Process and apparatus for catalytic cracking of silicone high boilers

Abstract

The application provides a method and device for catalytic cracking of silicone high-boiling residue by using a solid-organics-amine-based heterogeneous catalyst. The method uses a solid-organics-amine-based heterogeneous catalyst, and a slurry bed catalytic cracking system with gas-liquid-solid three-phase flow to catalytically crack silicone high-boiling residue to obtain catalytic cracking products rich in low-boiling silicone monomers, which are purified to obtain high-purity silicone monomers. The device used to realize the method mainly includes a slurry bed catalytic cracking device for silicone high-boiling residue cracking, a purification device for purifying gaseous cracking products to obtain high-purity silicone monomer products, and auxiliary equipment. The application can realize catalytic cracking of silicone high-boiling residue by using a solid-organics-amine-based heterogeneous catalyst, and obtain silicone monomer products, realize harmless and resourceful treatment of silicone high-boiling residue. At the same time, the catalyst used is a solid-organics-amine-based heterogeneous catalyst, which is not miscible with the reaction material and is in a solid state, effectively reducing or even avoiding the loss of the catalyst, reducing the catalyst loss, improving the catalyst use efficiency, and reducing the catalyst cost.

Description

Technical Field

[0001] This technology belongs to the field of organosilicon high-boiling-point treatment application technology, and in particular relates to a heterogeneous catalytic cracking method and apparatus for organosilicon high-boiling-point substances. Background Technology

[0002] Catalytic cracking of high-boiling-point organosilicon compounds to produce silane monomers (hereinafter referred to as catalytic cracking technology) is a very important technology for treating high-boiling-point organosilicon compounds. It can not only reduce the cracking temperature of high-boiling-point organosilicon compounds and reduce energy consumption, but also improve the yield of organosilicon monomers. It is currently the mainstream technology and future development trend for high-boiling-point organosilicon compounds.

[0003] Based on the catalysts used, organosilicon high-boiling-point catalytic cracking technologies can be classified into aluminum trichloride-based catalytic cracking technologies, palladium-phosphorus coordination compound-based catalytic cracking technologies, phosphate-based catalytic cracking technologies, molecular sieve-based catalytic cracking technologies, transition metal and its compound-based catalytic cracking technologies, and organic amine-based catalytic cracking technologies.

[0004] Among these technologies, organic amine catalytic cracking primarily uses organic amine compounds such as tertiary amines, N,N-dimethylaniline, and N,N-dimethylformamide as catalysts to react high-boiling-point substances with hydrogen chloride at 80-140℃ and atmospheric pressure to prepare silane monomers. The catalysts used are relatively mature, simple, and efficient, with mild reaction conditions and the ability to conduct the reaction continuously. The process is mature, the reaction conditions are relaxed, and components with high chlorine content are easily cracked, resulting in high yields of organosilicon monomers. Therefore, this type of technology is the mainstream and hot topic in the catalytic cracking of high-boiling-point organosilicon substances. However, the catalysts used in this technology are liquid and exist in a homogeneous state, miscible with the high-boiling-point organosilicon substances and cracking products. The catalyst is easily discharged from the device along with the organosilicon compounds and lost, resulting in significant catalyst loss and a large amount of catalyst used.

[0005] To overcome the aforementioned problems, the Institute of Process Engineering, Chinese Academy of Sciences, Hubei Three Gorges Laboratory, and Hubei Xingrui Silicon Materials Co., Ltd. have developed a supported organic amine-based heterogeneous catalyst (patent: 202211720473.x, hereinafter referred to as the catalyst unless otherwise specified). This catalyst is a porous solid catalyst and exists in a heterogeneous state that is immiscible with high-boiling organosilicon compounds and catalytic cracking products, thus overcoming the problem of catalyst loss. However, traditional production methods and equipment for the catalytic cracking of high-boiling organosilicon compounds using organic amine compounds as catalysts are all homogeneous reaction methods such as stirred reactors. For example, patents CN 112058193 A and CN201320797705.1 basically use mechanically stirred reactors for homogeneous reactions. These devices and production methods are difficult to apply to the catalytic cracking of high-boiling organosilicon compounds using heterogeneous catalysts.

[0006] Therefore, it is crucial to develop novel methods and apparatuses for the catalytic cracking of high-boiling-point organosilicon compounds using supported organic amine-based heterogeneous catalysts. Summary of the Invention

[0007] The present invention aims to solve at least one of the technical problems existing in the prior art or related art.

[0008] Therefore, this invention provides a method for the catalytic cracking of high-boiling-point organosilicon compounds capable of heterogeneous catalytic cracking. This method uses a supported organic amine-based heterogeneous catalyst as the catalyst and employs a gas-liquid-solid three-phase flow slurry bed catalytic cracking system to catalytically crack high-boiling-point organosilicon compounds, obtaining catalytic cracking products rich in low-boiling-point organosilicon monomers. These products are then purified to obtain high-purity organosilicon monomers, thereby achieving the harmless and resource-based treatment and utilization of high-boiling-point organosilicon compounds. The specific process flow is as follows:

[0009] A catalyst of a specific particle size is added to the slurry-bed catalytic cracking unit from the catalyst supply system. Then, hydrogen chloride gas is supplied from the hydrogen chloride supply system at a certain gas velocity through the bottom of the slurry-bed catalytic cracking unit via a hydrogen chloride supply pump, serving as the reaction fluidizing gas and the fluidizing gas. If the amount of hydrogen chloride gas is sufficient for the reaction but insufficient to fluidize the material within the slurry-bed catalytic cracking unit, a certain amount of inert gas can be added to the slurry-bed catalytic cracking unit from the inert gas supply system via an inert gas pump.

[0010] Simultaneously, high-boiling-point organosilicon raw materials are supplied to the high-boiling-point organosilicon preheater at a certain flow rate from the high-boiling-point organosilicon supply system. The high-boiling-point organosilicon raw materials are preheated into high-temperature high-boiling-point organosilicon by exchanging heat with the high-temperature heating medium. After heat exchange, the high-temperature heating medium becomes a low-temperature heating medium, which is then treated and reused. Then, the high-temperature high-boiling-point organosilicon is pumped into the slurry bed catalytic cracking equipment using an organosilicon pump. The high-temperature high-boiling-point organosilicon and catalyst added to the slurry bed catalytic cracking equipment are fully fluidized and mixed under the action of fluidized reaction gas to form a fluidized slurry, thereby achieving sufficient mixing and contact.

[0011] While feeding, a high-temperature heating medium is supplied to the heating system of the slurry bed catalytic cracking equipment. The high-temperature organosilicon high-boiling-point substance exchanges heat with the high-temperature heating medium and is heated to the temperature required for catalytic cracking. Under the action of the catalyst, it undergoes a cracking reaction to generate gaseous cracked products and a small amount of cracking residue. The high-temperature heating medium after heat exchange becomes a low-temperature heating medium and is discharged from the heating system of the slurry bed catalytic cracking equipment. After treatment, it is reused.

[0012] The gaseous pyrolysis product is discharged from the top of the slurry bed catalytic cracking equipment and enters the gaseous pyrolysis product purification equipment, where a small amount of carried matter [mainly liquid residues (containing cracking feedstock and cracking products) and solid catalyst] are removed to obtain clean gaseous pyrolysis product.

[0013] The removed material is returned to the slurry bed catalytic cracking unit, where the liquid residue is pyrolyzed again to increase the pyrolysis rate, and the catalyst is returned for reuse.

[0014] The clean gaseous pyrolysis products enter the purification equipment for further purification. Inside the purification equipment, the gaseous pyrolysis products flow upwards with the equipment and undergo heat and mass exchange with the liquid coming from above, resulting in purification. The purified gas, in the form of lighter components with lower boiling points, exits from the top of the purification equipment and enters the top condenser where it exchanges heat with a low-temperature cooling medium, cooling and liquefying it into high-purity organosilicon monomers and non-condensable non-condensable gases in liquid form. After heat exchange, the low-temperature cooling medium becomes a high-temperature cooling medium, which is then treated and reused.

[0015] The non-condensable gas generated in the purification equipment is passed into the tail gas treatment equipment for treatment, and the treated gas that meets the standards is discharged as tail gas.

[0016] The high-purity organosilicon monomers generated in the purification equipment are transported to a high-purity organosilicon monomer storage system for recycling as organosilicon monomer products.

[0017] The liquid flowing down from the purification equipment enters the bottom of the purification equipment, and then enters the reboiler of the purification equipment. The high-temperature heating medium is heated and vaporized, and the liquid is then re-entered into the purification equipment for further separation. The components with lower boiling points are extracted, while the components with higher boiling points that no longer vaporize are discharged from the bottom of the purification equipment as purification residue and are transported back to the slurry bed catalytic cracking equipment for further cracking. The high-temperature heating medium after heat exchange becomes a low-temperature heating medium and is reused after treatment.

