sectional area of the enlarged region is greater than the cross-sectional area of the low temperature reaction zone and/or the high temperature reaction zone, as measured by the area of the median cross-section.
[2] The apparatus according to [1], wherein the solid feed port and/or the discharge port is/are arranged in an enlarged region of the furnace body; the gas feed inlet is arranged at the bottom of the high-temperature reaction zone of the furnace body.
[3] The apparatus according to [1] or [2], wherein the stirring means is provided with stirring blades on the rotating shafts in both the low-temperature reaction zone and the high-temperature reaction zone; or the stirring device is provided with a spiral belt structure on a rotating shaft in the low-temperature reaction zone and is provided with stirring blades on the rotating shaft in the high-temperature reaction zone.
[4] The apparatus according to any one of [1] to [3], wherein the rotation of the rotating shaft rotates the stirring blade and generates an upward driving force on the gas; the axial included angle between the stirring paddle and the rotating shaft is 30-90 ℃.
[5] The apparatus according to any one of [1] to [4], wherein the arrangement density of the stirring blades on the rotating shaft in the high-temperature reaction zone is increased from top to bottom.
[6] The apparatus according to any one of [1] to [5], wherein the furnace body has a cylindrical structure at least in the high-temperature reaction zone, and in the high-temperature reaction zone, the horizontal distance between the outer end of the stirring blade and the inner wall of the furnace body is 1/60 to 1/30 of the inner radius of the cylinder of the high-temperature reaction zone.
[7] The apparatus according to any one of [1] to [6], wherein the outer end of the stirring blade is made of a high-temperature-resistant and wear-resistant alloy.
[8] The apparatus according to any one of [1] to [7], wherein the furnace body has heating means in the low-temperature reaction zone and the high-temperature reaction zone, and optionally, the heating means has a heating jacket having a spiral with 1 to 5 turns.
[9] The apparatus according to any one of [1] to [8], wherein the discharge port is provided with a filter screen.
[10] The apparatus according to any one of [1] to [9], wherein the height of the reaction apparatus is 2000 to 10000 mm.
[11] The apparatus according to any one of [1] to [10], wherein the length-to-diameter ratio of the reaction apparatus is 3 to 10.
[12] Further, the present invention also provides a method for producing phenylchlorosilane, which comprises a step of reacting a mixture of benzene chloride, solid silicon and a catalyst in the reaction apparatus according to any one of [1] to [11] above.
ADVANTAGEOUS EFFECTS OF INVENTION
Through the implementation of the technical scheme, the invention can realize the following technical effects:
(1) compared with the prior art, the synthesis method of the invention which generally carries out the reaction at more than 500 ℃, the invention can carry out the synthesis reaction at lower temperature.
(2) The stirring blades at least provided in the high-temperature reaction zone can fully mix the gas raw material entering from the bottom of the furnace body with the solid silicon powder and the catalyst powder, so that the reaction can be carried out at high efficiency;
(3) the gas generated by the stirring paddle rises and stirs, so that the movement of solid matters in the furnace body can be increased, and solid powder is prevented from settling at the bottom of the furnace body or attaching to the inner wall of the furnace body;
(4) the gas generated by the stirring paddle rises and is stirred, so that the gas reaction product can be smoothly discharged from the discharge hole;
(5) the spiral belt structure and the stirring blades arranged on the rotating shaft can play a wall scraping effect when solid substances are adsorbed on the inner wall of the furnace body, so that unreacted solid raw materials attached to the inner wall of the furnace body continue to react with gas raw materials, and the reaction efficiency is improved;
(6) the stirring blades are sequentially arranged from top to bottom, the ascending air flow generated by the stirring blade at the lower end can reduce the solid adsorption on the stirring blade at the upper end, and the rotation of the stirring blades can promote the temperature conduction, so that the reaction temperature at the central part of the furnace body is basically consistent with the reaction temperature at the peripheral part;
(7) the content of unreacted solid matters in the product gas flow discharged from the discharge port can be effectively reduced by using the reaction device.
