CN115608277A

CN115608277A - Production equipment containing phenyl chlorosilane, production equipment control method and preparation method

Info

Publication number: CN115608277A
Application number: CN202211101175.2A
Authority: CN
Inventors: 梁经永; 陈道伟; 胡家啟; 霍彪; 黄亮兵
Original assignee: ZHEJIANG KAIHUA SYNTHETIC MATERIAL CO Ltd
Current assignee: ZHEJIANG KAIHUA SYNTHETIC MATERIAL CO Ltd
Priority date: 2022-09-09
Filing date: 2022-09-09
Publication date: 2023-01-17

Abstract

The invention provides production equipment containing phenylchlorosilane, a production equipment control method and a preparation method. The production apparatus includes: the reactor is used for containing reaction raw materials and is provided with an outlet and an inlet; the catalyst circulating device is respectively communicated with the outlet and the inlet and is used for driving at least part of the catalyst to circularly enter and exit the reactor; wherein, the reaction raw material comprises chlorosilane and a benzene-containing compound, and the catalyst comprises boron trifluoride or boron trichloride. The method can realize the recycling of the catalyst in the production process of the phenyl-containing chlorosilane, and separate the catalyst from the hydrogen generated by the reaction, thereby improving the reaction efficiency of the catalyst and reducing the production cost of the phenyl-containing chlorosilane.

Description

Production equipment containing phenyl chlorosilane, production equipment control method and preparation method

Technical Field

The invention relates to the technical field of chemical processes, in particular to production equipment containing phenylchlorosilane, a production equipment control method and a preparation method.

Background

The phenyl chlorosilane-containing monomer is a special organosilicon monomer, is used for manufacturing special organosilicon polymers, and can meet special performances of high temperature resistance, radiation resistance, high light transmittance and the like. Among them, diphenyldichlorosilane is a key raw material for producing a catalyst for olefin stereoregular polymerization.

At present, there are two main types of phenyl-containing chlorosilane produced in China, namely a high-temperature gas-phase condensation method and a direct method. The phenylchlorosilane includes mainly methylphenyldichlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, methylphenyldichlorosilane, ethylphenyldichlorosilane, and the like.

Boron trifluoride and boron trichloride can be used as catalysts for the production of phenylchlorosilane-containing compounds. Although the boron trifluoride and the boron trichloride can effectively reduce the reaction temperature, the boron trifluoride and the boron trichloride have low boiling points, and hydrogen which is difficult to condense is generated in the reaction, so that the catalyst is easy to carry away, the catalytic reaction efficiency is seriously reduced, and the use of the process in the production process of chlorosilane containing phenyl is influenced.

Therefore, in the production process of phenyl chlorosilane, how to avoid the boron trifluoride and boron trichloride catalyst from being carried away by hydrogen which is difficult to condense becomes one of the technical problems to be solved urgently by the technical personnel in the field.

Disclosure of Invention

The technical problem to be solved by the invention is as follows: in the production process of phenyl chlorosilane, how to avoid the boron trifluoride and boron trichloride catalyst from being taken away by hydrogen which is difficult to condense.

In order to solve the above problems, the present invention provides a production apparatus for preparing phenyl-containing chlorosilane, the production apparatus comprising: the reactor is used for accommodating reaction raw materials and is provided with an outlet and an inlet; the catalyst circulating device is respectively communicated with the outlet and the inlet and is used for driving at least part of the catalyst to circularly enter and exit the reactor; wherein, the reaction raw material comprises chlorosilane and a benzene-containing compound, and the catalyst comprises boron trifluoride or boron trichloride.

In any of the above technical solutions, the production apparatus further includes: the porous gas distribution pipe is arranged in the reactor and positioned at the bottom of the reactor, and is used for driving the catalyst to flow through bubbling; wherein, the outlet is arranged at the top of the reactor, the inlet is arranged on the side wall of the reactor, and at least part of the catalyst circulating device extends to the porous gas distribution pipe through the inlet.

In any of the above technical solutions, the production apparatus further includes: the packing auger is arranged in the reactor and is used for promoting the rotational flow mixing of the reaction raw materials through rotation.

In any of the above embodiments, the reactor comprises: the feeding valve is arranged at the top of the reactor and used for feeding reaction raw materials into the reactor; and/or a discharge valve provided at the bottom of the reactor and adapted to discharge a reaction product obtained by reacting the reaction raw materials out of the reactor.

In any of the above solutions, the catalyst circulation device includes: the benzene removal and segregation device is arranged at the top of the reactor and is communicated with the reactor; the first cooling device is arranged at the top of the benzene removal and segregation device and is communicated with the benzene removal and segregation device; the three-way pipe fitting comprises a first pipeline, a second pipeline and a third pipeline; wherein the first pipeline is communicated with the top of the first cooling device and is used for collecting the catalyst from the reactor; the second pipeline is communicated with the first pipeline and is used for putting in a catalyst; the third pipeline is communicated with the first pipeline and is used for feeding the catalyst into the reactor and separating the catalyst from the hydrogen generated by the reaction.

