CN120420927A - Continuous synthesis system and method of gamma-chloropropyl trichlorosilane - Google Patents
Continuous synthesis system and method of gamma-chloropropyl trichlorosilaneInfo
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Abstract
本发明提供γ‑氯丙基三氯硅烷的连续合成系统，包括三氯氢硅储罐、氯丙烯储罐、催化剂储罐、静态混合器，n级串联的管式反应系统和精馏装置；管式反应系统包括管式反应器、背压阀、除气装置及冷凝器，除气装置的液相出口与冷凝器的液相出口一起连接下一级管式反应器；三氯氢硅储罐、氯丙烯储罐、催化剂储罐分别与静态混合器的入口连接，静态混合器的出口连接第一级管式反应器；第2至n级管式反应器的入口进料包括氯丙烯；第n级的除气装置的液相出口连接精馏装置的入口，精馏装置连回第一级的管式反应器，并输出γ‑氯丙基三氯硅烷的产品。本发明提高了反应效率和转化率，生产能耗和成本低。本发明还提供基于该系统的合成方法，工艺流程简单。
The present invention provides the continuous synthesis system of γ-chloropropyltrichlorosilane, including trichlorosilane storage tank, chloropropylene storage tank, catalyst storage tank, static mixer, n-stage tubular reaction system and rectification unit in series；Tubular reaction system includes tubular reactor, back pressure valve, degassing device and condenser, and the liquid phase outlet of degassing device is connected to next-stage tubular reactor together with the liquid phase outlet of condenser；Trichlorosilane storage tank, chloropropylene storage tank, catalyst storage tank are respectively connected to the inlet of static mixer, and the outlet of static mixer connects first-stage tubular reactor；The inlet feed of 2 to n-stage tubular reactor includes chloropropylene；The liquid phase outlet of the degassing device of n-stage connects the inlet of rectification unit, and rectification unit is connected back to the tubular reactor of first stage, and outputs the product of γ-chloropropyltrichlorosilane.The present invention improves reaction efficiency and conversion rate, and produces low energy consumption and cost.The present invention also provides the synthesis method based on the system, and process flow is simple.
Description
Technical Field
The invention belongs to the field of organosilicon production, and particularly relates to a continuous synthesis system and method of gamma-chloropropyl trichlorosilane.
Background
Gamma-chloropropyl trichlorosilane is the most basic monomer in silane coupling agents, tens of silane coupling agent products can be deeply processed by taking the gamma-chloropropyl trichlorosilane as a main raw material, and the production capacity of the gamma-chloropropyl trichlorosilane determines the production capacity of downstream products. The synthesis of gamma-chloropropyl trichlorosilane is mainly prepared by catalyzing hydrosilation reaction of chloropropene and trichlorosilane through a platinum complex (a Speier catalyst or a Karstedt catalyst), and industrial-grade gamma-chloropropyl trichlorosilane can be obtained through rectifying and separating reaction products, wherein the reaction equation is as follows:
The main reaction:
HSiCl3+ClCH2CH＝CH2→ClC3H6SiCl3△H=-80.89KJ/mol
side reaction:
HSiCl3+ClCH2CH＝CH2→SiCl4+CH3CH＝CH2 △H=-107.49KJ/mol
HSiCl3+CH3CH＝CH2→CH3CH2CH2SiCl3 △H＝-87.0KJ/mol
HSiCl3+ClCH2CH＝CH2→ClCH2CH(SiCl3)CH3 △H＝-87.48KJ/mol
The boiling points of reactants and byproducts are low except the product gamma-chloropropyl trichlorosilane at normal temperature and normal pressure, so that unreacted completely trichlorosilane, chloropropene, and byproducts silicon tetrachloride, propyl trichlorosilane and propylene inevitably exist in the synthesis tail gas of the gamma-chloropropyl trichlorosilane. In addition, the synthesis system is fed with nitrogen or pressurized, and trichlorosilane, gamma-chloropropyl trichlorosilane, silicon tetrachloride and propyl trichlorosilane can hydrolyze in water or humid air to release hydrogen chloride gas.