Drawings
FIG. 1A schematic view of a neutral reaction apparatus according to an embodiment of the present invention
FIG. 2A top view of a stirring blade according to an embodiment of the present invention
Description of the reference numerals
1: gas feed inlet
2: slag discharge port
3: solid raw material inlet
4: outlet for reaction products
5: flue gas inlet
6: flue gas outlet
7 heating jacket clamp
8: motor connecting device
9: motor for stirring
10: stirring shaft
11: spiral belt
12: stirring paddle
Detailed Description
The present invention will be described in detail below. The technical features described below are explained based on typical embodiments and specific examples of the present invention, but the present invention is not limited to these embodiments and specific examples. It should be noted that:
in the present specification, the numerical range represented by "numerical value a to numerical value B" means a range including the end point numerical value A, B.
In the present specification, the term "substantially" means that the error does not exceed 2%.
In this specification, the term "vertical" means that the reaction apparatus is located on the ground in a substantially vertical manner, and the materials (raw materials and/or reaction products) in the apparatus move up and down and along the normal direction of the ground level.
In the present specification, the term "plurality" means two or more.
In the present specification, "%" denotes mass% unless otherwise specified.
In this specification, the term "top-down" refers to from top to bottom along the normal direction of the horizon.
In the present specification, the "median cross-sectional area" refers to an area of a cross-section existing at a midpoint position in the vertical direction in a certain region.
In the present specification, the "particle diameter" refers to an average particle diameter, which can be measured by a commercial particle sizer.
In the present specification, the meaning of "may" includes both the meaning of performing a certain process and the meaning of not performing a certain process.
In this specification, "optional" or "optionally" means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where the event occurs and instances where it does not.
In the present specification, reference to "some particular/preferred embodiments," "other particular/preferred embodiments," "embodiments," and the like, means that a particular element (e.g., feature, structure, property, and/or characteristic) described in connection with the embodiment is included in at least one embodiment described herein, and may or may not be present in other embodiments. In addition, it is to be understood that the described elements may be combined in any suitable manner in the various embodiments.
< first aspect >
In a first aspect of the present invention, there is provided a reaction apparatus for producing phenylchlorosilane, the reaction apparatus being a vertical reaction apparatus comprising: the furnace body comprises an expansion area, a low-temperature reaction area and a high-temperature reaction area from top to bottom, and a stirring device is arranged in the furnace body. The stirring device penetrates through the expansion area, the low-temperature reaction area and the high-temperature reaction area through a rotating shaft, a plurality of stirring blades are arranged on the rotating shaft at least in the high-temperature reaction area, and the median cross-sectional area of the expansion area is larger than that of the low-temperature reaction area and/or the high-temperature reaction area. In some specific embodiments, the length-diameter ratio of the reaction device of the present invention can be 3 to 10, preferably 5 to 8.
Furnace body
In one embodiment of the present invention, the furnace body of the present invention is a multi-stage furnace body, i.e., the furnace body may include a plurality of spatial regions from top to bottom. As described above, these regions may be expanded regions, low temperature reaction regions, high temperature reaction regions, and the like. In addition, it should be noted that, for each of the above-mentioned zones, in some preferred embodiments of the present invention, there may be one or more of each in the furnace body. In a preferred embodiment of the present invention, the furnace body comprises an expansion region, a low-temperature reaction region and a high-temperature region from top to bottom. In addition, without limitation, one or more transition zones may also be provided between the expansion zone, the low temperature reaction zone, and the high temperature reaction zone.
In the present invention, the shape of each zone of the furnace body is not particularly limited, but from the viewpoint of promoting the completion of the reaction and reducing the inner wall of the solid matter adsorption reaction apparatus, each zone of the furnace body of the present invention has a cylindrical shape or a conical shape having a large top and a small bottom, and preferably, the cylindrical shape or the conical shape has a concentric structure.
In some specific embodiments of the invention, the cross-sectional area of the expanded region is greater than the cross-sectional area of the low temperature reaction zone, calculated as the area of the median cross-section of each zone. Preferably, the cross-sectional area of the expanded region is greater than 100% and less than 150% of the cross-sectional area of the low-temperature reaction region.