[0018] After the high-boiling-point organosilicon compounds in the slurry bed catalytic cracking equipment undergo sufficient catalytic cracking, most of the components are converted into gaseous cracking products and discharged from the top. A small amount of cracking residue that cannot be further catalytically cracked or that still has a high boiling point, along with the catalyst in the residue, is discharged from the bottom of the slurry bed catalytic cracking equipment in the form of cracking bottom material.

[0019] The pyrolysis feedstock discharged from the bottom of the slurry bed catalytic cracking unit is transported to a liquid-solid separation unit to separate and remove the catalyst from the residual liquid. The catalyst in the separated residual liquid is returned to the slurry bed catalytic cracking unit for reuse, while the pyrolysis residual liquid after catalyst removal is discharged from the liquid-solid separation unit.

[0020] When the amount of catalyst in the slurry bed catalytic cracking equipment is insufficient due to loss of catalyst returned from the separation and purification equipment and liquid-solid separation equipment caused by wear, carryover, or other reasons, fresh catalyst is supplied from the catalyst supply system to replenish it.

[0021] The pyrolysis residue discharged from the liquid-solid separation equipment is passed into the pyrolysis residue cooling equipment and cooled into low-temperature pyrolysis residue by exchanging heat with the low-temperature cooling medium. The low-temperature cooling medium becomes a high-temperature cooling medium. The resulting low-temperature pyrolysis residue is then passed into the pyrolysis residue storage system for collection and centralized processing. The high-temperature cooling medium is then processed and reused.

[0022] In this process, the high-boiling-point organosilicon feedstock is preheated into a high-temperature high-boiling-point organosilicon in a high-boiling-point organosilicon preheating device. The higher the temperature of the high-boiling-point organosilicon, the better, so as to form a low-viscosity high-boiling-point organosilicon liquid, which provides good flowability and fluidization within the slurry-bed catalytic cracking device. However, the temperature of the high-boiling-point organosilicon generally does not exceed the boiling point or the cracking temperature of the high-boiling-point organosilicon. Preferably, the temperature of the high-boiling-point organosilicon is the bubble point temperature, meaning the high-boiling-point organosilicon is fed into the slurry-bed catalytic cracking device at its bubble point.

[0023] The heterogeneous catalyst used is a solid particle, and its hydrodynamic properties are basically the same as those of the high-boiling organosilicon compound, that is, the minimum fluidization rate and entrained gas velocity of the catalyst and the high-boiling organosilicon compound are basically the same. Preferably, the particle size of the catalyst is 0.025-0.25 mm.

[0024] When supplying gas (hydrogen chloride gas or a mixture of hydrogen chloride gas and supplemented inert gas) to a slurry bed catalytic cracking unit, the gas supply rate should ensure that all liquid and solid materials, including the organosilicon high-boiling-point feedstock, its cracking products, and the catalyst, are in a stable fluidized state within the slurry bed. Preferably, under conditions not exceeding the entrainment gas velocity of the catalyst, the gas supply rate is 1-3 times the minimum fluidization velocity of the catalyst, approximately 0.025-0.25 m / s.

[0025] The inert gas used can be either a cracked non-condensable gas generated during the catalytic cracking of organosilicon high-boiling-point substances, rich in low-boiling-point components such as silane, disilane, and monochlorosilane; or a newly added non-reactive gas that does not react with any of the materials, including organosilicon high-boiling-point substances, their cracking products, catalysts, and hydrogen chloride, such as nitrogen or carbon dioxide; or a mixture of cracked non-condensable gas and the newly added gas. Preferably, a non-reactive gas such as nitrogen is used.

[0026] The purification of the gaseous pyrolysis product can be achieved using methods such as pressure swing adsorption (PSA) and distillation. Preferably, distillation is used for purification.

[0027] Another aspect of the present invention provides an apparatus capable of heterogeneous catalytic cracking of high-boiling organosilicon compounds.

[0028] The device mainly includes a catalyst supply system, a hydrogen chloride supply system, an inert gas supply system, a hydrogen chloride supply pump, an inert gas supply pump, a high-boiling-point organosilicon supply system, a high-boiling-point organosilicon preheating equipment, a high-boiling-point organosilicon supply pump, a slurry bed catalytic cracking equipment, a separation and purification equipment, a purification equipment, a tail gas treatment equipment, a high-purity organosilicon monomer storage system, a liquid-solid separation equipment, a cracking residue cooling equipment, and a cracking residue storage system.

[0029] The catalyst supply system mainly provides catalysts for the catalytic cracking of high-boiling-point organosilicon compounds. Its outlet is connected to the catalyst inlet of the slurry bed catalytic cracking equipment and the catalyst outlet of the liquid-solid separation equipment.

[0030] The hydrogen chloride supply system is designed to provide hydrogen chloride gas as the reaction gas used in the catalytic cracking of high-boiling organosilicon compounds, and its outlet is connected to the inlet of the hydrogen chloride supply pump.

[0031] If the inert gas supply system is to be supplemented with fluidizing gas, its outlet is connected to the inlet of the inert gas supply pump.

[0032] The hydrogen chloride supply pump is mainly used to transport hydrogen chloride gas. Its inlet is connected to the outlet of the hydrogen chloride supply system, and its outlet is connected to the inlet of the slurry bed catalytic cracking equipment.

[0033] The inert gas pump is mainly used to transport inert gas. Its inlet is connected to the outlet of the inert gas supply system, and its outlet is connected to the inlet of the slurry bed catalytic cracking equipment.

[0034] The organosilicon high-boiling-point system mainly provides organosilicon high-boiling-point raw materials, and its outlet is connected to the inlet of the organosilicon high-boiling-point preheating equipment.

[0035] The organosilicon high-boiling-point preheating equipment is mainly used to preheat organosilicon high-boiling-point raw materials. Its inlet is connected to the outlet of the organosilicon high-boiling-point system, its outlet is connected to the inlet of the organosilicon high-boiling-point pump, and its inlet and outlet are connected to the heating medium system.

[0036] The pump for supplying high-boiling-point organosilicon is mainly used to transport high-boiling-point organosilicon. Its inlet is connected to the outlet of the high-boiling-point organosilicon preheating equipment, and its inlet is connected to the inlet of the high-boiling-point organosilicon in the slurry bed catalytic cracking equipment.

[0037] The slurry-bed catalytic cracking equipment is used for the catalytic cracking of high-boiling-point organosilicon compounds. It is a slurry-bed reactor equipped with a heating system to provide the heat required for the catalytic cracking of these compounds. Its catalyst inlet is connected to the outlet of the catalyst supply system and the catalyst outlet of the liquid-solid separation equipment. Its gas inlet is connected to the outlets of the hydrogen chloride pump and the inert gas pump. Its high-boiling-point organosilicon inlet is connected to the outlet of the high-boiling-point organosilicon pump. Its gas outlet is connected to the inlet of the separation and purification equipment. Its liquid-solid feed inlet is connected to the outlet of the separation and purification equipment. Its bottom liquid inlet is connected to the bottom liquid outlet of the purification equipment. Its bottom feed outlet is connected to the feed inlet of the liquid-solid separation equipment. Its medium inlet and outlet are connected to the heating medium supply system.

[0038] The separation and purification equipment is mainly used to remove carryover substances from gaseous pyrolysis products, purify the gaseous pyrolysis products, and recover the carryover substances. Its inlet is connected to the outlet of the slurry bed catalytic cracking equipment, its outlet is connected to the liquid-solid feed inlet of the slurry bed catalytic cracking equipment, and its outlet is connected to the feed inlet of the purification equipment.

[0039] Purification equipment is mainly used to purify organosilicon monomers produced by the cracking of high-boiling-point organosilicon compounds to obtain high-purity organosilicon monomer products. It can be pressure swing adsorption equipment, distillation equipment, etc., with distillation equipment being preferred.

[0040] The inlet of the purification equipment is connected to the outlet of the separation and purification equipment, the outlet of the purification equipment is connected to the inlet of the tail gas treatment equipment, the product outlet of the purification equipment is connected to the inlet of the organosilicon monomer storage system, the bottom liquid outlet of the purification equipment is connected to the bottom liquid outlet of the slurry bed catalytic cracking equipment, the inlet and outlet of the cooling medium are connected to the cooling medium supply system, and the inlet and outlet of the heating medium are connected to the heating medium supply system.

[0041] The exhaust gas treatment equipment is mainly used to treat exhaust gas so that it can meet emission standards. Its inlet is connected to the outlet of the purification equipment, and its outlet is directly open to the atmosphere.