The hydrosilylation reaction is a strong exothermic reaction, the main reaction and the side reaction of the addition are exothermic in nature, a large amount of heat is easily released in the process, and the problems of excessively high local temperature and increased pressure of a reaction system, isomerization of unsaturated bonds, increase of secondary addition products, reduction of selectivity and the like are easily caused by improper heat transfer and mass transfer control. In addition, the reaction temperature increases to accelerate the reaction rate, resulting in too severe a reaction and a danger. Therefore, a large amount of cooling systems or heat exchange devices are needed in the existing production process of the gamma-chloropropyl trichlorosilane to remove the reaction heat in time, and the materials of a temperature control system and equipment for the reaction are also required to meet strict requirements.
At present, the industrial production method of gamma-chloropropyl trichlorosilane adopts a traditional kettle type batch method and is generally divided into three process control modes, namely (1) adding a catalyst into a reaction kettle, mixing two raw materials in an overhead tank, adding the two raw materials into the reaction kettle in a dropwise manner, (2) adding one raw material and the catalyst into the reaction kettle, adding the other raw material into the reaction kettle in a dropwise manner, and (3) adding the two raw materials and the catalyst into the reaction kettle in a dropwise manner respectively. The first control mode has the advantages of intense reaction in the early stage, large heat release, slow reaction in the later stage and additional compensation of heat, and the second control mode and the third control mode have the problems of slow reaction in the early stage, easy unbalance of reaction heat control and great potential safety hazard.
In order to realize continuous production of gamma-chloropropyl trichlorosilane, a great deal of researches are carried out by a plurality of enterprises, and a certain result is obtained. Patent US6472549B1 discloses a process for the production of 3-functionalized propyl silanes by recycling most of the product mixture at the top of a tubular reactor with n stages in series running continuously, achieving a real-time excess of trichlorosilane during the reaction. The two-stage tubular reactors were connected in series, the initial molar ratio of trichlorosilane to chloropropene was set to 3.4:1, and the recycle ratio was set to 10:1, with a yield of 84% in terms of chloropropene. However, the initial mole ratio of trichlorosilane to chloropropene is high, and a large amount of unreacted trichlorosilane improves the subsequent treatment difficulty, so that the method is not beneficial to industrialization. Patent CN113121585A discloses a micro-reaction system and a method for continuously preparing gamma-chloropropyl trichlorosilane, raw materials and a catalyst are uniformly mixed in a micro-mixer and then are sent to a micro-reactor for hydrosilylation, and the yield can reach more than 85 percent. However, the reaction pressure of the micro-reaction system is high, the requirements on the micro-reactor are high, and the equipment cost is high.
In summary, the existing gamma-chloropropyl trichlorosilane production has the defects of complex reaction process control, unstable reaction process, long reaction period, long whole production period of products, high catalyst unit consumption, high byproducts, low product yield and the like.
Therefore, a method for preparing gamma-chloropropyl trichlorosilane with high reaction speed, low energy consumption and low byproducts needs to be developed, so that the production efficiency of gamma-chloropropyl trichlorosilane is improved, the production cost is reduced, and continuous production is performed.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a continuous synthesis system and a continuous synthesis method of gamma-chloropropyl trichlorosilane, wherein the continuous synthesis system improves the reaction efficiency and the conversion rate, and reduces the production energy consumption and the production cost. The continuous synthesis method has simple process flow and realizes efficient continuous production.