In any of the above technical solutions, the first pipeline gradually inclines upward from the end close to the first cooling device to the end far away from the first cooling device; the second pipeline is vertically and upwards arranged; the third pipeline is vertically arranged downwards; a first stop valve is arranged between the first cooling device and the first pipeline; the top of the second pipeline is connected with a cryogenic dephlegmation device, the top of the cryogenic dephlegmation device is connected with a second cooling device, the top of the second cooling device is respectively connected with a pressure release valve and a high-pressure gas cylinder for supplying a catalyst, a second stop valve is arranged between the pressure release valve and the second cooling device, and a third stop valve is arranged between the high-pressure gas cylinder and the second cooling device; a fourth stop valve is arranged between the third pipeline and the reactor; the third pipeline is sleeved with a metering pipe; the third pipeline is sleeved with a third cooling device; the third pipeline is a U-shaped pipe for forming liquid level difference.

In order to solve the above problems, the present invention provides a method for controlling a production facility for preparing phenylchlorosilane, the method for controlling the production facility according to any one of the above technical solutions, the method comprising: controlling a feeding valve of the reactor to open so as to feed reaction raw materials into the reactor; controlling the third stop valve to be opened, and controlling the first stop valve, the second stop valve, the fourth stop valve and the cryogenic fractional condensation device to be closed, so that the high-pressure gas cylinder fills gaseous catalyst into the closed three-way pipe fitting, and the catalyst is limited and liquefied in the metering pipe through the catalyst, and the catalyst is metered; and sequentially controlling the cryogenic segregating device, the first stop valve, the fourth stop valve and the second stop valve to be opened, and controlling the temperature of the reactor to rise to the reaction temperature.

In any of the above technical solutions, the control method further includes: collecting the hydrogen discharge amount of the pressure release valve, and controlling the reaction temperature and/or the reaction time of the reactor according to the hydrogen discharge amount; and/or opening a porous gas distribution tube in the reactor, so that the porous gas distribution tube drives the catalyst to flow through bubbling.

In order to solve the above problems, the present invention provides a preparation method for preparing phenyl-containing chlorosilane, the preparation method adopts the production equipment in any one of the above technical schemes, and the preparation method comprises: feeding reaction raw materials into a reactor, and supplying a catalyst into the reactor; wherein the reaction pressure in the reactor is 10MPa, the reaction temperature is 200 ℃, the reaction time is 8h, and the addition amount of the catalyst is 1-5% of the reaction raw materials.

In order to solve the problems, the invention provides phenyl chlorosilane which is obtained by adopting the method in any one technical scheme.

The production apparatus of the present invention comprises: a reactor and a catalyst circulation device. The reactor is used for accommodating reaction raw materials and is provided with an outlet and an inlet. The catalyst circulating device is respectively communicated with the outlet and the inlet and is used for driving at least part of the catalyst to circulate in and out of the reactor. Thus, the catalyst can be recycled. Wherein, the reaction raw material comprises chlorosilane and a benzene-containing compound, and the catalyst comprises boron trifluoride or boron trichloride. In the production process of phenyl chlorosilane, boron trifluoride and boron trichloride catalysts are taken away by hydrogen which is difficult to condense. For this purpose, the invention is characterized in that a catalyst circulation device is communicated between the reactor and the outlet and the inlet, and the catalyst circulation device continuously separates the catalyst discharged from the reactor from the hydrogen and sends the catalyst back to the reactor. Therefore, the method can realize the cyclic utilization of the catalyst in the production process of the phenyl-containing chlorosilane, and improve the reaction efficiency of the catalyst, thereby reducing the production cost of the phenyl-containing chlorosilane.

Drawings

FIG. 1 is a schematic diagram of a production facility for preparing phenylchlorosilane-containing compounds according to an embodiment of the present invention;

FIG. 2 is a schematic diagram of a process for preparing phenyl chlorosilane according to an embodiment of the invention.

Description of the reference numerals

Reactor-100; outlet-100 a; inlet-100 b; catalyst circulation unit-200; a porous gas distribution pipe-300; a feeding valve-101; -102, a discharge valve; a benzene removal and segregation device-201; a first cooling device-202; a tee fitting-203; a first conduit-203 a; a second conduit-203 b; a third line-203 c; a first cutoff valve-204; a cryogenic fractional condensation device-205; a second cooling device-206; a pressure relief valve-207; a high-pressure gas cylinder-208; a second stop valve-209; a third stop valve-210; a fourth cut-off valve-211; a metering tube-212; a third cooling device-213.

Detailed Description

In order that the above objects, features and advantages of the present invention can be more clearly understood, the present invention will be described in further detail with reference to specific embodiments. It should be noted that the embodiments and features of the embodiments of the present application may be combined with each other without conflict.