[0042] The high-purity organosilicon monomer storage system is mainly used to store organosilicon monomer products, and its inlet is connected to the product outlet of the purification equipment.

[0043] The liquid-solid separation equipment is mainly used to separate the pyrolysis feedstock produced by the slurry bed catalytic cracking equipment in order to recover the catalyst stored therein. Its inlet is connected to the pyrolysis feedstock outlet of the slurry bed catalytic cracking equipment, its catalyst outlet is connected to the outlet of the catalyst supply system and the catalyst inlet of the slurry bed catalytic cracking equipment, and its liquid outlet is connected to the liquid inlet of the pyrolysis residue cooling equipment.

[0044] The inlet of the pyrolysis residue cooling equipment is connected to the outlet of the liquid-solid separation equipment, and its outlet is connected to the inlet of the pyrolysis residue storage system. Its inlet and outlet of the cooling medium are connected to the cooling medium supply system.

[0045] The feed inlet of the pyrolysis residue storage system is connected to the outlet of the pyrolysis residue cooling equipment.

[0046] This invention provides a method and apparatus for catalytic cracking of high-boiling organosilicon compounds capable of heterogeneous catalytic cracking, which has the following beneficial technical effects:

[0047] This invention employs a gas-liquid-solid three-phase flow slurry bed catalytic cracking system to catalytically crack high-boiling-point organosilicon compounds. It can realize the catalytic cracking of high-boiling-point organosilicon compounds using a supported organic amine-based heterogeneous catalyst. As can be seen from the characteristics of the slurry bed reactor, the material flows vigorously within the slurry bed catalytic cracking equipment, resulting in good mixing and contact between the high-boiling-point organosilicon compounds, catalyst, and reaction gas, and strong heat and mass transfer, which enables the reaction to proceed rapidly and thoroughly, significantly improving the catalytic cracking effect of high-boiling-point organosilicon compounds. Furthermore, the catalyst used has good catalytic effect, which also promotes the cracking effect of high-boiling-point organosilicon compounds.

[0048] Meanwhile, the catalyst used is a supported organic amine-based heterogeneous catalyst. The catalyst is immiscible with the reactants and is solid, which effectively reduces or even avoids catalyst loss, reduces catalyst consumption, improves catalyst efficiency, and reduces catalyst cost. Attached Figure Description

[0049] Figure 1 Flowchart of a heterogeneous catalytic cracking process for high-boiling-point organosilicon compounds

[0050] Figure 2 Schematic diagram of a heterogeneous catalytic cracking device for high-boiling-point organosilicon compounds

[0051] 1: Catalyst supply system; 1-1: Outlet; 2: Hydrogen chloride supply system; 2-1: Gas outlet; 3: Inert gas supply system; 3-1: Gas outlet; 4: Hydrogen chloride pump; 4-1: Inlet; 4-2: Outlet; 5: Inert gas pump; 5-1: Inlet; 5-2: Outlet; 6: Organosilicon high-boiling-point system; 6-1: Outlet; 7: Organosilicon high-boiling-point preheating equipment; 7-1: Inlet; 7-2: Outlet; 7-3: Medium inlet; 7-4: Medium outlet; 8: Organosilicon high-boiling-point pump; 8-1: Inlet; 8-2: Outlet; 9: Slurry bed catalytic cracking equipment; 9A : Heating system; 9-1: Catalyst inlet; 9-2: Gas inlet; 9-3: High-boiling-point organosilicon inlet; 9-4: Gas outlet; 9-5: Liquid-solid feed inlet; 9-6: Bottom liquid inlet; 9-7: Crack bottom feed outlet; 9-8: Heating medium inlet; 9-9: Heating medium outlet; 10: Separation and purification equipment; 10-1: Gas inlet; 10-2: Feed outlet; 10-3: Gas outlet; 11: Purification equipment; 11-1: Feed inlet; 11-2: Gas outlet; 11-3: Product outlet; 11-4: Bottom liquid outlet; 11-5: Cooling medium inlet; 11-6: Cooling medium outlet; 11-7: 11-8: Heating medium outlet; 12: Tail gas treatment equipment; 12-1: Gas inlet; 12-2: Gas outlet; 13: High-purity organosilicon monomer storage system; 13-1: Feed inlet; 14: Liquid-solid separation equipment; 14-1: Feed inlet; 14-2: Catalyst outlet; 14-3: Liquid outlet; 15: Pyrolysis residue cooling equipment; 15-1: Liquid inlet; 15-2: Liquid outlet; 15-3: Cooling medium inlet; 15-4: Cooling medium outlet; 16: Pyrolysis residue storage system; 16-1: Feed inlet; a: Catalyst; b: Hydrogen chloride; c: Fluidized reaction gas; d: Inert gas Gas; e: Low-temperature high-boiling-point organosilicon feedstock; f: High-temperature high-boiling-point organosilicon; g: Gaseous pyrolysis product; h: Clean gaseous pyrolysis product; i: Carrier; j: Non-condensable gas; k: Tail gas; l: High-purity organosilicon monomer; m: Purification base liquid; n: Pyrolysis base material; o: Catalyst in residual liquid; p: Pyrolysis residual liquid; q: Low-temperature pyrolysis residual liquid; r: Catalyst in residual liquid; s: High-temperature heating medium; t: Low-temperature heating medium; u: High-temperature heating medium; v: Low-temperature heating medium; w: Low-temperature cooling medium; x: High-temperature cooling medium; y: Low-temperature cooling medium; z: High-temperature cooling medium; α: High-temperature heating medium; β: Low-temperature heating medium Detailed Implementation

[0052] This invention discloses a method and apparatus for heterogeneous catalytic cracking of high-boiling-point organosilicon compounds. Those skilled in the art can refer to the content of this document and appropriately modify the process parameters to achieve the desired result. It should be particularly noted that all similar substitutions and modifications are obvious to those skilled in the art and are considered to be included within the scope of this invention. The method and application of this invention have been described through preferred embodiments. Those skilled in the art can clearly modify or appropriately change and combine the methods and applications described herein without departing from the content, spirit, and scope of this invention to realize and apply the technology of this invention.

[0053] The present invention will be further illustrated below with reference to the embodiments: Specific Implementation Example 1

[0055] This embodiment uses a 0.025 mm supported organic amine heterogeneous catalyst to catalytically crack a high-boiling organosilicon with a boiling point of 90 °C and a cracking temperature of 250 °C to obtain methylchlorosilane as an example to illustrate the process in detail.

[0056] The process flow and equipment used in this embodiment are as follows: Figure 1 and Figure 2 As shown.

[0057] The equipment used mainly includes a catalyst supply system 1, a hydrogen chloride supply system 2, an inert gas supply system 3, a hydrogen chloride supply pump 4, an inert gas supply pump 5, an organosilicon high-boiling-point substance supply system 6, an organosilicon high-boiling-point substance preheating equipment 7, an organosilicon high-boiling-point substance pump 8, a slurry bed catalytic cracking equipment 9, a separation and purification equipment 10, a purification equipment 11, a tail gas treatment equipment 12, a high-purity organosilicon monomer storage system 13, a liquid-solid separation equipment 14, a cracking residue cooling equipment 15, and a cracking residue storage system 16.

[0058] The catalyst supply system 1 mainly provides the catalyst used for the catalytic cracking of high-boiling organosilicon compounds. Its outlet 1-1 is connected to the catalyst inlet 9-1 of the slurry bed catalytic cracking equipment 9 and the catalyst outlet 14-2 of the liquid-solid separation equipment 14.

[0059] The hydrogen chloride supply system 2 is for supplying hydrogen chloride gas as the reaction gas used in the catalytic cracking of organosilicon high-boiling substances, and its outlet 2-1 is connected to the inlet 4-1 of the hydrogen chloride supply pump 4.

[0060] If the inert gas supply system 3 is to replenish fluidizing gas, its outlet 3-1 is connected to the inlet 5-1 of the inert gas supply pump 5.

[0061] The hydrogen chloride pump 4 is mainly used to transport hydrogen chloride gas. It is a centrifugal blower. Its inlet 4-1 is connected to the outlet 2-1 of the hydrogen chloride supply system 2, and its outlet 4-2 is connected to the inlet 9-2 of the slurry bed catalytic cracking equipment 9.

[0062] The inert gas pump 5 is mainly used to transport inert gas. It is a centrifugal blower. Its inlet 5-1 is connected to the outlet 3-1 of the inert gas supply system 3, and its outlet 5-2 is connected to the inlet 9-2 of the slurry bed catalytic cracking equipment 9.