The basic conception of the technical scheme adopted by the invention is as follows:
A continuous synthesis system of gamma-chloropropyl trichlorosilane comprises a trichlorosilane storage tank, a chloropropyl storage tank, a catalyst storage tank, a static mixer, an n-level serial tubular reaction system and a rectifying device, wherein n is an integer of 3-9;
The tubular reaction system comprises a tubular reactor, a back pressure valve, a degassing device and a condenser connected with a gas phase outlet of the degassing device, wherein the tubular reactor, the back pressure valve and the degassing device are sequentially connected, and a liquid phase outlet of the degassing device is connected with a tubular reactor in a next-stage tubular reaction system after being converged with a liquid phase outlet of the condenser;
the trichlorosilane storage tank, the chloropropene storage tank and the catalyst storage tank are respectively connected with the inlet of the static mixer through respective metering pumps, and the outlet of the static mixer is connected with a tubular reactor in a first-stage tubular reaction system; the inlets of the 2 nd-nth stage tubular reactors are simultaneously connected with a chloropropene storage tank for the feeding of new chloropropene;
The liquid phase outlet of the degassing device in the nth-stage tubular reaction system is connected with the inlet of the rectifying device, the first outlet of the rectifying device is connected with the tubular reactor of the first-stage tubular reaction system, and the second outlet of the rectifying device outputs the gamma-chloropropyl trichlorosilane product.
As an embodiment, the internal element of the tubular reactor is selected from any one of SK type, SV type, SX type, SH type, SL type mixing unit, and mixing element supported by a curved tube.
As one embodiment, the internal element of the tubular reactor is a mixing element supported by a bent tube, and the effective specific surface area of heat exchange is 30-150 m 2/m3.
As one embodiment, the degassing device is a two-stage vertical gas-liquid separator.
The invention also provides a continuous synthesis method of gamma-chloropropyl trichlorosilane, which operates in the continuous synthesis system and comprises the following steps:
(1) Conveying chloropropene, trichlorosilane and a catalyst to a static mixer for mixing, and feeding the obtained mixed solution to an n-level serial tubular reaction system for reaction;
(2) The crude product obtained by the tubular reactor in the first-stage tubular reaction system sequentially passes through a back pressure valve and a degassing device to remove gas phase, and the liquid phase flows to the tubular reactor of the next-stage tubular reaction system to continue reaction;
(3) After passing through the n-level serial tubular reaction systems, the product enters a rectifying device from a liquid phase outlet of a degassing device in the n-level tubular reaction system for rectification to obtain the product gamma-chloropropyl trichlorosilane, and the residual liquid at the bottom of the rectifying kettle is returned to a tubular reactor in the first-level tubular reaction system after being recovered to continue to participate in the reaction.
In one embodiment, the raw material of chloropropene is divided into n parts and is respectively added from the inlet of each tubular reactor, wherein in the 2 nd-nth tubular reactors, the raw material of the chloropropene which is newly added continuously reacts with the reactant materials of the previous stage.
As one embodiment, the total feed molar ratio of trichlorosilane to chloropropene is (1.00-1.50): 1, preferably 1.10:1.
As one embodiment, the reaction temperature of the tubular reactor of the first n-1 stage tubular reaction system is controlled to be 70-90 ℃, the reaction temperature of the tubular reactor of the nth stage tubular reaction system is controlled to be 100-120 ℃, and the total reaction time is 0.5-3.5 h.
In one embodiment, in the step (1), the concentration of the catalyst in the obtained mixed solution is 2-8 ppm, preferably 2-4 ppm, and preferably, the outlet flow of each tubular reactor is back-pressed to 1-2 MPa through a back-pressure valve.
As one implementation mode, the outlet material of each tubular reactor comprises unreacted trichlorosilane, chloropropene and byproducts of propylene and silicon tetrachloride, gas-phase byproducts of propylene and silicon tetrachloride are separated in real time through each degassing device, and liquid-phase trichlorosilane and chloropropene raw materials are recovered.
The gamma-chloropropyl trichlorosilane continuous synthesis system and method have the following beneficial effects:
(1) The gamma-chloropropyl trichlorosilane continuous synthesis system is used together with other devices through the combination of the back pressure valve and the degassing device, so that the by-product propylene is effectively removed in real time in the reaction process, the generation of by-products such as the propyl trichlorosilane is avoided, the loss of raw materials is reduced, and the utilization rate of the raw materials and the selectivity of products are improved.