Further, in some specific embodiments of the present invention, the cross-sectional area of the low-temperature reaction zone is the same as the cross-sectional area of the high-temperature reaction zone, calculated as the area of the median cross-section; in other specific embodiments, the cross-sectional area of the low-temperature reaction zone is larger than that of the high-temperature reaction zone, in which case, the whole furnace body structure corresponding to the low-temperature reaction zone and the high-temperature reaction zone presents a solid cone shape with a large top and a small bottom.
In other specific embodiments of the present invention, there is a transition zone between the expanded zone and the low temperature reaction zone; and the low-temperature reaction zone and the high-temperature reaction zone are integrated.
In the invention, a feed inlet of solid raw materials, a feed inlet of gas raw materials and a discharge outlet of reaction products are arranged in the furnace body. The specific position of each of the above feed ports or discharge ports is not particularly limited, but in the present invention, it is preferable to provide the solid raw material inlet on the enlarged region, particularly on the upper side of the enlarged region, from the viewpoint of facilitating the mixing of the reactants, improving the reaction efficiency, and facilitating the transport of the reaction product. Likewise, it is preferred that the discharge opening is also provided in the enlarged region, in particular in the upper part of the enlarged region on the side opposite to the solid raw material inlet.
The gas reactant enters the furnace body from the bottom of the high-temperature reaction zone of the furnace body, and contacts and mixes with the solid reaction raw material entering from the upper part of the furnace body, so that the reaction is carried out at high temperature to generate a gas product, and the process is carried out under the rotating and stirring action of the stirring blades, so that the gas reaction product in the furnace body actually has the power of moving from the bottom space of the furnace body to the upper space. Therefore, in the present invention, in consideration of the above-mentioned circumstances, the cross-sectional area of the expanded region is set larger than that of the low-temperature reaction region, and the purpose thereof is: on one hand, after the solid reaction raw materials enter the furnace body from the feeding hole, a relatively large dispersion space can be formed, which is beneficial to the full dispersion and mixing of the solid reaction raw materials and the gas reaction raw materials; on the other hand, since the gas product obtained by the reaction has upward movement power in the furnace body, the obtained reaction product gas has relatively high upward movement rate in the high-temperature reaction zone and the low-temperature reaction zone, and the higher movement rate means that more unreacted solid reaction raw materials can be entrained in the reaction product gas flow. After the reaction product gas moves to the expanded region through the low-temperature reaction region, because the median cross-sectional area of the expanded region is larger than that of the low-temperature reaction region, the upward movement rate of the reaction product gas can be effectively reduced, and the amount of unreacted solid reaction raw materials of a winding belt in the reaction gas-generating body is further reduced, so that only the reaction product gas is ensured to be smoothly discharged from the discharge hole.
In addition, in some embodiments of the present invention, it is advantageous to further provide a filter screen at the discharge port of the furnace body of the reaction device to further reduce the possibility of solid matter being discharged from the reaction device.
In the present invention, the solid reaction material may contain solid silicon in the form of solid particles or solid powder, and a solid catalyst in the form of particles or powder as a reaction catalyst. In the present invention, the composition of the catalyst is not particularly limited. Similarly, the particle size of each solid reaction raw material is not particularly limited, and may be generally 50 to 500 mesh, preferably 100 to 300 mesh. Too small a particle size, which leads to an increase in the surface energy of the solid particles, in addition to increasing the procurement cost of the raw material, and therefore, a tendency to agglomerate during transportation or use; if the particle size is too large, the surface area of the solid reaction material in contact with the gaseous reaction material may be reduced, and the reaction efficiency may be lowered.
In addition, the furnace body of the invention is provided with a heating device to provide the heat required by the reaction of reactants in the furnace body. Generally, the reaction mixture in the low-temperature reaction zone and the high-temperature reaction zone inside the furnace body can be maintained at a temperature of 450 to 550 ℃, preferably 460 to 490 ℃ by using a heating device.
In some specific embodiments of the present invention, the heating device of the present invention is a heating jacket surrounding at least the outer wall of the high temperature reaction zone of the furnace body, and preferably, the heating device has a spiral heating jacket with 1-5 spiral ends. The bottom of the heating collet is provided with a fuel inlet and the upper end of the heating collet is provided with an outlet for exhaust gas. The heat required for the reaction in the furnace body is provided by the combustion of the fuel in the jacket. In the present invention, there is no particular limitation on the fuel in principle, but it is preferable to use clean energy such as natural gas as the fuel to reduce pollutants in the exhaust gas. In some preferred embodiments of the present invention, a spiral deflector is further disposed in the heating jacket clamp of the outer wall of the furnace body to increase the heat exchange capacity. The number and the interval of the baffles are not particularly limited, and may be set according to actual needs.