[0063] The organosilicon high-boiling-point system 6 mainly provides organosilicon high-boiling-point raw materials, and its outlet 6-1 is connected to the inlet 7-1 of the organosilicon high-boiling-point preheating equipment 7.

[0064] The organosilicon high-boiling-point preheating equipment 7 is mainly used to preheat organosilicon high-boiling-point raw materials. Its inlet 7-1 is connected to the outlet 6-1 of the organosilicon high-boiling-point supply system 6, its outlet 7-2 is connected to the inlet 8-1 of the organosilicon high-boiling-point pump 8, and its inlet 7-3 and outlet 7-4 are connected to the heating medium supply system.

[0065] The high-boiling-point pump 8 for organosilicon is mainly used to transport high-boiling-point organosilicon. It is a plunger-type feed pump. Its inlet 8-1 is connected to the outlet 7-2 of the high-boiling-point organosilicon preheating equipment 7, and its inlet 8-2 is connected to the high-boiling-point organosilicon inlet 9-3 of the slurry bed catalytic cracking equipment 9.

[0066] The slurry-bed catalytic cracking unit 9 is used for the catalytic cracking of high-boiling-point organosilicon compounds. It is a slurry-bed reactor equipped with a heating system 9A, which is an outer jacket heating system used to provide the heat required for the catalytic cracking of high-boiling-point organosilicon compounds. Its catalyst inlet 9-1 is connected to the outlet 1-1 of the catalyst supply system 1 and the catalyst outlet 14-2 of the liquid-solid separation device 14; its gas inlet 9-2 is connected to the outlet 4-2 of the hydrogen chloride pump 4 and the outlet 5-2 of the inert gas pump 5; its organosilicon high-boiling-point inlet 9-3 is connected to the outlet 8-2 of the organosilicon high-boiling-point pump 8; its gas outlet 9-4 is connected to the gas inlet 10-1 of the separation and purification device 10; its liquid-solid material inlet 9-5 is connected to the outlet 10-2 of the separation and purification device 10; its bottom liquid inlet 9-6 is connected to the bottom liquid outlet 11-4 of the purification device 11; its bottom material outlet 9-7 is connected to the inlet 14-1 of the liquid-solid separation device 14; and its medium inlet 9-8 and medium outlet 9-9 are connected to the heating medium supply system.

[0067] The separation and purification equipment 10 is mainly used to remove the carry-on substances from the gaseous pyrolysis products, purify the gaseous pyrolysis products, and recover the carry-on substances. It is a settling chamber separation device. Its air inlet 10-1 is connected to the air outlet 9-4 of the slurry bed catalytic cracking equipment 9, its material outlet 10-2 is connected to the liquid-solid inlet 9-5 of the slurry bed catalytic cracking equipment 9, and its air outlet 10-3 is connected to the material inlet 11-1 of the purification equipment 11.

[0068] Purification equipment 11 is mainly used to purify organosilicon monomers produced by the cracking of high-boiling organosilicon compounds to obtain high-purity organosilicon monomer products. It is a tray distillation column.

[0069] The inlet 11-1 of the purification equipment 11 is connected to the outlet 10-3 of the separation and purification equipment 10, the outlet 11-2 of the purification equipment 11 is connected to the inlet 12-1 of the tail gas treatment equipment 12, the product outlet 11-2 of the purification equipment 11 is connected to the inlet 13-1 of the organosilicon monomer storage system 13, the bottom liquid outlet 11-4 of the purification equipment 11 is connected to the bottom liquid outlet 9-6 of the slurry bed catalytic cracking equipment 9, the cooling medium inlet 11-5 and the cooling medium outlet 11-6 of the purification equipment 11 are connected to the cooling medium supply system, and the heating medium inlet 17-7 and the heating medium outlet 11-8 of the heating medium supply system are connected to the heating medium supply system.

[0070] The exhaust gas treatment device 12 is mainly used to treat exhaust gas so that it can meet emission standards. Its inlet 12-1 is connected to the outlet 11-2 of the purification device 11, and its outlet 12-2 is directly connected to the atmosphere.

[0071] The high-purity organosilicon monomer storage system 12 is mainly used to store organosilicon monomer products, and its inlet 13-1 is connected to the product outlet 11-3 of the purification equipment 11.

[0072] The liquid-solid separation device 14 is mainly used to separate the pyrolysis feedstock produced by the slurry bed catalytic cracking device 9 in order to recover the catalyst stored therein. Its inlet 14-1 is connected to the pyrolysis feedstock outlet 11-7 of the slurry bed catalytic cracking device 9, its catalyst outlet 14-2 is connected to the outlet 1-1 of the catalyst supply system 1 and the catalyst inlet 11-1 of the slurry bed catalytic cracking device 9, and its liquid outlet 14-3 is connected to the liquid inlet 15-1 of the pyrolysis residue cooling device 15.

[0073] The inlet 15-1 of the pyrolysis residue cooling device 15 is connected to the outlet 14-3 of the liquid-solid separation device 14, and its outlet 15-2 is connected to the inlet 16-1 of the pyrolysis residue storage system 16. Its inlet cooling medium 15-3 and outlet cooling medium 15-4 are connected to the cooling medium supply system.

[0074] The feed inlet 16-1 of the pyrolysis residue storage system 16 is connected to the outlet 15-2 of the pyrolysis residue cooling device 15.

[0075] The specific process flow of this embodiment is as follows:

[0076] 50 kg of catalyst a with a particle size of 0.025 mm is added to the slurry bed catalytic cracking device 9 from the catalyst supply system 1; then, hydrogen chloride gas b is supplied from the hydrogen chloride supply system 2 at a rate of 2.5 kg / h (gas velocity of 0.025 m / s in the slurry bed catalytic cracking device 9) through the bottom of the slurry bed catalytic cracking device 9 using the hydrogen chloride supply pump 4. This hydrogen chloride gas b serves as the reaction fluidizing gas c for both the reaction gas and the fluidizing gas. This gas volume is sufficient to fluidize the material, eliminating the need to add inert gas.

[0077] Simultaneously, high-boiling-point organosilicon raw material e is supplied to the high-boiling-point organosilicon preheater 7 at a feed rate of -125 kg / h from the high-boiling-point organosilicon supply system 6. The high-boiling-point organosilicon raw material e exchanges heat with the high-temperature heating medium (heat transfer oil at 280°C) u and is preheated to a high-temperature high-boiling-point organosilicon f at 90°C. After heat exchange, the high-temperature heating medium u becomes a low-temperature heating medium v ​​at 120°C, which is then recycled after treatment. Then, the high-temperature high-boiling-point organosilicon f is pumped into the slurry bed catalytic cracking equipment 9 using the high-boiling-point organosilicon pump 8. The high-temperature high-boiling-point organosilicon f and the catalyst added to the slurry bed catalytic cracking equipment 9 are fully fluidized and mixed under the action of the fluidizing reaction gas c to form a fluidized slurry, thereby achieving full mixing and contact.

[0078] Simultaneously with feeding, a high-temperature heating medium s (heat transfer oil at 320°C) is supplied to the heating system 9A of the slurry bed catalytic cracking equipment 9. The high-temperature organosilicon high-boiling-point substance f exchanges heat with the high-temperature heating medium s and is heated to 250°C. Under the action of the catalyst, it undergoes a cracking reaction to generate gaseous cracked product g and a small amount of cracking residue. The high-temperature heating medium s after heat exchange becomes a low-temperature heating medium t at 270°C and is discharged from the heating system 9A of the slurry bed catalytic cracking equipment 9. After treatment, it is reused.

[0079] The gaseous pyrolysis product g is discharged from the top of the slurry bed catalytic cracking device 9 and enters the gaseous pyrolysis product purification device 10, where a small amount of carried matter i [mainly liquid residues (containing cracking feedstock and cracking products) and solid catalyst] is removed from the gaseous pyrolysis product to obtain clean gaseous pyrolysis product h.

[0080] The removed carrier material i is returned to the slurry bed catalytic cracking unit 9, where the liquid residue is pyrolyzed again to increase the pyrolysis rate, and the catalyst is returned for reuse.

[0081] The clean gaseous pyrolysis product h enters the purification equipment 11 for purification. Inside the purification equipment 11, the gaseous pyrolysis product flows upwards with the equipment and undergoes heat and mass exchange with the liquid coming from above, resulting in purification. The purified gas, in the form of lighter components with lower boiling points, exits from the top of the purification equipment and enters the top condenser where it exchanges heat with the low-temperature cooling medium y (-20℃ heat transfer oil) to cool and liquefy it into a high-purity organosilicon monomer l (methylchlorosilane) with a purity of 99.99% at a temperature of 6℃, and non-liquefiable non-condensable gas j (a small amount of hydrogen chloride gas and a small amount of nitrogen gas). After heat exchange, the low-temperature cooling medium y becomes the high-temperature cooling medium z (0℃ heat transfer oil), which is then treated and reused.