(2) Based on the continuous synthesis system, the synthesis method adopts a special feeding mode, so that the selectivity of the product is further improved, for example, the selectivity of the product is as high as 84.8% under the condition that the total feeding mole ratio of trichlorosilane to chloropropene is 1.10:1. The low total feed molar ratio obviously reduces the residual quantity of the raw material trichlorosilane, prevents a large quantity of unreacted trichlorosilane from entering the subsequent process, reduces the difficulty and the operation risk of rectification and purification, and is more beneficial to realizing industrialization.
(3) As a more optimized scheme, 80 ℃ hot water is used as a heating and heat transfer medium of a first n-1 (n is an integer of 3-9) stage reactor, the early reaction temperature is strictly controlled within the optimal temperature range of 75-85 ℃ for synthesizing gamma-chloropropyl trichlorosilane through the excellent mixing performance of the tubular reactor, local hot spots are eliminated, and the reaction is prevented from moving to the side reaction direction due to local overheating. Compared with the prior art, the selectivity is improved by 4% -8% and is not lower than 80%.
In addition, the heat conduction oil is used as a heat conduction medium of the nth-stage tubular reactor, the reaction is controlled to be carried out in a high-temperature area, the reaction can be ensured to be fully carried out, and the product yield is improved.
Drawings
FIG. 1 is a schematic diagram of a continuous synthesis system of gamma-chloropropyl trichlorosilane according to the present invention.
The figure shows that a1, trichlorosilane storage tank, a2, chloropropene storage tank, a 3, a catalyst storage tank, a 4, a static mixer, an R-1, a first-stage reaction system, an R-2, a second-stage reaction system, an R-3, a third-stage reaction system, an R-n, an nth-stage reaction system, a 11, a tubular reactor, a 12, a back pressure valve, a 13, a degassing device, a 14, a condenser and a 5, rectifying device are marked;
Wherein n is an integer of 3 to 9.
Detailed Description
The following description of the embodiments of the present invention will be made more apparent, and the embodiments described in detail, but not necessarily all, in connection with the accompanying drawings. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to fall within the scope of the invention.
The source of the reaction raw material in the present invention is not particularly limited and may be commercially available, and the catalyst may be a homogeneous catalyst well known to those skilled in the art, and chloroplatinic acid is particularly preferably used in the present invention.
A continuous synthesis system of gamma-chloropropyl trichlorosilane is shown in figure 1, and comprises a trichlorosilane storage tank 1, a chloropropene storage tank 2, a catalyst storage tank 3, a static mixer 4, an n-level serial tubular reaction system and a rectifying device 5;n, wherein n is an integer of 3-9, for example, n is 3, 4, 5, 6, 7, 8 or 9;
the tubular reaction system comprises a tubular reactor 11, a back pressure valve 12, a degassing device 13 and a condenser 14 connected with a gas phase outlet of the degassing device 13, which are sequentially connected, wherein a liquid phase outlet of the degassing device 13 is converged with a liquid phase outlet of the condenser 14 and then connected with the tubular reactor 11 in the next-stage tubular reaction system;
The trichlorosilane storage tank 1, the chloropropene storage tank 2 and the catalyst storage tank 3 are respectively connected with the inlet of the static mixer 4 through respective metering pumps, the three are mixed in the static mixer 4 in proportion under the regulation and control of the metering pumps, the outlet of the static mixer 4 is connected with the tubular reactor 11 in the first-stage tubular reaction system R-1, and the inlets of the 2 nd-nth-stage tubular reactors are simultaneously connected with the chloropropene storage tank for standby feeding of new chloropropene.
The liquid phase outlet of the degassing device 13 in the nth-stage tubular reaction system is connected with the inlet of the rectifying device 5, the first outlet of the rectifying device 5 is connected with the tubular reactor 11 of the first-stage tubular reaction system R-1, and the second outlet outputs the product of gamma-chloropropyl trichlorosilane.