Preferably, in the present invention, the heating jacket is wrapped around the outer walls of the furnace body corresponding to the low temperature reaction zone and the high temperature reaction zone. The high temperature reaction zone is generally at a higher temperature than the low temperature reaction zone due to the bottom-up combustion of the fuel.
The volume of the reaction apparatus of the present invention is not particularly limited. Generally, the height of the reaction apparatus of the present invention may be set to 2000 to 10000mm, and preferably, may be 4000 to 8000 mm. If the height of the reaction apparatus is too high, the cost of the reaction apparatus may be too high, and discharge of the reaction product gas may be difficult. For the areas of the middle cross sections of the expanded zone, the low-temperature reaction zone and the high-temperature reaction zone in the furnace body of the reaction device, the areas are calculated by the equal-area circular areas: the diameter of the median cross section of the expanded region is 600-2000 mm, preferably 800-1800 mm; the diameters of the median cross sections of the low-temperature reaction zone and the high-temperature reaction zone can be 400-1500 mm, preferably 600-1200 mm.
In the present invention, the material of the furnace body is not particularly required, and any material may be used as long as it is a common material that is resistant to high temperature and wear. Typically, the furnace material may be steel from the viewpoint of cost and workability.
In addition, in some specific embodiments of the present invention, the inner wall of the furnace body is provided with a smooth inner wall to reduce the probability of solid matter adsorbing to the inner wall of the furnace body when the reaction is performed. The inner wall of the furnace body is not limited, and various treatments of corrosion prevention and protective coatings can be adopted to increase the strength of the furnace body and reduce the corrosion of the inner wall of the furnace body.
Stirring device
The direct process reaction for producing phenylchlorosilane according to the present invention is carried out in the presence of a stirring apparatus in the above-mentioned reaction apparatus.
The stirring device of the present invention includes a rotating shaft and a plurality of stirring blades provided on the rotating shaft. The rotating shaft at least penetrates through the expansion area, the low-temperature reaction area and the high-temperature reaction area of the furnace body. In some embodiments of the invention, the axis of rotation is substantially coincident with the furnace centerline.
The rotating shaft of the present invention is driven to rotate by a motor, and in some preferred embodiments, the motor is disposed at the top of the reaction apparatus of the present invention and is disposed outside the furnace body. In addition, in order to maintain the stability of the rotating shaft during operation, the present invention provides a support part at the bottom of the reaction apparatus (i.e., the bottom of the high temperature reaction zone). The supporting part is used for supporting the whole furnace body on the one hand, and on the other hand, the shaft sleeve can be arranged in the bottom supporting part to guarantee the upper and lower concentricity of the rotating shaft and avoid the influence on the stability of the reaction device caused by unstable rotation in the rotating process of the rotating shaft.
In the present invention, the stirring device is provided with a plurality of stirring blades at least on the rotating shaft in the high-temperature reaction zone. In other preferred embodiments, the stirring device is provided with stirring blades on the rotating shaft in the low-temperature reaction zone and the high-temperature reaction zone; or the stirring device is provided with a spiral belt structure on a rotating shaft in the low-temperature reaction zone and is provided with stirring blades on the rotating shaft in the high-temperature reaction zone.
The shape of the stirring blade is not particularly limited, and in some preferred embodiments, may be a shape having a propeller, for example, as long as it can generate an upward lift force during rotation. The arrangement of the stirring blades on the rotating shaft is not particularly limited, and may be a layered arrangement or a spiral-up arrangement. Preferably, the stirring blades are arranged in layers on the rotating shaft, and the stirring blades in each layer can be considered to be substantially in the same plane. In addition, no matter the stirring blades are arranged in a layered mode or in a spiral lifting mode, the included angle of the horizontal plane projection formed by the two adjacent stirring blades by taking the center of the rotating shaft as the vertex is 50-65 degrees. In other embodiments, the stirring blade is set at an angle of 45 degrees with respect to the rotation axis to better ensure a better stirring effect of the gas-solid reaction.