In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, however, the present invention may be practiced otherwise than as specifically described herein and, therefore, the scope of the present invention is not limited by the specific embodiments disclosed below. The following technical features of the embodiments of the present invention may be combined with each other without conflict.

As shown in fig. 1, an embodiment of the present invention provides a production apparatus for preparing phenyl-containing chlorosilane, including: a reactor 100, the reactor 100 being for accommodating reaction raw materials and provided with an outlet 100a and an inlet 100b; a catalyst circulation device 200, the catalyst circulation device 200 being communicated with the outlet 100a and the inlet 100b, respectively, and being configured to drive at least a portion of the catalyst to circulate into and out of the reactor 100; wherein, the reaction raw materials comprise chlorosilane and a benzene-containing compound, and the catalyst comprises boron trifluoride or boron trichloride.

In the above examples, the reactor 100 is a high-pressure reactor for a pilot plant or a heating medium heating coil reactor for the batch process for preparing phenylchlorosilane or a tubular reactor for the continuous process for preparing phenylchlorosilane.

Optionally, a heater is attached to the wall of the reactor 100, and the heater is used to control the temperature in the reactor 100. Illustratively, the heater is one of: cast iron heater, cast aluminum heater, cast copper heater.

In one example, taking an autoclave for a pilot plant as the reactor 100, the reactor 100 has dimensions of 89mm x 5mm x 600mm. The material of the reactor 100 is 347 stainless steel. The reactor 100 is shaped as a vertical cylinder;

the product obtained by the reaction in the reactor 100 is phenylchlorosilane containing phenylchlorosilane such as methylphenyldichlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, methylphenyldichlorosilane, ethylphenyldichlorosilane.

Illustratively, the chlorosilane in the reaction raw materials is monohydroxy dichlorosilane, the benzene-containing compound is benzene, and the adding amount ratio of the monohydroxy dichlorosilane to the benzene is 143.

In one example, the amount of the raw materials for the reaction in the reactor 100 is 1200g, wherein 715g of monohydroxy dichlorosilane and 485g of benzene are contained, the reaction pressure in the reactor 100 is 10MPa, the reaction temperature is 200 ℃, the reaction time is 8h, the amount of the catalyst is 1 to 5 percent of the raw materials for the reaction, the reaction product obtained in the reactor 100 is methyl phenyl dichlorosilane, and the yield of the methyl phenyl dichlorosilane is 38 percent.

Preferably, the catalyst is boron trifluoride and the amount of catalyst added is 1% of the reaction feed.

In the above embodiment, the catalyst circulation device 200 is used to drive the catalyst to circulate between the outlet 100a and the inlet 100b of the reactor 100, and to separate the catalyst from the hydrogen generated by the reaction, so as to improve the utilization efficiency of the catalyst and avoid unnecessary loss of the catalyst.

As shown in fig. 1, in some embodiments of the present invention, the production apparatus further comprises: and the porous gas distribution pipe 300 is arranged in the reactor 100 and is positioned at the bottom of the reactor 100, and the porous gas distribution pipe 300 is used for driving the catalyst to flow through bubbling. Wherein the outlet 100a is disposed at the top of the reactor 100, the inlet 100b is disposed at the side wall of the reactor 100, and at least a portion of the catalyst circulation device 200 extends to the porous gas distribution pipe 300 through the inlet 100 b.

Since the inlet 100b is provided on the side wall of the reactor 100, the tail end of the U-shaped tube of the catalyst circulation device 200 can enter the reactor 100 through the side wall of the reactor 100 and extend from the top to the bottom from the porous gas distribution tube 300 located at the bottom of the reactor 100. Thus, the porous gas distribution pipe 300 can preferably bubble the catalyst from the catalyst circulation device 200 to drive the uniform and effective circulation of the catalyst.

As shown in fig. 1, in some embodiments of the invention, reactor 100 comprises: and a feeding valve 101, wherein the feeding valve 101 is arranged at the top of the reactor 100 and is used for feeding reaction raw materials into the reactor 100.

As shown in fig. 1, in some embodiments of the invention, reactor 100 comprises: a discharge valve 102, the discharge valve 102 being provided at the bottom of the reactor 100, and serving to discharge a reaction product obtained by reacting the reaction raw materials out of the reactor 100.

In some embodiments of the invention, the production facility further comprises: and an auger (not shown) disposed in the reactor 100 and configured to induce rotational mixing of the reaction raw materials by rotation.

It will be appreciated that the production facility of embodiments of the present invention may be used in pilot plant applications, as well as in the actual production of batch processes, or continuous processes, after fine tuning of parts of the facility or equipment.

Wherein, when used for the actual production of the continuous process, the reactor 100 is a tubular reactor made of 347 stainless steel circular straight tubes with the size of phi 108X 8X 10000. An auger is arranged inside the reactor 100.

