TWI658001B - Catalyst for promoting silane reaction generation and full process byproduct recovery system - Google Patents

Abstract

A catalyst enhances the silane reaction generation and the full recovery of by-products in the process. Among them: the newly developed separation and purification system and technology are used to separate the silane mixture generated from the reaction and the solid raw materials participating in the reaction. Silane is separated from gas mixture by low temperature gas-liquid according to its physical characteristics, and the silanol fractionation system is used to recover ammonia raw material in silane and purify silane and remove its impurities. The ethane and ammonia feedstocks are also fractionated and purified by a ethane distillation system. In conjunction with the developed unique catalyst use technology, the silane conversion rate is improved, and new feeding methods and developed equipment are implemented. It is used again as a reaction raw material, thereby stabilizing the production capacity and purification process of silicon methane and silicon.

Description

Catalyst for promoting silane reaction generation and full process byproduct recovery system

The present invention relates to a silane process system, in particular to a system for promoting silane reaction generation and full recovery of process by-products with catalyst

According to the silicon-magnesium alloy method, which is one of the known industrial processes, a synthetic method for producing special semiconductor gas materials such as silicon methane and silicon oxide. It is known to use the silicon-magnesium alloy method for the production of silane, and its reaction with silicon. The selection rate is too low, and with the advancement and cost reduction of high-purity silane production technology, and the environmental impact caused by the storage of reaction slag and complicated and energy-intensive processing procedures, the silane-magnesium alloy method is used to produce silane. The manufacturing process is difficult to meet the economic benefits. Due to this deficiency, the improved silicon-magnesium alloy method has been gradually developed, and the selectivity, yield and purity of the silane reaction production have been improved, but the disposal of the reaction slag is still an obstacle to this silane production method, and There are still many technical related problems in the production process. For example, silane is oxidized to produce silicon dioxide particles or crystals due to the operating conditions of the process and the environment, which leads to a decrease in equipment efficiency and production efficiency and an increase in the frequency of disassembly and maintenance. Therefore, the author intends to design and develop advanced production technology and equipment systems to make up for and improve the defects in the technology and process of producing silane by using the improved silicon-magnesium alloy method, and then develop into a perfect high-purity silane production method and system.

In view of this, the present inventors have engaged in the manufacturing, development and design of related products for many years. After careful design and careful evaluation of the above-mentioned goals, they finally have a practical invention.

The technical problem to be solved by the present invention is to provide a system for improving the silane reaction generation and the full recovery of by-products of the process in response to the above-mentioned defects existing in the prior art.

A silane reaction system includes a magnesium silicide powder suction barrel, an magnesium silicide automatic feeding device, a jacketed reaction tank, a condenser, and an air pump. The magnesium silicide powder suction barrel stores magnesium silicide and contact in an oxygen-free state. And the mixing ratio of the catalyst is 15% to 30% of magnesium silicide, and the catalyst is composed of 20 ~ 50wt% silicon powder and 50 ~ 80wt% metal powder to form a bimetal composite, and the magnesium silicide automatically The feeding device is connected between the magnesium silicide suction bucket and the jacketed reaction tank, and the jacketed reaction tank is equipped with a stirrer, and the top of the jacketed reaction tank is connected to the condenser and connected to the bottom end. The pneumatic pump and the jacketed reaction tank are first charged with ammonium chloride powder, and the sealed nitrogen replacement and vacuum deoxidation operations are performed. After the introduction of pure ammonia, the -30 ° C refrigerant is condensed to form liquid ammonia, and the mixer is started. Pre-dissolution of ammonium chloride and liquid ammonia is performed, and magnesium silicide and catalyst are fed into the jacketed reaction tank at a fixed rate by the magnesium silicide automatic feeding device, thereby triggering the reaction to generate a mixture of silicic acid and hydrogen and pass through The condenser output is supplemented by a heat medium at 90 ° C The reacted liquid ammonia and silicon are cooked by the condenser and recovered through the condenser, and the reacted slag is discharged by the pneumatic pump and stored in a slag buffer tank. A gas-liquid separation tank is connected to the condenser, and the The upper end of the gas-liquid separation tank is connected with a temporary silanol tank for storing vaporized silicon methane, and the gas-liquid separation tank is connected with a temporary silanol tank for storing liquefied silicon and liquid ammonia. The alkane distillation system includes a desiliconization tower, an ammonia purification tower, and a silicon purification tower. The temporary storage tank is connected to the desiliconization tower, and the upper end of the desiliconization tower is connected to the ammonia purification tower. And the lower end of the desiliconizer tower is connected to the ethane purification tower, the desiliconizer tower separates ammonia into the ammonia purification tower at a pressure of 18 to 24 kg / cm ² and a temperature of 25 ° C to 70 ° C, and silicon Ethane is separated into the silane purification tower, and the ammonia purification tower separates a small amount of silane from the temperature difference and returns to the silane temporary storage tank, and the silane purification tower further purifies the silicon at a temperature of 30 ° C to 100 ° C. Ethane, and store the purified silicon in a liquefied silicon buffer tank Alkoxy the reaction selectivity can reach 5 ~ 25vol%, and the ammonia is separated with the silicon oxide purification column purified liquid ammonia to an ammonia storage column buffer tank.