In some preferred embodiments of the present invention, the outer end portion (i.e., the end away from the rotating shaft) of the stirring blade used in the present invention is made of a high-temperature-resistant, wear-resistant alloy. By using such an alloy for the outer end portion, the wall scraping effect between the end portion and the solid matter adhered to the inner wall of the furnace body can be improved, and the damage or corrosion of the equipment can be reduced. The kind of the alloy is not particularly limited in the present invention, and for example, an iron-nickel alloy or the like can be used.
With respect to the length of the outer end portion of the stirring blade described above, the length is 1% to 15%, preferably 5% to 10%, of the total length of the stirring blade in some specific embodiments. In addition, in the high-temperature reaction zone, the horizontal distance between the outer end of the stirring blade and the inner wall of the furnace body is preferably 1/60-1/30, and preferably 1/50-1/40 of the radius of the cylinder of the high-temperature reaction zone.
In a preferred embodiment of the present invention, in order to further improve the gas-solid reaction efficiency and reduce the deposition of solid substances at the bottom of the reaction device (i.e., at the bottom of the high temperature reaction zone), when the stirring blades are arranged on the rotating shaft, the arrangement density of the stirring blades on the rotating shaft in the high temperature reaction zone is increased from top to bottom to increase the upward transmission power of substances in the lower zone.
As mentioned previously, the stirring device is provided with a helical band structure on the rotating shaft within the low temperature reaction zone. On one hand, the spiral belt structure can increase the disturbance of air flow in a low-temperature reaction area and is beneficial to the dispersion of solid reaction raw materials in a furnace body; on the other hand, the low-temperature reaction zone at the relative upper end of the rotating shaft is provided with the spiral belt structure, so that the probability of solid matters attached to the inner wall of the furnace body can be reduced, and the wall scraping force possibly encountered by the stirring blades below the furnace body can be reduced.
By using the stirring paddle, on one hand, the mixing effect of the gas-solid reactants is improved, and the reaction efficiency is improved, and on the other hand, the problems that solid substances are deposited at the bottom of the high-temperature reaction zone and block the gas reactant inlet are greatly avoided. In addition, in the gas-solid reaction process, the material transfer of a gas-solid reaction system is promoted through the rotation of the stirring paddle, so that the reaction temperature of the central area and the reaction temperature of the peripheral area in the high-temperature reaction area are distributed more evenly, and the effect of balancing temperature transfer is achieved.
Surprisingly, the use of the stirring device according to the invention plays a crucial role in particular in the temperature equalization of the reaction system in the furnace, in contrast to the knowledge that stirring measures are generally only considered to be effective only for mixing the materials. In the invention, when the gas-solid materials are mixed, the reaction product is presented in a gas form along with chemical reaction, so that not only is system heat exchange generated between substances in a reaction system and the reaction-product, but also heat conversion exists among the substances due to chemical and physical changes, so that the heat transfer process is more complicated. The stirring device can better transfer heat and balance the heat distribution among different areas of the material flow. So that the reaction can be maintained at a lower temperature than in the conventional reaction apparatus. Therefore, the reaction temperature in the furnace body can be set to be 450-550 ℃, preferably 460-490 ℃ for the reaction mixture in the low-temperature reaction zone and the high-temperature reaction zone in the furnace body.
The material of the rotating shaft used in the present invention is not particularly limited, and for example, a high-temperature resistant and corrosion resistant steel material can be used. In some specific embodiments of the present invention, the rotating shaft may be further provided in a hollow form, and at least one through hole may be provided at least at a bottom of the rotating shaft. Hot and dry inert gas can be introduced into the bottom of the high-temperature reaction zone through the hollow structure of the rotating shaft so as to be matched with the stirring blades to realize full mixing in the reaction system, and the temperature distribution in the reaction system is more uniform through heating of hot gas at the center part. As mentioned previously, the use of such means tends to result in a decrease in reaction efficiency in some cases, and therefore, this means is merely an unnecessary supplementary means, and the above means may not be used in a preferred embodiment of the present invention.