An example of a manufacturing process of the packing auger in the reactor 100 used for the continuous production is as follows, the size of the built-in 304 stainless steel packing auger of the reactor 100 is 90X 38X 90X 3, and the packing auger is welded and fixed by a 347 stainless steel pipe with the diameter of 38X 2 at the center. The arrangement of the packing auger enables the reaction materials to generate rotational flow mixing when flowing in the tube. When the packing auger is manufactured, the phi 108 multiplied by 8 multiplied by 10000 pipelines can be flatly and compactly stacked in a horizontally placed square frame with the width of 3200mm, the length of 12m and the height of 1400mm, and the movement of the section of the pipeline in all directions is firmly limited by alternately using a transverse grid plate and a vertical grid plate by using a manufacturing method of a rod baffle heat exchanger, so that the aim of inhibiting the vibration damage caused by gas-liquid mixed flow is fulfilled. Wherein, the size of the grid plate using the square fixing rod is 30 multiplied by 30 or 32 multiplied by 32. The pipes are tightly fixed in a layered mode, each layer is provided with 22 pipes with the diameter of 108 multiplied by 8 multiplied by 10000, 9 layers are arranged in a box, the number of the pipes is 198, and the pipe spacing is 140mm. Starting from the bottom layer, the customized omega-shaped large-rotation elbow (the elbow is a key structure for enabling the pipeline to be compactly arranged, the supply of the large-rotation elbow can be divided into two elbows for enabling the elbow to be easily manufactured, although 3 welding seams can be added during installation, two welding seams can be constructed by a welding robot, the rest 1 welding seam needs to be manually completed but has good operation conditions, so that the efficiency and the reliability are higher) is sequentially connected in series by assembly welding, then the assembly welding is connected in series with the previous layer, and finally a folding pipeline with the length of 2265 meters is formed in a square frame.

It should be noted that for the continuous production, a spiral packing auger needs to be installed in the straight pipe section of the reaction pipe, and the gap between the packing auger and the inner wall of the high-pressure pipe is less than 2mm, so as to meet the requirements of preventing the packing auger from vibrating and reducing the gas-liquid short circuit flow.

It can be understood that when the actual manufacturing of continuous method apparatus for producing, for convenience, the elbow of welding both ends passes through positioning die and laminates the elbow of pipeline assembly welding layer by layer earlier and becomes an organic whole, and hoist and mount stack carry out layer by layer welded fastening in the square frame again. Stacking 10 frames of the pipe arrangement, and welding and connecting the upper layer pipe orifice of the lower layer frame and the lower layer pipe orifice of the upper layer frame of the pipe of the adjacent upper and lower frames to form a set of reaction furnace with a single pipeline with the length of 22650 meters, wherein the total height of the equipment is 16 meters, the occupied area is 12000 multiplied by 4000, the volume in the high-pressure reaction pipe is 150 cubic meters, the calculation is carried out according to the reaction effect of a small test device, when boron trifluoride is used as a catalyst, the liquid speed of the inlet of the pipe of the reactor 100 can be set to be 0.33m/s, the conversion per pass is more than 35%, the annual reaction time is 8600 hours, the operating pressure is 10MPa, the high-temperature liquid density and the gas phase volume are considered, the capacity of the obtained methyl phenyl dichlorosilane is 18000 tons/year, the manufacturing cost of the reactor 100 is about 4000 ten thousand yuan, and the economy is still good. Because the reaction process is a weak endothermic reaction between 8 and 25KJ/mol to 25KJ/mol, the heat can be supplied to control the reaction temperature by using the circulating flow of the hot air with normal pressure outside the reaction pipe. Because the leaked materials are easy to self-ignite, the circulating hot air preferably adopts nitrogen to ensure the safety, and the heat of the heating furnace is transferred to the circulating hot nitrogen through the low-pressure-drop separated heat pipe heat exchanger. Abnormal conditions are timely discovered by monitoring the purity of the circulating nitrogen through online chromatography so as to facilitate emergency treatment.

In some embodiments of the present invention, the catalyst circulation device 200 includes: the benzene removal and segregation device 201, the benzene removal and segregation device 201 is arranged at the top of the reactor 100 and is communicated with the reactor 100; the first cooling device 202 is arranged at the top of the benzene removal and segregation device 201, and the first cooling device 202 is communicated with the benzene removal and segregation device 201; tee 203, tee 203 comprising first, second, and

third lines

203a, 203b, 203c; wherein the first pipe 203a communicates with the top of the first cooling device 202 and serves to collect the catalyst from the reactor 100; the second pipeline 203b is communicated with the first pipeline 203a and is used for putting in catalyst; the third pipe 203c communicates with the first pipe 203a for feeding the catalyst into the reactor 100 and separating the catalyst from the hydrogen gas generated by the reaction.

It will be appreciated that the production facility of embodiments of the present invention may be used in pilot plant applications, as well as in the actual production of batch processes, or continuous processes, after fine tuning of parts of the facility or equipment. Wherein, the segregation device can be a segregation column used for a small test, or a bubble cap rectifying tower used for preparing phenylchlorosilane by a batch method. The cooling device can be a cooling jacket for a pilot plant or a vertical tube-in-tube condenser for the batchwise preparation of phenylchlorosilanes.