[0082] The non-condensable gas j generated in the purification equipment 11 is fed into the tail gas treatment equipment 12 for treatment. The treated gas that meets the standards is discharged as tail gas k (mainly nitrogen).

[0083] The 114.5 kg / h high-purity organosilicon monomer l (methylchlorosilane) l generated in the purification equipment 11 is transported to the high-purity organosilicon monomer storage system 13 for recycling as organosilicon monomer products, with a yield of 90% for methylchlorosilane.

[0084] The liquid flowing down from the purification device 11 enters the bottom of the purification device 11, and then enters the reboiler of the purification device 11. It is vaporized by heat exchange with the high-temperature heating medium α (40℃ heat transfer oil) and re-enters the purification device 11 for further separation. The components with lower boiling points are extracted, while the components with higher boiling points that no longer vaporize are discharged from the bottom of the purification device 11 as purification residue m and are transported back to the slurry bed catalytic cracking device 9 for further cracking. The high-temperature heating medium α after heat exchange becomes a low-temperature heating medium β at a temperature of 25℃, which is then treated and reused.

[0085] After the high-boiling-point organosilicon compounds in the slurry bed catalytic cracking equipment 9 undergo sufficient catalytic cracking, most of the components are converted into gaseous cracking products and discharged from the top. A small amount of cracking residue that cannot be further catalytically cracked or that still has a high boiling point, as well as the catalyst in the residue, are discharged from the bottom of the slurry bed catalytic cracking equipment 9 in the form of cracking bottom material n.

[0086] The pyrolysis substrate n discharged from the bottom of the slurry bed catalytic cracking unit 9 is transported to the liquid-solid separation unit 14 to separate and remove the catalyst o in the residual liquid. The separated catalyst o in the residual liquid is returned to the slurry bed catalytic cracking unit 9 for reuse. The pyrolysis residual liquid p after the catalyst is removed is discharged from the liquid-solid separation unit 14.

[0087] When the catalyst returned from the separation and purification equipment 10 and the liquid-solid separation equipment 14 is lost due to wear, carryover and other reasons, the amount of catalyst in the slurry bed catalytic cracking equipment will gradually become insufficient. Fresh catalyst r will be supplied from the catalyst supply system 1 at a feeding rate of 5 kg / h to replenish it. The catalyst loss rate is 10%.

[0088] The pyrolysis residue p discharged from the liquid-solid separation device 14 is introduced into the pyrolysis residue cooling device 15 and cooled into low-temperature pyrolysis residue q by exchanging heat with the low-temperature cooling medium w (25℃ heat transfer oil). The low-temperature cooling medium w becomes high-temperature cooling medium x (40℃ heat transfer oil). The low-temperature pyrolysis residue q obtained after cooling is introduced into the pyrolysis residue storage system 16 for collection and centralized treatment. The high-temperature cooling medium x is recycled after treatment.

[0089] This embodiment demonstrates that a gas-liquid-solid three-phase flow slurry bed catalytic cracking system can be used to catalytically crack high-boiling-point organosilicon compounds. This system utilizes a supported organic amine-based heterogeneous catalyst to catalytically crack high-boiling-point organosilicon compounds. After catalytic cracking, 90% of the high-boiling-point organosilicon compounds can be converted into high-purity organosilicon monomers (methylchlorosilane) with a purity of 99.99%, which is 10 percentage points higher than the approximately 80% conversion rate of traditional technologies. The catalytic cracking effect is significantly improved.

[0090] Meanwhile, the catalyst used is a supported organic amine-based heterogeneous catalyst. The catalyst is immiscible with the reactants and is solid, which effectively reduces or even avoids catalyst loss. The catalyst loss rate is 10%, which is about 10 percentage points lower than the loss rate of about 20% in traditional technology. This reduces catalyst loss, improves catalyst efficiency, and lowers catalyst cost. Specific Implementation Example 2

[0092] This embodiment uses a 0.05 mm supported organic amine heterogeneous catalyst to catalytically crack a high-boiling organosilicon with a boiling point of 90 °C and a cracking temperature of 250 °C to obtain methylchlorosilane as an example to illustrate the process in detail.

[0093] The process flow and equipment used in this embodiment are as follows: Figure 1 and Figure 2 As shown.

[0094] The equipment used mainly includes a catalyst supply system 1, a hydrogen chloride supply system 2, an inert gas supply system 3, a hydrogen chloride supply pump 4, an inert gas supply pump 5, an organosilicon high-boiling-point substance supply system 6, an organosilicon high-boiling-point substance preheating equipment 7, an organosilicon high-boiling-point substance pump 8, a slurry bed catalytic cracking equipment 9, a separation and purification equipment 10, a purification equipment 11, a tail gas treatment equipment 12, a high-purity organosilicon monomer storage system 13, a liquid-solid separation equipment 14, a cracking residue cooling equipment 15, and a cracking residue storage system 16.

[0095] The catalyst supply system 1 mainly provides the catalyst used for the catalytic cracking of high-boiling organosilicon compounds. Its outlet 1-1 is connected to the catalyst inlet 9-1 of the slurry bed catalytic cracking equipment 9 and the catalyst outlet 14-2 of the liquid-solid separation equipment 14.

[0096] The hydrogen chloride supply system 2 is for supplying hydrogen chloride gas as the reaction gas used in the catalytic cracking of organosilicon high-boiling substances, and its outlet 2-1 is connected to the inlet 4-1 of the hydrogen chloride supply pump 4.

[0097] If the inert gas supply system 3 is to replenish fluidizing gas, its outlet 3-1 is connected to the inlet 5-1 of the inert gas supply pump 5.

[0098] The hydrogen chloride pump 4 is mainly used to transport hydrogen chloride gas. It is a centrifugal blower. Its inlet 4-1 is connected to the outlet 2-1 of the hydrogen chloride supply system 2, and its outlet 4-2 is connected to the inlet 9-2 of the slurry bed catalytic cracking equipment 9.

[0099] The inert gas pump 5 is mainly used to transport inert gas. It is a Roots blower. Its inlet 5-1 is connected to the outlet 3-1 of the inert gas supply system 3, and its outlet 5-2 is connected to the inlet 9-2 of the slurry bed catalytic cracking equipment 9.

[0100] The organosilicon high-boiling-point system 6 mainly provides organosilicon high-boiling-point raw materials, and its outlet 6-1 is connected to the inlet 7-1 of the organosilicon high-boiling-point preheating equipment 7.

[0101] The organosilicon high-boiling-point preheating equipment 7 is mainly used to preheat organosilicon high-boiling-point raw materials. Its inlet 7-1 is connected to the outlet 6-1 of the organosilicon high-boiling-point supply system 6, its outlet 7-2 is connected to the inlet 8-1 of the organosilicon high-boiling-point pump 8, and its inlet 7-3 and outlet 7-4 are connected to the heating medium supply system.

[0102] The high-boiling-point pump 8 for organosilicon is mainly used to transport high-boiling-point organosilicon. It is a plunger-type feed pump. Its inlet 8-1 is connected to the outlet 7-2 of the high-boiling-point organosilicon preheating equipment 7, and its inlet 8-2 is connected to the high-boiling-point organosilicon inlet 9-3 of the slurry bed catalytic cracking equipment 9.

[0103] The slurry-bed catalytic cracking unit 9 is used for the catalytic cracking of high-boiling-point organosilicon compounds. It is a slurry-bed reactor equipped with a heating system 9A, which is a built-in coil heating system used to provide the heat required for the catalytic cracking of high-boiling-point organosilicon compounds. Its catalyst inlet 9-1 is connected to the outlet 1-1 of the catalyst supply system 1 and the catalyst outlet 14-2 of the liquid-solid separation device 14; its gas inlet 9-2 is connected to the outlet 4-2 of the hydrogen chloride pump 4 and the outlet 5-2 of the inert gas pump 5; its organosilicon high-boiling-point inlet 9-3 is connected to the outlet 8-2 of the organosilicon high-boiling-point pump 8; its gas outlet 9-4 is connected to the gas inlet 10-1 of the separation and purification device 10; its liquid-solid material inlet 9-5 is connected to the outlet 10-2 of the separation and purification device 10; its bottom liquid inlet 9-6 is connected to the bottom liquid outlet 11-4 of the purification device 11; its bottom material outlet 9-7 is connected to the inlet 14-1 of the liquid-solid separation device 14; and its medium inlet 9-8 and medium outlet 9-9 are connected to the heating medium supply system.