Other auxiliary devices
Without being limited thereto, the reaction apparatus for producing phenylchlorosilane according to the present invention may be used in combination with other auxiliary components in addition to the various components disclosed above.
In some specific embodiments, the reaction apparatus of the present invention is provided with an upper head and a lower head at the top and the bottom, respectively. The upper and lower end enclosures are used for sealing the space in the furnace body and have the function of heat preservation. The heat insulating material of the upper and lower end enclosures can adopt inorganic fiber layers, such as aluminum silicate fiber and the like.
In addition, the bottom of the reaction device is also provided with a slag discharge port so as to clean solid substances remained at the bottom.
In other specific embodiments, since the chlorobenzene is introduced into the high-temperature reaction zone from the bottom of the reaction apparatus in a gaseous manner, a chlorobenzene heating or gasifying apparatus may be additionally provided at the bottom or outside of the apparatus of the present invention, and optionally a pressurized conveying apparatus may be further used, so that the gaseous reaction raw material can be introduced into the high-temperature reaction zone of the reaction apparatus of the present invention more smoothly.
In addition, the reaction apparatus of the present invention may also employ temperature monitoring and temperature control means. The monitoring and control device is not particularly limited in the present invention, and any device commonly used in the art may be used. In some embodiments of the present invention, a plurality of temperature monitoring sensors may be disposed at different positions of the high temperature reaction zone or the low temperature reaction zone in the furnace body, and when the temperature sensors indicate that the internal temperature is insufficient, the supply of fuel in the heating jacket may be increased by the temperature control device to increase the heat supply to the furnace body; when the temperature sensor shows that the temperature distribution in the reaction zone is not uniform, the rotating speed of the rotating shaft can be increased, and the movement of the substances in the reaction zone is increased.
Also, optionally, other devices such as a vacuum-pumping device, a protective gas supply device, and a pressure monitoring device may be added to the reaction apparatus of the present invention.
The vertical reaction device provided by the invention can be used for continuous production or batch production of phenyl chlorosilane prepared by a direct method.
< second aspect >
In a second aspect of the invention, a direct method production method for preparing phenyl chlorosilane by reacting silicon powder with chlorobenzene is disclosed. It is to be noted that the reaction feed in the direct process of the present invention does not include silicon tetrachloride.
The direct process of the present invention is realized by the reaction apparatus disclosed in the above < first aspect >.
The specific reaction equation is as follows (only the main reaction is shown):
wherein the catalyst is a metal catalyst, typically the catalyst may comprise copper. The reaction temperature may be 450 ℃ to 550 ℃.
In some preferred embodiments of the present invention, the solid silicon powder and the catalyst are separately subjected to a preliminary drying treatment and then mixed, and are fed into the furnace body of the reaction apparatus through the solid raw material feed port of the reaction apparatus. The amount of the catalyst may be 10 to 40% by weight based on the total weight of the solid raw material.
The gasified chlorobenzene can be fed from the bottom of the reaction apparatus at the same time as or before the solid raw material is fed into the furnace body. So that the gas phase and the solid phase are mixed in a high-temperature reaction zone in the furnace body and react to obtain the diphenyl dichlorosilane.
The flow rates of the solid and gas feed ports of the reaction apparatus are not particularly limited, and reference may be made to the conventional means of operation in the art. In the reaction process, the furnace body is heated through the heating jacket clamp wrapped on the outer wall, and meanwhile, the rotation of the rotating shaft of the stirring device in the furnace body drives the stirring blades to mix the reactant flow.
The reaction product obtained by the reaction is discharged or collected through a discharge hole. In some preferred embodiments of the present invention, a pressure difference exists between each feeding port and each discharging port of the reaction device, and the pressure difference between any feeding port and any discharging port is 0.02 to 0.1MPa, preferably 0.03 to 0.5 MPa.
After the product obtained by the reaction is discharged through a discharge hole, the product can be connected with other purification equipment through a pipeline, and optionally, the product can be subjected to dust removal, purification or fractionation.
Examples
The following examples of the present invention are described, but the present invention is not limited to the following examples.