As one way, the internal components of the tubular reactor chosen in the present invention are industry standard SK-type, SV-type, SX-type, SH-type, SL-type mixing units or non-standard mixing elements supported by curved tubes. The heat exchange efficiency specific surface area of the mixing element supported by the bending tube is preferably 30-150 m 2/m3.
As one mode, the tubular reactor in the first n-1 stage tubular reaction system uses hot water as a heat transfer medium, and the tubular reactor in the nth stage tubular reaction system uses heat transfer oil as a heat transfer medium.
As one mode, the degassing device is a two-stage vertical gas-liquid separator with a compact structure. The compact construction minimizes separator size, weight, footprint and cost. Particularly preferred are the PFA gas-liquid separator of the Xiamen Baifluoroda technology Co., ltd., the compact oil mist separator of Kanger group, and the HIPERTWINLINE TM tube gas-liquid separator of the Sulfan pump Co., ltd., more preferred is the HIPERTWINLINE TM tube gas-liquid separator of the Sulfan pump Co., ltd., because of its unique on-line operating window.
According to the invention, by adopting the preferable tubular reactor, a large amount of reaction heat released by hydrosilylation is timely removed from the tubular reactor based on the mixing element supported by the inner bent tube, so that the temperature of a reaction system is stabilized, the reaction is restrained from deviating to the side reaction direction, and the reaction efficiency and the conversion rate are improved. Meanwhile, the gas-liquid separator is preferably used for removing the doped byproduct gas-phase propylene from the reaction crude product on line, and a condenser connected with a gas-phase outlet is used for recycling gasified raw materials of trichlorosilane and chloropropene, so that the loss of raw materials is reduced, the further reaction of the byproduct propylene is prevented to generate byproduct propyl trichlorosilane, and the selectivity of the product is improved.
The invention provides a continuous synthesis method of gamma-chloropropyl trichlorosilane, which is operated in the continuous synthesis system as described in any one of the above, and comprises the following steps:
(1) Conveying chloropropene, trichlorosilane and a catalyst to a static mixer for mixing, and feeding the obtained mixed solution to an n-level serial tubular reaction system for reaction;
(2) The crude product obtained by the tubular reactor in the first-stage tubular reaction system sequentially passes through a back pressure valve and a degassing device to remove gas phase, and the liquid phase flows to the tubular reactor of the next-stage tubular reaction system to continue reaction;
(3) After passing through the n-level serial tubular reaction systems, the product enters a rectifying device from a liquid phase outlet of a degassing device in the n-level tubular reaction system for rectification to obtain the product gamma-chloropropyl trichlorosilane, and the residual liquid at the bottom of the rectifying kettle is returned to a tubular reactor in the first-level tubular reaction system after being recovered to continue to participate in the reaction.
As one mode, the raw material of chloropropene is divided into n parts, and the n parts are respectively added from the inlets of each tubular reactor, wherein in the 2 nd-nth tubular reactors, the raw material of the chloropropene which is newly added continuously reacts with the reactant materials of the previous stage.
As one mode, the total feed mole ratio of trichlorosilane to chloropropene is 1.00-1.50:1.
As one mode, the reaction temperature of the tubular reactor of the first n-1 stage tubular reaction system is controlled to be 70-90 ℃, the reaction temperature of the tubular reactor of the nth stage tubular reaction system is controlled to be 100-120 ℃, and the total reaction time is 0.5-3.5 h.
In one embodiment, in the step (1), the concentration of the catalyst in the obtained mixed solution is 2 to 8ppm, preferably 2 to 4ppm.
Preferably, the outlet flow of each tubular reactor is back-pressed to 1-2 MPa through a back-pressure valve.
The method comprises the steps of separating gas-phase byproduct propylene and silicon tetrachloride in real time through the degassing devices, and recovering liquid-phase trichlorosilane and chloropropene raw materials.