[0104] The separation and purification equipment 10 is mainly used to remove the carry-on substances from the gaseous pyrolysis products, purify the gaseous pyrolysis products, and recover the carry-on substances. It is a cyclone separator. Its air inlet 10-1 is connected to the air outlet 9-4 of the slurry bed catalytic cracking equipment 9, its material outlet 10-2 is connected to the liquid-solid inlet 9-5 of the slurry bed catalytic cracking equipment 9, and its air outlet 10-3 is connected to the material inlet 11-1 of the purification equipment 11.

[0105] Purification equipment 11 is mainly used to purify organosilicon monomers produced by the cracking of high-boiling-point organosilicon compounds to obtain high-purity organosilicon monomer products. It is a packed distillation column.

[0106] The inlet 11-1 of the purification equipment 11 is connected to the outlet 10-3 of the separation and purification equipment 10, the outlet 11-2 of the purification equipment 11 is connected to the inlet 12-1 of the tail gas treatment equipment 12, the product outlet 11-2 of the purification equipment 11 is connected to the inlet 13-1 of the organosilicon monomer storage system 13, the bottom liquid outlet 11-4 of the purification equipment 11 is connected to the bottom liquid outlet 9-6 of the slurry bed catalytic cracking equipment 9, the cooling medium inlet 11-5 and the cooling medium outlet 11-6 of the purification equipment 11 are connected to the cooling medium supply system, and the heating medium inlet 17-7 and the heating medium outlet 11-8 of the heating medium supply system are connected to the heating medium supply system.

[0107] The exhaust gas treatment device 12 is mainly used to treat exhaust gas so that it can meet emission standards. Its inlet 12-1 is connected to the outlet 11-2 of the purification device 11, and its outlet 12-2 is directly connected to the atmosphere.

[0108] The high-purity organosilicon monomer storage system 12 is mainly used to store organosilicon monomer products, and its inlet 13-1 is connected to the product outlet 11-3 of the purification equipment 11.

[0109] The liquid-solid separation device 14 is mainly used to separate the pyrolysis feedstock produced by the slurry bed catalytic cracking device 9 in order to recover the catalyst stored therein. Its inlet 14-1 is connected to the pyrolysis feedstock outlet 11-7 of the slurry bed catalytic cracking device 9, its catalyst outlet 14-2 is connected to the outlet 1-1 of the catalyst supply system 1 and the catalyst inlet 11-1 of the slurry bed catalytic cracking device 9, and its liquid outlet 14-3 is connected to the liquid inlet 15-1 of the pyrolysis residue cooling device 15.

[0110] The inlet 15-1 of the pyrolysis residue cooling device 15 is connected to the outlet 14-3 of the liquid-solid separation device 14, and its outlet 15-2 is connected to the inlet 16-1 of the pyrolysis residue storage system 16. Its inlet cooling medium 15-3 and outlet cooling medium 15-4 are connected to the cooling medium supply system.

[0111] The feed inlet 16-1 of the pyrolysis residue storage system 16 is connected to the outlet 15-2 of the pyrolysis residue cooling device 15.

[0112] The specific process flow of this embodiment is as follows:

[0113] 50 kg of catalyst a with a particle size of 0.05 mm is added to the slurry bed catalytic cracking device 9 from the catalyst supply system 1. Then, hydrogen chloride gas b is supplied from the hydrogen chloride supply system 2 at a rate of 2.5 kg / h (gas velocity of 0.01 m / s in the slurry bed catalytic cracking device 9) through the bottom of the slurry bed catalytic cracking device 9 using the hydrogen chloride supply pump 4. This hydrogen chloride gas is used as the reaction gas and fluidizing gas c. Since the catalyst particle size is relatively large, hydrogen chloride gas alone cannot fluidize the liquid. In order to fluidize the material, an inert gas needs to be added. The inert gas used is nitrogen. An inert gas d (nitrogen) is supplied to the slurry bed catalytic cracking device 9 at a certain rate to make the gas velocity in the slurry bed catalytic cracking device 9 reach 0.06 m / s.

[0114] Simultaneously, high-boiling-point organosilicon raw material e is supplied to the high-boiling-point organosilicon preheater 7 at a feeding rate of 125 kg / h from the high-boiling-point organosilicon supply system 6. The high-boiling-point organosilicon raw material e exchanges heat with the high-temperature heating medium (heat transfer oil at 280°C) u and is preheated to a high-temperature high-boiling-point organosilicon f at 90°C. After heat exchange, the high-temperature heating medium u becomes a low-temperature heating medium v ​​at 120°C, which is then recycled after treatment. Then, the high-temperature high-boiling-point organosilicon f is pumped into the slurry bed catalytic cracking device 9 using the high-boiling-point organosilicon pump 8. The high-temperature high-boiling-point organosilicon f and the catalyst added to the slurry bed catalytic cracking device 9 are fully fluidized and mixed under the action of the fluidizing reaction gas c to form a fluidized slurry, thereby achieving sufficient mixing and contact.

[0115] Simultaneously with feeding, a high-temperature heating medium s (heat transfer oil at 320°C) is supplied to the heating system 9A of the slurry bed catalytic cracking equipment 9. The high-temperature organosilicon high-boiling-point substance f exchanges heat with the high-temperature heating medium s and is heated to 250°C. Under the action of the catalyst, it undergoes a cracking reaction to generate gaseous cracked product g and a small amount of cracking residue. The high-temperature heating medium s after heat exchange becomes a low-temperature heating medium t at 270°C and is discharged from the heating system 9A of the slurry bed catalytic cracking equipment 9. After treatment, it is reused.

[0116] The gaseous pyrolysis product g is discharged from the top of the slurry bed catalytic cracking device 9 and enters the gaseous pyrolysis product purification device 10, where a small amount of carried matter i [mainly liquid residues (containing cracking feedstock and cracking products) and solid catalyst] is removed from the gaseous pyrolysis product to obtain clean gaseous pyrolysis product h.

[0117] The removed carrier material i is returned to the slurry bed catalytic cracking unit 9, where the liquid residue is pyrolyzed again to increase the pyrolysis rate, and the catalyst is returned for reuse.

[0118] The clean gaseous pyrolysis product h enters the purification equipment 11 for purification. Inside the purification equipment 11, the gaseous pyrolysis product flows upwards with the equipment and undergoes heat and mass exchange with the liquid coming from above, resulting in purification. The purified gas, in the form of lighter components with lower boiling points, exits from the top of the purification equipment and enters the top condenser where it exchanges heat with the low-temperature cooling medium y (-20℃ heat transfer oil) to cool and liquefy it into a high-purity organosilicon monomer l (methylchlorosilane) with a purity of 99.99% at a temperature of 6℃, and non-liquefiable non-condensable gas j (a small amount of hydrogen chloride gas and a small amount of nitrogen gas). After heat exchange, the low-temperature cooling medium y becomes the high-temperature cooling medium z (0℃ heat transfer oil), which is then treated and reused.

[0119] The non-condensable gas j generated in the purification equipment 11 is fed into the tail gas treatment equipment 12 for treatment. The treated gas that meets the standards is discharged as tail gas k (mainly nitrogen).

[0120] The 112.2 kg / h high-purity organosilicon monomer l (methylchlorosilane) l generated in the purification equipment 11 is transported to the high-purity organosilicon monomer storage system 13 as organosilicon monomer product for recycling, and the yield of methylchlorosilane is 88%.

[0121] The liquid flowing down from the purification device 11 enters the bottom of the purification device 11, and then enters the reboiler of the purification device 11. It is vaporized by heat exchange with the high-temperature heating medium α (40℃ heat transfer oil) and re-enters the purification device 11 for further separation. The components with lower boiling points are extracted, while the components with higher boiling points that no longer vaporize are discharged from the bottom of the purification device 11 as purification residue m and are transported back to the slurry bed catalytic cracking device 9 for further cracking. The high-temperature heating medium α after heat exchange becomes a low-temperature heating medium β at a temperature of 25℃, which is then treated and reused.

[0122] After the high-boiling-point organosilicon compounds in the slurry bed catalytic cracking equipment 9 undergo sufficient catalytic cracking, most of the components are converted into gaseous cracking products and discharged from the top. A small amount of cracking residue that cannot be further catalytically cracked or that still has a high boiling point, as well as the catalyst in the residue, are discharged from the bottom of the slurry bed catalytic cracking equipment 9 in the form of cracking bottom material n.

[0123] The pyrolysis substrate n discharged from the bottom of the slurry bed catalytic cracking unit 9 is transported to the liquid-solid separation unit 14 to separate and remove the catalyst o in the residual liquid. The separated catalyst o in the residual liquid is returned to the slurry bed catalytic cracking unit 9 for reuse. The pyrolysis residual liquid p after the catalyst is removed is discharged from the liquid-solid separation unit 14.