In the case of use in a pilot plant, the benzene-removing and dephlegmating apparatus 201 is embodied as a cooling jacket having dimensions of phi 10mm x 2mm x 1500mm. The shape of the benzene removing and segregating device 201 is a vertical cylinder. The reactor 100 is in direct smooth transition with the benzene removal and segregation apparatus 201 for preventing flooding. The cooling temperature of the first cooling device 202 was-5 deg.c and was used to remove benzene having a high melting point to provide a segregated reflux. The cooling temperature of the first cooling device 202 is controlled by the low-temperature coolant circulating pump DLSB-5/10. The length of the first cooling device 202 is 200mm.

The tee 203 is formed by welding three inner pipes with the size of phi 10 multiplied by 2 through a 90-degree tee with the size of phi 14 multiplied by 2, and the tee is used for preventing the blanking material from the deep cooling segregation device 205 from entering the first pipe 203a which inclines upwards.

In some embodiments of the present invention, the first pipeline 203a gradually inclines upwards from the end close to the first cooling device 202 to the end far away from the first cooling device 202; the second pipeline 203b is vertically opened upwards; the third pipeline 203c is vertically opened downwards; a first stop valve 204 is arranged between the first cooling device 202 and the first pipeline 203a; the top of the second pipeline 203b is connected with a cryogenic segregating device 205, the top of the cryogenic segregating device 205 is connected with a second cooling device 206, the top of the second cooling device 206 is respectively connected with a pressure relief valve 207 and a high-pressure gas cylinder 208 for supplying catalyst, a second stop valve 209 is arranged between the pressure relief valve 207 and the second cooling device 206, and a third stop valve 210 is arranged between the high-pressure gas cylinder 208 and the second cooling device 206; a fourth stop valve 211 is arranged between the third pipeline 203c and the reactor 100; the third pipeline 203c is sleeved with a metering pipe 212; the third pipeline 203c is sleeved with a third cooling device 213; the third pipe 203c is a U-shaped pipe for forming a liquid level difference.

The first stop valve 204 is a high pressure resistant stop valve. The catalyst vaporized in the reactor 100 enters the first line 203a, which is slightly inclined at-20 c (i.e., enters the jacketed cooling zone) via the open first shut-off valve 204. The first pipe 203a is a phi 10 x 2 inclined upward horizontal pipe which does not obstruct the upward flow of hydrogen.

The tee 203 is provided with a metering tube 212 having an inner volume of 45ml, which meters the amount of catalyst such as boron trifluoride charged. Illustratively, each pilot experiment was actually charged with 50g of boron trifluoride, but only 10g to 12g was retained in the reactor 100 to cause catalysis. The inner pipe is composed of two specifications of pipes phi 10 x 2 and phi 6 x 1.5 x 2000, wherein phi 10 x 2 is the metering pipe 212, and phi 6 x 1.5 x 2000 is the third pipeline 203c. The third line 203c is a U-shaped pipe with accompanying cooling, which is temperature-controlled by the low-temperature cooling liquid circulating pump DLSB-10/30. The third line 203c is used to return condensed catalyst, such as boron trifluoride, through a head difference back to the reactor 100, after the catalyst enters the middle of the reactor 100. Is bent downwards to the bottom, enters the porous air distribution pipe 300 which is horizontally arranged, and is bubbled and flows out. Wherein the reflux liquid leaves the cooling-accompanying pipe (i.e., the third pipe 203 c) and passes through the fourth cut-off valve 211 before entering the reactor 100. The top of the second pipeline 203b is connected with a cryogenic segregating device 205, the size of the cryogenic segregating device 205 is phi 10 multiplied by 2 multiplied by 1200, the cryogenic segregating device 205 is used for preventing substances with boiling points higher than that of the catalyst from reaching the second cooling device 206, and the second cooling device 206 is a cryogenic jacket (-100 ℃) (the melting point of the ethanol coolant is-114 ℃). By using a cryogenic jacket (which is temperature controlled by the cryogenic coolant circulating pump DLSB-5/120), the carryover loss of catalyst due to hydrogen bleed can be reduced.

The embodiment of the invention also provides a control method for the production equipment for preparing the phenylchlorosilane, which is used for controlling the production equipment in any technical scheme and comprises the following steps:

s101, controlling a feeding valve of a reactor to open so as to feed reaction raw materials into the reactor;

s102, controlling the third stop valve to be opened, and controlling the first stop valve, the second stop valve, the fourth stop valve and the cryogenic fractional condensation device to be closed, so that the high-pressure gas cylinder fills gaseous catalyst into the closed three-way pipe fitting, the catalyst is liquefied in the metering pipe in a limited manner, and the catalyst is metered;

s103, sequentially controlling the cryogenic segregation device, the first stop valve, the fourth stop valve and the second stop valve to be opened, and controlling the reactor to be heated to the reaction temperature.