Examples 1 to 4
The series of n=6 stages was used in the continuous synthesis system of gamma-chloropropyl trichlorosilane shown in fig. 1. The internal element is a mixing element supported by a bending pipe, the effective specific surface area of heat exchange is 150m 2/m3, the back pressure of outlet material flows of each tubular reactor is 2MPa through a back pressure valve, the two-stage vertical gas-liquid separator is a HIPERTWINLINE TM separator of Sulfan pump industry Co., ltd, and the device has an online operation window and a wide pressure-resistant range.
The molar ratio of trichlorosilane to chloropropene is 1.10:1, the concentration of the catalyst chloroplatinic acid is 4ppm, the reaction temperature of the first 5-stage tubular reactor is controlled to be 80 ℃, the reaction temperature of the 6-stage tubular reactor is controlled to be 110 ℃, and the reaction time is 3 hours. The feed rates of trichlorosilane and chloropropene were adjusted, and the reaction conversion and the product selectivity in terms of chloropropene at different feed rates were measured, and are shown in table 1.
TABLE 1
In Table 1, from example 1 to example 4, the total trichlorosilane and chloropropene feed rates were continuously reduced, and the reaction conversion and the product selectivity were continuously improved. However, examples 3 and 4 correspond to lower capacity, and it is more desirable to consider the total feed rate of preferred example 2.
Examples 5 to 6
The continuous synthesis reaction system of example 1 was used.
In examples 5-6, the total feed flow rate is 104.72mL/min, the concentration of the catalyst chloroplatinic acid is 4ppm, the total feed mole ratio of trichlorosilane to chloropropene is controlled to be 1.00:1 and 1.50:1 respectively, and the reaction conversion rate and the product selectivity of the different total feed mole ratios of trichlorosilane to chloropropene in terms of chloropropene are measured, and are specifically shown in Table 2.
TABLE 2
In the reaction process, the increase of the total feed molar ratio of trichlorosilane is favorable for improving the reaction conversion rate and the product selectivity calculated by chloropropene, but can also lead to the increase of the residual quantity of trichlorosilane after the reaction is ended, thereby improving the rectification difficulty and the operation risk of crude products.
Therefore, considering the combination of comparative examples 1-4 and examples 5-6, it is preferred that the molar ratio of total feed trichlorosilane to chloropropene be 1.10:1.
Examples 7 to 9
The continuous synthesis reaction system of example 1 was used.
In examples 7-9, the total feeding molar ratio of trichlorosilane to chloropropene is 1.10:1, and the total feeding flow is 104.72mL/min. Wherein the concentrations of the chloroplatinic acid in the catalysts of examples 7 and 8 are 2ppm and 8ppm, respectively, the back pressure of the outlet stream of each tubular reactor through a back pressure valve is 2MPa, the concentration of the chloroplatinic acid in the catalyst of example 9 is 4ppm, the back pressure of the outlet stream of each tubular reactor through the back pressure valve is 1MPa, and the reaction conversion and the product selectivity in terms of chloropropene at different total feed trichlorosilane and chloropropene molar ratios are measured, and are specifically shown in Table 3.
TABLE 3 Table 3
Examples 2, 7-8 demonstrate that increasing the chloroplatinic acid concentration exhibits a first promotion and then inhibition of the reaction conversion and product selectivity in terms of chloropropene, and examples 2 and 9 demonstrate that increasing the back pressure valve outlet pressure at each stage facilitates more complete separation of propylene produced by side reactions, thereby increasing the reaction conversion and product selectivity in terms of chloropropene.
Examples 10 to 22
The continuous synthesis reaction system of example 1 was used.