[0124] When the catalyst returned from the separation and purification equipment 10 and the liquid-solid separation equipment 14 is lost due to wear, carryover and other reasons, the amount of catalyst in the slurry bed catalytic cracking equipment will gradually become insufficient. Fresh catalyst r is supplied from the catalyst supply system 1 at a feeding rate of 2.5 kg / h to replenish it. The catalyst loss rate is 5%.

[0125] The pyrolysis residue p discharged from the liquid-solid separation device 14 is introduced into the pyrolysis residue cooling device 15 and cooled into low-temperature pyrolysis residue q by exchanging heat with the low-temperature cooling medium w (25℃ heat transfer oil). The low-temperature cooling medium w becomes high-temperature cooling medium x (40℃ heat transfer oil). The low-temperature pyrolysis residue q obtained after cooling is introduced into the pyrolysis residue storage system 16 for collection and centralized treatment. The high-temperature cooling medium x is recycled after treatment.

[0126] Compared with Example 1, this example also demonstrates the catalytic cracking of high-boiling-point organosilicon compounds using a gas-liquid-solid three-phase flow slurry bed catalytic cracking system. It realizes the catalytic cracking of high-boiling-point organosilicon compounds using a supported organic amine heterogeneous catalyst. After catalytic cracking, 90% of the high-boiling-point organosilicon compounds can be converted into high-purity organosilicon monomers (methylchlorosilane) with a purity of 99.99%, which is 8 percentage points higher than the conversion rate of about 80% in the traditional technology, and the catalytic cracking effect is significantly improved.

[0127] Meanwhile, the catalyst used is a supported organic amine-based heterogeneous catalyst. The catalyst is immiscible with the reactants and is solid, which effectively reduces or even avoids catalyst loss. The catalyst loss rate is 5%, which is about 15 percentage points lower than the loss rate of about 20% in traditional technology. This reduces catalyst loss, improves catalyst efficiency, and lowers catalyst cost.

[0128] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A method for catalytic cracking of high-boiling-point organosilicon compounds capable of heterogeneous catalytic cracking, wherein the method uses a supported organic amine-based heterogeneous catalyst as the catalyst and employs a gas-liquid-solid three-phase flow slurry bed catalytic cracking system to catalytically crack high-boiling-point organosilicon compounds to obtain catalytic cracking products rich in low-boiling-point organosilicon monomers. These products are purified to obtain high-purity organosilicon monomers, thereby achieving the harmless and resource-based treatment and utilization of high-boiling-point organosilicon compounds. The specific process flow is as follows: A catalyst of a specific particle size is added to the slurry-bed catalytic cracking unit from the catalyst supply system. Then, hydrogen chloride gas is supplied from the hydrogen chloride supply system at a certain gas velocity through the bottom of the slurry-bed catalytic cracking unit via a hydrogen chloride supply pump. This hydrogen chloride gas serves as the reaction fluidizing gas, acting as both the reaction gas and the fluidizing gas. If the amount of hydrogen chloride gas is sufficient for the reaction but insufficient to fluidize the material in the slurry bed catalytic cracking unit, a certain amount of inert gas is supplied to the slurry bed catalytic cracking unit from the inert gas supply system via an inert gas pump. Simultaneously, high-boiling-point organosilicon raw materials are supplied to the high-boiling-point organosilicon preheater at a certain flow rate from the high-boiling-point organosilicon supply system. The high-boiling-point organosilicon raw materials are preheated into high-temperature high-boiling-point organosilicon by exchanging heat with the high-temperature heating medium. After heat exchange, the high-temperature heating medium becomes a low-temperature heating medium, which is then treated and reused. Then, the high-temperature high-boiling-point organosilicon is pumped into the slurry bed catalytic cracking equipment using an organosilicon pump. The high-temperature high-boiling-point organosilicon and catalyst added to the slurry bed catalytic cracking equipment are fully fluidized and mixed under the action of fluidizing reaction gas to form a fluidized slurry, thereby achieving full mixing and contact. While feeding, a high-temperature heating medium is supplied to the heating system of the slurry bed catalytic cracking equipment. The high-temperature organosilicon high-boiling-point substance exchanges heat with the high-temperature heating medium and is heated to the temperature required for catalytic cracking. Under the action of the catalyst, it undergoes a cracking reaction to generate gaseous cracked products and a small amount of cracking residue. The high-temperature heating medium after heat exchange becomes a low-temperature heating medium and is discharged from the heating system of the slurry bed catalytic cracking equipment. After treatment, it is reused. The gaseous pyrolysis product is discharged from the top of the slurry bed catalytic cracking equipment and enters the gaseous pyrolysis product purification equipment to remove the small amount of solid catalyst and liquid residues composed of cracking feedstock and cracking products in the gaseous pyrolysis product, so as to obtain clean gaseous pyrolysis product; The removed material is returned to the slurry bed catalytic cracking unit, where the liquid residue is pyrolyzed again to increase the pyrolysis rate, and the catalyst is returned for reuse. Clean gaseous pyrolysis products enter the purification equipment for purification. The gaseous pyrolysis products flow upward in the purification equipment and are purified by heat and mass exchange with the liquid coming from the top. The purified gas is discharged from the top of the purification equipment in the form of light components with lower boiling points. Then it enters the top condenser of the tower and is cooled and liquefied by exchanging heat with the low temperature cooling medium. It is then liquefied into high-purity organosilicon monomers and non-liquefiable non-condensable gases in liquid form. After heat exchange, the low temperature cooling medium becomes a high temperature cooling medium and is reused after treatment. The non-condensable gas generated in the purification equipment is passed into the tail gas treatment equipment for treatment, and the treated gas that meets the standards is discharged as tail gas. The high-purity organosilicon monomers generated in the purification equipment are transported to the high-purity organosilicon monomer storage system for recycling as organosilicon monomer products. The liquid flowing down from the purification equipment enters the bottom of the purification equipment, and then enters the reboiler of the purification equipment. The high-temperature heating medium is heated and vaporized, and the liquid is then re-entered into the purification equipment for further separation. The components with lower boiling points are extracted, while the components with higher boiling points that no longer vaporize are discharged from the bottom of the purification equipment as purification residue and are transported back to the slurry bed catalytic cracking equipment for further cracking. The high-temperature heating medium after heat exchange becomes a low-temperature heating medium and is reused after treatment. After the high-boiling-point organosilicon compounds in the slurry bed catalytic cracking equipment undergo sufficient catalytic cracking, most of the components are converted into gaseous cracking products and discharged from the top. A small amount of cracking residue that cannot be further catalytically cracked or that still has a high boiling point, as well as the catalyst in the residue, are discharged from the bottom of the slurry bed catalytic cracking equipment in the form of cracking bottom material. The pyrolysis feedstock discharged from the bottom of the slurry bed catalytic cracking unit is transported to a liquid-solid separation unit to separate and remove the catalyst from the residual liquid. The separated catalyst in the residual liquid is returned to the slurry bed catalytic cracking unit for reuse, while the pyrolysis residual liquid after catalyst removal is discharged from the liquid-solid separation unit. When the amount of catalyst in the slurry bed catalytic cracking equipment is insufficient due to the loss of catalyst returned from the separation and purification equipment and the liquid-solid separation equipment, fresh catalyst is supplied from the catalyst supply system to replenish it; The pyrolysis residue discharged from the liquid-solid separation equipment is passed into the pyrolysis residue cooling equipment and cooled into low-temperature pyrolysis residue by exchanging heat with the low-temperature cooling medium. The low-temperature cooling medium becomes a high-temperature cooling medium. After cooling, the low-temperature pyrolysis residue is passed into the pyrolysis residue storage system for collection and centralized processing. The high-temperature cooling medium is treated and then reused.

2. The method for catalytic cracking of high-boiling organosilicon compounds capable of heterogeneous catalytic cracking according to claim 1, characterized in that, This method uses a solid-supported organic amine-based heterogeneous catalyst and a gas-liquid-solid three-phase flow slurry bed catalytic cracking system to catalytically crack high-boiling-point organosilicon compounds to obtain catalytic cracking products rich in low-boiling-point organosilicon monomers. These products are then purified to obtain high-purity organosilicon monomers, thereby achieving the harmless and resource-based treatment and utilization of high-boiling-point organosilicon compounds.