The production is carried out by adopting the device as shown in the attached figure 1:
solid feed and catalyst are added at inlet 3 and gaseous feed is heated at the inlet at the bottom 1. The motor 9 is started, the rotating shaft 10 is driven to rotate, and the heating jacket clamp 7 supplies heat to the reaction device through combustion of natural gas, so that the internal temperature of the reaction device is kept within the range of 470-550 ℃.
The gaseous products of the reaction are conducted away from the reaction product outlet 4.
The equipment continuously operates for 72-240 h, the product quality is kept stable, and the phenomenon of blockage or instability of reaction equipment does not occur.
It should be noted that, although the technical solutions of the present invention are described by specific examples, those skilled in the art can understand that the present disclosure should not be limited thereto.
Having described embodiments of the present disclosure, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the disclosed embodiments. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments. The terms used herein were chosen in order to best explain the principles of the embodiments, the practical application, or technical improvements to the techniques in the marketplace, or to enable others of ordinary skill in the art to understand the embodiments disclosed herein.
Industrial applicability
The reaction apparatus and the reaction method provided by the present invention can be industrially carried out.
Claims (12)
1. A reaction unit for producing phenylchlorosilane, characterized in that the reaction unit is a vertical reaction unit, which comprises:
a furnace body, a solid raw material feeding port, a gas raw material feeding port and a discharging port,
the furnace body comprises an expansion area, a low-temperature reaction area and a high-temperature reaction area from top to bottom, and a stirring device is arranged in the furnace body,
the stirring device penetrates through the expansion area, the low-temperature reaction area and the high-temperature reaction area through a rotating shaft, a plurality of stirring blades are arranged on the rotating shaft at least in the high-temperature reaction area, a spiral belt structure is arranged on the rotating shaft in the low-temperature reaction area,
the cross-sectional area of the enlarged region is greater than the cross-sectional area of the low temperature reaction zone and/or the high temperature reaction zone, as measured by the area of the median cross-section.
2. The apparatus of claim 1, wherein the solids inlet and/or the outlet are disposed in an enlarged region of the furnace body; the gas feed inlet is arranged at the bottom of the high-temperature reaction zone of the furnace body.
3. The apparatus according to claim 1 or 2, wherein the stirring device is provided with stirring blades on the rotating shafts in the low-temperature reaction zone and the high-temperature reaction zone; or the stirring device is provided with a spiral belt structure on a rotating shaft in the low-temperature reaction zone and is provided with stirring blades on the rotating shaft in the high-temperature reaction zone.
4. The apparatus according to any one of claims 1 to 3, wherein the rotation of the rotating shaft causes the stirring blade to rotate and generate an upward driving force on the gas; the axial included angle between the stirring paddle and the rotating shaft is 30-90 ℃.
5. The apparatus according to any one of claims 1 to 4, wherein the arrangement density of the stirring blades on the rotating shaft in the high-temperature reaction zone increases from top to bottom.
6. The apparatus according to any one of claims 1 to 5, wherein the furnace body has a cylindrical structure at least in the high-temperature reaction zone, and the outer ends of the stirring blades are horizontally spaced from the inner wall of the furnace body within the high-temperature reaction zone by 1/60 to 1/30 of the inner radius of the cylindrical body of the high-temperature reaction zone.
7. The apparatus according to any one of claims 1 to 6, wherein the outer end of the stirring blade is made of a high temperature resistant and wear resistant alloy.
8. The apparatus according to any one of claims 1 to 7, wherein the furnace body has heating means in the low temperature reaction zone and the high temperature reaction zone, optionally the heating means has a spiral heating jacket with a spiral number of 1 to 5.
9. The device according to any one of claims 1 to 8, wherein the discharge port is provided with a filter screen.
10. The apparatus according to any one of claims 1 to 9, wherein the height of the reaction apparatus is 2000 to 10000 mm.
11. The apparatus of any one of claims 1 to 10, wherein the length-to-diameter ratio of the reaction apparatus is 3 to 10.
12. A method for preparing phenylchlorosilane, which is characterized by comprising the step of mixing benzene chloride, solid silicon and a catalyst in a reaction device according to any one of claims 1 to 11 for reaction.
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| CN114653313A (en) * | 2022-04-07 | 2022-06-24 | 邬丛睿 | Organosilicon fluidized bed reactor |
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