In examples 10-22, the total feeding molar ratio of trichlorosilane to chloropropene is 1.10:1, and the total feeding flow is 104.72mL/min. The initial raw material mole ratio of each stage of serial tubular reaction system is adjusted by changing the feeding mode of trichlorosilane and chloropropene raw materials, wherein in the embodiment 10-15, trichlorosilane is adopted to feed from the inlet of the first stage of reaction system, chloropropene is divided into 6 parts to feed from the inlet of each stage of reaction system respectively, and the distribution ratio of the chloropropene is (1:1:1:1:1:1:1), (2:1:1:1:1:1:1), (3:1:1:1:1:1:1:1), (4:1:1:1:1:1), (5:1:1:1:1:1) and (6:1:1:1:1:1:1);
In the embodiment 16, the trichlorosilane is directly fed from the inlet of the first-stage tubular reaction system according to the mol ratio of the trichlorosilane to the chloropropene of 1.10:1, in the embodiment 17-22, the chloropropene is adopted to be fed from the inlet of the first-stage tubular reaction system, 6 parts of the trichlorosilane is respectively fed from the inlets of the reaction systems of all stages, and the distribution ratio of the trichlorosilane from the first stage to the sixth stage is (1:1:1:1:1:1), (2:1:1:1:1:1:1:1), (3:1:1:1:1:1:1), (4:1:1:1:1:1), (5:1:1:1:1:1) and (6:1:1:1:1). The molar ratio of trichlorosilane to chloropropene as a raw material at the inlet of the first-stage tubular reactor was measured and is shown in Table 4.
TABLE 4 Table 4
The reaction conversion and the product selectivity in terms of chloropropene were analyzed by taking the example of feeding trichlorosilane directly from the inlet of the first-stage tubular reactor, dividing the trichlorosilane into 6 parts on average, feeding the same from each stage of the tubular reactor (example 10), feeding trichlorosilane and chloropropene directly from the inlet of the first-stage tubular reactor (example 16), and feeding chloropropene directly from the inlet of the first-stage tubular reactor, dividing the same into 6 parts, feeding the same from each stage of the tubular reactor (example 17).
TABLE 5
Examples 23 to 26
The gamma-chloropropyl trichlorosilane continuous synthesis system used in example 1 was used.
The mol ratio of the trichlorosilane to the chloropropene is 1.10:1, the total feeding flow is 104.72mL/min, the trichlorosilane is directly fed from the inlet of the first-stage tubular reactor at one time, and the chloropropene is evenly divided into 6 parts and is respectively fed from each stage of tubular reactors. The reaction conversion and the product selectivity in terms of chloropropene were measured by changing the heat transfer medium of the first 5-stage tubular reactor, and the results are shown in Table 6.
TABLE 6
The optimal synthesis temperature of gamma-chloropropyl trichlorosilane is 80 ℃ under the same heat conducting medium, and meanwhile, the temperature control effect of hot water relative to heat conducting oil is better under the optimal synthesis temperature.
The method is characterized by comprehensively considering the factors of reaction conversion rate and product selectivity calculated by chloropropene, gamma-chloropropyl trichlorosilane productivity, residual trichlorosilane treatment difficulty and the like, preferably, the mol ratio of trichlorosilane to chloropropene is 1.10:1, the total feed flow is 104.72mL/min, the concentration of catalyst chloroplatinic acid is 4ppm, the process adopts the process that the trichlorosilane is fed from the inlet of a first-stage reaction system, the chloropropene is divided into 6 parts and is respectively fed from the inlets of all stages of reaction systems, the distribution ratio of the chloropropene (1:1:1:1:1), the reaction temperature of the first 5-stage tubular reactor is controlled to be 80 ℃ (hot water), the reaction temperature of the 6-stage tubular reactor is controlled to be 110 ℃ (heat conducting oil), the reaction duration is 3 hours, and the back pressure of outlet material flows of all the tubular reactors is 2MPa through back pressure valves.