3. The method for catalytic cracking of high-boiling organosilicon compounds capable of heterogeneous catalytic cracking according to claim 1, characterized in that, The temperature of the high-boiling-point organosilicon compound added to the slurry bed catalytic cracking unit should be as high as possible, ensuring that it does not exceed the boiling point and cracking temperature of the organosilicon compound, so as to form a low-viscosity organosilicon compound liquid, which is beneficial to its good fluidity and fluidization in the slurry bed catalytic cracking unit.

4. The method for catalytic cracking of high-boiling organosilicon compounds capable of heterogeneous catalytic cracking according to claim 1, characterized in that, Supported organic amine heterogeneous catalysts are heterogeneous solid catalysts that are immiscible with the reactants. Their hydrodynamic properties are basically the same as those of high-boiling organosilicon compounds, that is, the minimum fluidization rate and entrainment gas rate of the catalyst and the high-boiling organosilicon compounds are the same.

5. The method for catalytic cracking of high-boiling-point organosilicon compounds capable of heterogeneous catalytic cracking according to claim 1, characterized in that, The reaction fluidizing gas serves not only as the reaction gas but also as the fluidizing gas used to fluidize the material in the slurry bed catalytic cracking unit. Its gas velocity is between the minimum fluidizing gas velocity and the entrained gas velocity of the material in the slurry bed catalytic cracking unit. The reaction fluidizing gas is hydrogen chloride. If there is insufficient hydrogen chloride, an inert gas is introduced to supplement it. The inert gas is a cracking non-condensable gas composed of low-boiling-point components rich in silane, disilane and monochlorosilane generated during the catalytic cracking of organosilicon high-boiling-point substances, or a newly added non-reactive gas that does not react with organosilicon high-boiling-point substances and all materials including cracking products, catalysts and hydrogen chloride, or a mixture of cracking non-condensable gas and newly added gas.

6. The method for catalytic cracking of high-boiling-point organosilicon compounds capable of heterogeneous catalytic cracking according to claim 1, characterized in that, The purification of gaseous pyrolysis products is carried out by pressure swing adsorption or distillation.

7. An apparatus for realizing a method for heterogeneous catalytic cracking of organosilicon high-boiling-point substances, the apparatus comprising a catalyst supply system, a hydrogen chloride supply system, an inert gas supply system, a hydrogen chloride supply pump, an inert gas supply pump, an organosilicon high-boiling-point substance supply system, an organosilicon high-boiling-point substance preheating equipment, an organosilicon high-boiling-point substance supply pump, a slurry bed catalytic cracking equipment, a separation and purification equipment, a purification equipment, a tail gas treatment equipment, a high-purity organosilicon monomer storage system, a liquid-solid separation equipment, a cracking residue cooling equipment, and a cracking residue storage system; The catalyst supply system provides the catalyst for the catalytic cracking of high-boiling-point organosilicon compounds. Its outlet is connected to the catalyst inlet of the slurry bed catalytic cracking equipment and the catalyst outlet of the liquid-solid separation equipment. The hydrogen chloride supply system is to provide hydrogen chloride gas as the reaction gas used for the catalytic cracking of high-boiling organosilicon compounds, and its outlet is connected to the inlet of the hydrogen chloride supply pump. If the inert gas supply system is to be supplemented with fluidizing gas, its outlet is connected to the inlet of the inert gas supply pump. The hydrogen chloride pump is used to transport hydrogen chloride gas. Its inlet is connected to the outlet of the hydrogen chloride supply system, and its outlet is connected to the inlet of the slurry bed catalytic cracking equipment. An inert gas pump is used to transport inert gas. Its inlet is connected to the outlet of the inert gas supply system, and its outlet is connected to the inlet of the slurry bed catalytic cracking equipment. The organosilicon high-boiling-point system is used to provide organosilicon high-boiling-point raw materials, and its outlet is connected to the inlet of the organosilicon high-boiling-point preheating equipment. The organosilicon high-boiling-point preheating equipment is used to preheat organosilicon high-boiling-point raw materials. Its inlet is connected to the outlet of the organosilicon high-boiling-point system, its outlet is connected to the inlet of the organosilicon high-boiling-point pump, and its inlet and outlet are connected to the heating medium system. A pump for supplying high-boiling-point organosilicon is used to transport high-boiling-point organosilicon. Its inlet is connected to the outlet of the high-boiling-point organosilicon preheating equipment, and its inlet is connected to the inlet of the high-boiling-point organosilicon in the slurry bed catalytic cracking equipment. Slurry bed catalytic cracking equipment is used for the catalytic cracking of high-boiling-point organosilicon compounds. It is a slurry bed reactor equipped with a heating system to provide the heat required for the catalytic cracking of high-boiling-point organosilicon compounds. Its catalyst inlet is connected to the outlet of the catalyst supply system and the catalyst outlet of the liquid-solid separation equipment; its gas inlet is connected to the gas outlet of the hydrogen chloride pump and the gas outlet of the inert gas pump; its organosilicon high-boiling-point inlet is connected to the outlet of the organosilicon high-boiling-point pump; its gas outlet is connected to the gas inlet of the separation and purification equipment; its liquid-solid material inlet is connected to the outlet of the separation and purification equipment; its bottom liquid inlet is connected to the bottom liquid outlet of the purification equipment; its bottom material outlet is connected to the inlet of the liquid-solid separation equipment; and its medium inlet and medium outlet are connected to the heating medium supply system. Separation and purification equipment is used to remove the carriers from gaseous pyrolysis products, purify the gaseous pyrolysis products, and recover the carriers therein. The air inlet of the separation and purification equipment is connected to the air outlet of the slurry bed catalytic cracking equipment, its outlet is connected to the liquid-solid feed inlet of the slurry bed catalytic cracking equipment, and its air outlet is connected to the feed inlet of the purification equipment. Purification equipment is used to purify organosilicon monomers produced by the cracking of high-boiling-point organosilicon compounds in order to obtain high-purity organosilicon monomer products. It can be a pressure swing adsorption device or a distillation device. The inlet of the purification equipment is connected to the outlet of the separation and purification equipment, the outlet of the purification equipment is connected to the inlet of the tail gas treatment equipment, the product outlet of the purification equipment is connected to the inlet of the organosilicon monomer storage system, the bottom liquid outlet of the purification equipment is connected to the bottom liquid outlet of the slurry bed catalytic cracking equipment, the inlet and outlet of the cooling medium are connected to the cooling medium supply system, and the inlet and outlet of the heating medium are connected to the heating medium supply system. The exhaust gas treatment equipment is used to treat exhaust gas so that it can meet emission standards. Its inlet is connected to the outlet of the purification equipment, and its outlet is directly open to the atmosphere. The high-purity organosilicon monomer storage system is used to store organosilicon monomer products, and its inlet is connected to the product outlet of the purification equipment. Liquid-solid separation equipment is used to separate the pyrolysis feedstock produced by slurry bed catalytic cracking equipment in order to recover the catalyst stored therein; The feed inlet of the liquid-solid separation equipment is connected to the pyrolysis bottom material outlet of the slurry bed catalytic cracking equipment, its catalyst outlet is connected to the outlet of the catalyst supply system and the catalyst inlet of the slurry bed catalytic cracking equipment, and its liquid outlet is connected to the liquid inlet of the pyrolysis residue cooling equipment. The inlet of the pyrolysis residue cooling equipment is connected to the outlet of the liquid-solid separation equipment, its outlet is connected to the inlet of the pyrolysis residue storage system, and its inlet and outlet of the cooling medium are connected to the cooling medium supply system. The feed inlet of the pyrolysis residue storage system is connected to the outlet of the pyrolysis residue cooling equipment.

8. The apparatus for the catalytic cracking method of organosilicon high-boiling compounds capable of heterogeneous catalytic cracking according to claim 7, characterized in that, This device is used for the catalytic cracking of high-boiling-point organosilicon compounds and to purify the gaseous cracking products to obtain high-purity organosilicon monomer products. It includes a slurry-bed catalytic cracking device for cracking high-boiling-point organosilicon compounds, a purification device for purifying the gaseous cracking products to obtain high-purity organosilicon monomer products, and supporting auxiliary equipment.

9. The apparatus for the catalytic cracking method of organosilicon high-boiling compounds capable of heterogeneous catalytic cracking according to claim 7, characterized in that, The slurry bed catalytic cracking equipment is used for the catalytic cracking of high-boiling organosilicon compounds. This equipment is a gas-liquid-solid multiphase flow slurry bed reactor.

10. The apparatus for the catalytic cracking method of organosilicon high-boiling compounds capable of heterogeneous catalytic cracking according to claim 7, characterized in that, Purification equipment is used to purify the gaseous pyrolysis products produced by the cracking of high-boiling-point organosilicon compounds, thereby obtaining high-purity organosilicon monomer products. It can be a pressure swing adsorption device or a distillation device.

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