Specifically, in S101, the charging of the reaction material is completed before the charging of the catalyst. After the feeding is finished, the feeding valve can be controlled to be closed. Subsequently, the third stop valve is controlled to be opened, and the first stop valve, the second stop valve, the fourth stop valve, and the cryogenic segregating device are controlled to be closed, through S102. Therefore, the first stop valve, the second stop valve and the fourth stop valve can form a closed catalyst receiving cavity after being closed. The third stop valve is opened and high pressure charge can be applied via a 12Mpa high pressure gas cylinder, metering the catalyst by limited liquefaction using a-20 c third cooling means 213 (e.g., a cooling jacket). When receiving material, the cryogenic condensation device (such as a cryogenic jacket) is not started.

Regarding step S103, the order of opening each component or device in this step is in a sequential relationship. Particularly, treat catalyst reinforced completion back, need start earlier the cryrogenic device that realizes the cryrogenic refrigeration effect, its normal back of working opens first stop valve again, makes the catalyst get into the reactor, and the catalyst gets into the reactor and can lead to pressure to rise, and noncondensable gas is caught up to the cryrogenic device, opens the fourth stop valve after that, makes the catalyst form flow circulation, lasts the tympanic bulla to material in the reactor, treats to observe the pressure and rises the change condition slowly after, opens the second stop valve. The operation steps can ensure that the deep cooling dephlegmation device is fully liquefied in the closed space, accurate metering is realized, and then the catalyst enters the reactor, gasification and circular flow are carried out, the pressure of the reactor caused by the catalyst rises, and non-condensable gas is driven to the deep cooling dephlegmation device and is discharged. Therefore, the control method not only can realize accurate metering and feeding of the catalyst, but also can ensure that the non-condensable gas is effectively discharged.

It should be noted that the opening degree of the second stop valve is small, and the second stop valve has a damping effect. The second stop valve is a high-pressure back pressure valve which is matched with a high-pressure buffer tank, and the stop valve is arranged at the outlet of the back pressure valve, so that severe pressure fluctuation caused by large pressure difference and easy overshoot during the action of the back pressure valve is prevented. After the above operations are completed, the reactor is controlled to be heated to the reaction temperature.

In some embodiments of the present invention, the control method further comprises: and opening the porous gas distribution pipe in the reactor, so that the porous gas distribution pipe drives the catalyst to flow through bubbling.

In some embodiments of the present invention, the control method further comprises: and collecting the hydrogen discharge amount of the pressure release valve, and controlling the reaction temperature and/or the reaction time of the reactor according to the hydrogen discharge amount.

In other words, the hydrogen generated by the reaction can be discharged into the gas collecting device. The gas collection device can be a 600-liter atmospheric plastic gas holder. And (3) metering the hydrogen discharged into the gas collecting device, and recording the change of the gas volume along with the time so as to calculate the reaction rate.

The gas collecting device is arranged in the lime water tank, and tail gas bubbles from the lime water to remove active poisons such as boron fluoride and the like, and then enters the gas holder for metering.

The embodiment of the invention also provides a preparation method for preparing phenyl-containing chlorosilane, the preparation method adopts the production equipment of any one of the technical schemes, and the preparation method comprises the following steps:

feeding reaction raw materials into a reactor, and supplying a catalyst into the reactor;

wherein the reaction pressure in the reactor 100 is 10MPa, the reaction temperature is 200 ℃, the reaction time is 8h, and the addition amount of the catalyst is 1-5% of the reaction raw materials.

Illustratively, in the production of diphenyldichlorosilane, the embodiment of the invention firstly uses trichlorosilane, hydrogen chloride and hydrogen in a molar ratio of 1: 1-3, 4-6, reacting with silicon powder with the purity of more than 98% to obtain mixed hydrogen-containing chlorosilane with the dichlorosilane content of 10-80% (the process is the same as the silicon tetrachloride chlorohydrination process adopted in polysilicon production, and is used for replacing a trichlorosilane disproportionation method and reducing the production cost of dichlorosilane), and then mixing the mixture and benzene in a molar ratio of 1: 1-2.5 in a high-pressure pipeline at 180-270 ℃ to obtain high-yield diphenyldichlorosilane and byproducts phenyltrichlorosilane and triphenylmonochlorosilane;

illustratively, the embodiment of the invention can produce the methyl phenyl dichlorosilane by reacting the hydrogen monochlorosilane and the benzene in a molar ratio of 1.

Illustratively, the methyl chlorophenyldichlorosilane can be produced by reacting monohydrodichlorosilane and chlorobenzene in a molar ratio of 1 in a high pressure tube at 120-280 ℃.