Claims (10)
1. A continuous synthesis system of gamma-chloropropyl trichlorosilane is characterized by comprising a trichlorosilane storage tank, a chloropropene storage tank, a catalyst storage tank, a static mixer, an n-level serial tubular reaction system and a rectifying device, wherein n is an integer of 3-9;
The tubular reaction system comprises a tubular reactor, a back pressure valve, a degassing device and a condenser connected with a gas phase outlet of the degassing device, wherein the tubular reactor, the back pressure valve and the degassing device are sequentially connected, and a liquid phase outlet of the degassing device is connected with a tubular reactor in a next-stage tubular reaction system after being converged with a liquid phase outlet of the condenser;
the trichlorosilane storage tank, the chloropropene storage tank and the catalyst storage tank are respectively connected with the inlet of the static mixer through respective metering pumps, and the outlet of the static mixer is connected with a tubular reactor in a first-stage tubular reaction system; the inlets of the 2 nd-nth stage tubular reactors are simultaneously connected with a chloropropene storage tank for the feeding of new chloropropene;
The liquid phase outlet of the degassing device in the nth-stage tubular reaction system is connected with the inlet of the rectifying device, the first outlet of the rectifying device is connected with the tubular reactor of the first-stage tubular reaction system, and the second outlet of the rectifying device outputs the gamma-chloropropyl trichlorosilane product.
2. The continuous synthesis system of gamma-chloropropyl trichlorosilane according to claim 1, wherein the internal elements of the tubular reactor are selected from any one of SK type, SV type, SX type, SH type, SL type mixing units and mixing elements supported by curved tubes.
3. The continuous synthesis system of gamma-chloropropyl trichlorosilane according to claim 2, wherein the internal elements of the tubular reactor are mixed elements supported by bent tubes, and the effective specific surface area of heat exchange is 30-150 m 2/m3.
4. The continuous synthesis system of gamma-chloropropyl trichlorosilane according to claim 1, wherein the degassing device is a two-stage vertical gas-liquid separator.
5. A continuous synthesis process of gamma-chloropropyl trichlorosilane operating in a continuous synthesis system according to any one of claims 1 to 4, comprising the steps of:
(1) Conveying chloropropene, trichlorosilane and a catalyst to a static mixer for mixing, and feeding the obtained mixed solution to an n-level serial tubular reaction system for reaction;
(2) The crude product obtained by the tubular reactor in the first-stage tubular reaction system sequentially passes through a back pressure valve and a degassing device to remove gas phase, and the liquid phase flows to the tubular reactor of the next-stage tubular reaction system to continue reaction;
(3) After passing through the n-level serial tubular reaction systems, the product enters a rectifying device from a liquid phase outlet of a degassing device in the n-level tubular reaction system for rectification to obtain the product gamma-chloropropyl trichlorosilane, and the residual liquid at the bottom of the rectifying kettle is returned to a tubular reactor in the first-level tubular reaction system after being recovered to continue to participate in the reaction.
6. The continuous process for the synthesis of gamma-chloropropyl trichlorosilane according to claim 5, wherein the raw material of chloropropene is divided into n parts and is respectively added from the inlet of each tubular reactor, wherein the raw material of chloropropene newly added in the 2 nd to nth tubular reactors is continuously reacted with the reaction materials of the previous stage.
7. The continuous synthesis method of gamma-chloropropyl trichlorosilane according to claim 5, wherein the total feed molar ratio of trichlorosilane to chloropropene is (1.00-1.50): 1, preferably 1.10:1.
8. The continuous synthesis method of gamma-chloropropyl trichlorosilane according to claim 5, wherein the reaction temperature of the tubular reactor of the first n-1 stage tubular reaction system is controlled to be 70-90 ℃, the reaction temperature of the tubular reactor of the nth stage tubular reaction system is controlled to be 100-120 ℃, and the total reaction time is 0.5-3.5 h.
9. The continuous synthesis method of gamma-chloropropyl trichlorosilane according to claim 5, wherein in the step (1), the concentration of the catalyst in the obtained mixed solution is 2-8 ppm, preferably 2-4 ppm;
preferably, the outlet flow of each tubular reactor is back-pressed to 1-2 MPa through a back-pressure valve.
10. The continuous synthesis method of gamma-chloropropyl trichlorosilane according to claim 5, wherein the outlet material of each tubular reactor comprises unreacted trichlorosilane, chloropropene, by-product propylene and silicon tetrachloride, gas-phase by-product propylene and silicon tetrachloride are separated in real time through each degassing device, and liquid-phase trichlorosilane and chloropropene raw materials are recovered.
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