As shown in fig. 2, an example of a reactor system process flow for a continuous process is as follows: mixing fresh raw materials of benzene, recycled benzene, hydrogen-containing chlorosilane, a fresh inhibitor and the recycled inhibitor, pressurizing the mixed material to be more than 12MPa by using a high-lift pump, heating the mixed material to 150 ℃ by using water vapor, mixing the mixed material with a low-temperature mixed material from a catalyst recycling system to prevent the benzene from being frozen to cause blockage, heating the mixed material to a reaction temperature by using heat conduction oil as required, and then feeding the heated mixed material into a reaction furnace tube, wherein the reaction furnace tube maintains the reaction temperature by heating circulating hot air. The discharge of the reaction furnace tube firstly reaches a high-pressure pre-separation tower, and the rectification section of the reaction furnace tube is used for rectifying and removing benzene in ascending gas to prevent a cryogenic system from being blocked by freezing; the stripping section removes the catalyst in the downflow liquid by heating the stripping section in the column bottom with a small amount of heat energy to form a strip; the tower bottom liquid is sent to a rectification working section of low-pressure operation to separate and recycle unreacted raw materials; ascending gas at a rectification section of the high-pressure pre-separation tower sequentially passes through water cooling-primary pre-cooling to obtain condensed reflux liquid, and then sequentially exchanges heat with low-temperature tail gas for cooling-deep cooling-cooling at 80 ℃, washing with low-temperature fresh hydrogen-containing chlorosilane and treating by a demister to condense, separate and recover unreacted raw materials and a catalyst from hydrogen, and after the obtained low-temperature recovered mixed liquid is pressurized by a high-lift pump, the low-temperature recovered mixed liquid is firstly used as a primary pre-cooling cold source of the high-pressure pre-separation tower and then mixed with the preheated benzene-containing mixed material to enter a reactor. Precooling fresh hydrogen-containing chlorosilane, and then cooling to-80 ℃ by deep cooling to be used as a washing liquid of high-pressure hydrogen to absorb and remove a gas catalyst in the hydrogen. Purified hydrogen is discharged out of the tail gas under the control of a backpressure high-pressure stabilizing valve for post-treatment and utilization. Like the batch process, the continuous process is also provided with a washing treatment system for the discharged gas of the reactor system in case of power failure with the same function to ensure safety.

For a reactor of a batch production device, the system flow is similar to that of a laboratory test, and the difference is that a bubble-cap rectifying tower section is used for replacing a segregation column, a special vertical tubular condenser is used for replacing a cooling jacket, an amplified high-pressure reaction kettle is changed into a safer heating medium heating coil, and a power failure accident emptying tail gas treatment system is additionally arranged; and the second stage uses lime water to wash and remove hydrogen chloride and hydrogen fluoride, the tail gas component after washing is hydrogen which is safely discharged at a high place through a pipeline, and the safety requirement of capacity amplification is met. When the bottom of the reactor discharges materials, the valve is closed to cut off the catalyst circulation, the reaction kettle maintains high temperature without cooling, and a high-pressure-resistant discharge buffer tank is adopted to ensure that liquid is not discharged during each discharge, so that the gas catalyst is prevented from being discharged. And feeding again and starting to add reaction raw materials into the high-temperature reactor through a high-lift metering pump.

In general, the embodiment of the invention uses boron trifluoride or boron trichloride with low boiling point as a catalyst, and the reaction raw material maintains rotating mixed flow in a high-pressure pipeline, so that the phenyl-containing chlorosilane is continuously produced by reaction at the temperature of below 300 ℃, the phenomena of coking and blockage caused by pyrolysis of the raw material can be avoided, equipment is prevented from bearing high-temperature chlorine corrosion and serious abrasion, the utilization rate of the raw material is high, the catalyst can be continuously recycled, high-toxicity byproducts are not produced, the product is easy to purify, the byproducts are easy to harmlessly utilize, the equipment can be compactly arranged, the energy utilization rate is high, the occupied area is small when the capacity is amplified, and the production cost of a large-scale device is favorably reduced. In addition, the embodiment of the invention designs a pilot plant suitable for preparing phenyl chlorosilane by using boron trifluoride and boron trichloride for catalysis, the pilot plant realizes a gas catalyst circulating bubbling process, the catalytic efficiency is improved, and a production device for producing the phenyl chlorosilane by using boron trifluoride or boron trichloride for catalytic reaction in an intermittent method can be designed by using the design principle of the pilot plant, so that the requirement of reducing the cost during small-batch production is met.

In the present invention, the terms "first", "second", and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance; the term "plurality" means two or more unless explicitly defined otherwise. The terms "mounted," "connected," "fixed," and the like are used broadly and should be construed to include, for example, "connected" may be a fixed connection, a detachable connection, or an integral connection; "coupled" may be direct or indirect through an intermediary. The specific meanings of the above terms in the present invention can be understood by those skilled in the art according to specific situations.

In the description of the present specification, the description of "one embodiment," "some embodiments," "specific embodiments," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A production facility for preparing phenyl-containing chlorosilane, characterized in that the production facility comprises:

a reactor (100), the reactor (100) being used for containing reaction raw materials and provided with an outlet (100 a) and an inlet (100 b);

a catalyst circulation device (200), said catalyst circulation device (200) being in communication with said outlet (100 a) and said inlet (100 b), respectively, and being adapted to drive at least a portion of the catalyst to circulate into and out of said reactor (100);

wherein the reaction raw materials comprise chlorosilane and a benzene-containing compound, and the catalyst comprises boron trifluoride or boron trichloride.

2. The production apparatus according to claim 1, further comprising:

the porous gas distribution pipe (300) is arranged in the reactor (100) and positioned at the bottom of the reactor (100), and the porous gas distribution pipe (300) is used for driving the catalyst to flow through bubbling;

wherein the outlet (100 a) is arranged at the top of the reactor (100), the inlet (100 b) is arranged on the side wall of the reactor (100), and at least part of the catalyst circulation device (200) extends to the porous gas distribution pipe (300) through the inlet (100 b).

3. The production apparatus according to claim 1, further comprising:

the packing auger is arranged in the reactor (100) and is used for promoting the reaction raw materials to be mixed in a rotational flow manner through rotation.

4. The production plant according to claim 1, wherein the reactor (100) comprises:

the feeding valve (101) is arranged at the top of the reactor (100), and is used for feeding the reaction raw materials into the reactor (100); and/or

A discharge valve (102), the discharge valve (102) being provided at the bottom of the reactor (100) and being for discharging a reaction product obtained by reacting the reaction raw materials out of the reactor (100).

5. The production plant according to any of claims 1 to 4, wherein the catalyst circulation device (200) comprises:

the benzene removal and segregation device (201) is arranged at the top of the reactor (100), and the benzene removal and segregation device (201) is communicated with the reactor (100);

the first cooling device (202) is arranged at the top of the benzene removal and segregation device (201), and the first cooling device (202) is communicated with the benzene removal and segregation device (201);

a tee (203), said tee (203) comprising a first pipe (203 a), a second pipe (203 b), and a third pipe (203 c);

wherein the first conduit (203 a) communicates with the top of the first cooling device (202) and is used for collecting the catalyst from the reactor (100); the second line (203 b) is in communication with the first line (203 a) and is used for the introduction of the catalyst; the third line (203 c) is in communication with the first line (203 a) for feeding the catalyst to the reactor (100) and separating the catalyst from the hydrogen produced by the reaction.

6. The production apparatus according to claim 5,

the first pipeline (203 a) gradually inclines upwards from one end close to the first cooling device (202) to one end far away from the first cooling device (202); the second pipeline (203 b) is vertically and upwards arranged; the third pipeline (203 c) is vertically and downwards opened;

a first stop valve (204) is arranged between the first cooling device (202) and the first pipeline (203 a);

the top of the second pipeline (203 b) is connected with a cryogenic segregating device (205), the top of the cryogenic segregating device (205) is connected with a second cooling device (206), the top of the second cooling device (206) is respectively connected with a pressure release valve (207) and a high-pressure gas cylinder (208) used for supplying the catalyst, a second stop valve (209) is arranged between the pressure release valve (207) and the second cooling device (206), and a third stop valve (210) is arranged between the high-pressure gas cylinder (208) and the second cooling device (206);

a fourth stop valve (211) is arranged between the third pipeline (203 c) and the reactor (100); the third pipeline (203 c) is sleeved with a metering pipe (212); the third pipeline (203 c) is sleeved with a third cooling device (213); the third pipeline (203 c) is a U-shaped pipe for forming a liquid level difference.

7. A control method for a production facility for producing phenylchlorosilane-containing compounds, the control method being used for controlling the production facility as defined in claim 6, the control method comprising:

controlling a feeding valve of the reactor to open so as to feed the reaction raw materials into the reactor;

controlling the third stop valve to be opened, and controlling the first stop valve, the second stop valve, the fourth stop valve and the cryogenic fractional condensation device to be closed, so that the high-pressure gas cylinder fills the gaseous catalyst into the closed three-way pipe fitting, and the catalyst is metered by limiting liquefaction of the catalyst in the metering pipe;

and sequentially controlling the deep cooling and dephlegmation device, the first stop valve, the fourth stop valve and the second stop valve to be opened, and controlling the temperature of the reactor to rise to the reaction temperature.

8. The control method according to claim 7, characterized by further comprising:

collecting the hydrogen discharge amount of the pressure release valve, and controlling the reaction temperature and/or the reaction time of the reactor according to the hydrogen discharge amount; and/or

And opening the porous gas distribution pipe in the reactor, so that the porous gas distribution pipe drives the catalyst to flow through bubbling.

9. A production method for producing phenylchlorosilane-containing compounds, which is characterized by using the production apparatus according to any one of claims 1 to 6, comprising:

feeding the reaction feedstock to the reactor and supplying the catalyst to the reactor;

wherein the reaction pressure in the reactor is 10MPa, the reaction temperature is 200 ℃, the reaction time is 8h, and the addition amount of the catalyst is 1-5% of the reaction raw material.

10. A phenylchlorosilane-containing compound obtained by the process of claim 9.