Among them, the condenser is sequentially connected with a second condenser and a third condenser, and preliminary silane separation is performed by using the physical characteristics of different substances at different boiling points. The condenser is sequentially introduced into the first condenser at a constant pressure of 2 to 7 kg / cm ² . The second condenser is condensed at -30 ° C and the third condenser is condensed at -75 ° C to form liquid silicon and liquefied ammonia, as well as gaseous silicon methane and hydrogen, and separated in the gas-liquid separation tank.

Wherein, a filter is installed between the condenser and the second condenser. Due to the mixture of silicon methane generated in the reaction process of the jacketed reaction tank and the ammonia and ethane distilled out after the reaction, it will be accompanied by A small amount of raw material or slag powder carried by the differential pressure airflow uses this filter to intercept particles larger than 3 to 100 μm.

Among them, the silicon stored in the liquefied silicon buffer tank can reach a purity of 4N8 (99.998%). When the silicon is filled with silicon, the silicon can be liquefied by low-temperature vacuum condensation at -75 ℃. The silicon buffer tank is filled in at least one steel cylinder, and the same vacuum condensation technology can also be used to purify small amounts of silicon and remove trace impurities.

Among them, the silicide temporary storage tank is connected with a silicide fractionation system, the silicide fractionation system includes a silicide recovery tower, a silicide molecular sieve, and a silicide purification tower. And the silicic acid molecular sieve is connected to the silicic acid purification tower. The silicic acid recovery tower stores most of the ammonia in the liquid ammonia buffer tank at a pressure of 8 to 15 kg / cm ² and a changing temperature of -60 ° C to 40 ° C. The fractionated silicon dioxide gas and a small amount of ammonia are then adsorbed and removed by the 3A-5A silicon dioxide molecular sieve to remove ammonia and other impurities. The silicon dioxide is then introduced into the silicon dioxide purification tower and the temperature is -160 ° C to -50 ° C. The hydrogen contained is removed and separated, and the purified silicon methane is stored in a liquefied silicon methane buffer tank.

Among them, the liquefied silicic acid buffer tank has a purity of 6N (99.9999%), and the liquefied silicic acid buffer tank adopts an inner and outer double-layer structure. The liquefied silicic acid is stored in the inner layer, and the outer layer is in a vacuum. A ring-shaped coil is arranged around the coil. The ring-shaped coil is used to circulate the temperature control and pressure control of the refrigerant up to -50 ° C. When it is needed, the refrigerant is used as the condensate of the silicic acid, and the liquefied silicic acid buffer bucket Connected with a vaporizer, when silicic acid is filled, the silicic acid is introduced into the vaporizer and controlled to a stable flow with -30 ° C refrigerant to a finished product pressor, and the product pressurizer is pressurized to 100 ~ Silica is filled into at least one cylinder or at least one tanker at a pressure of 160 kg / cm ² .

Wherein, the slag buffer tank is sequentially connected with a centrifugal filter, an ammonia solution buffer tank, a magnesium hydroxide filter and an ammonia buffer tank in series, and the centrifugal filter and the magnesium hydroxide filter are connected at the same time to a dry state. A grinding device, and a high-pressure forming brick making system is connected to the drying grinding device. The slag discharged into the slag buffer tank is added with water and stirred in the jacketed reaction tank to partially convert it into insoluble magnesium hydroxide. The solid powder and the salt products dissolved therein, and the slurry-like slag is flowed into the centrifugal filter under the uninterrupted stirring of the slag buffer tank, and the centrifugal filter is used to spin off the liquid to make the slag The liquid part flows to the ammonia solution buffer tank, and the solid part is discharged to the drying and milling device, and the drying and milling device uses electric heating and spiral stirring to perform heating and drying of the solid slag and ammonia release, and discharges to the The high-pressure forming brick making system is used as the raw material for making bricks, and ammonia water is added to the ammonia solution buffer tank, so that the magnesium chloride in the solution can react to form ammonium chloride and magnesium hydroxide powder, and then pass through the hydrogen. Magnesium filters in 1 ~ 30μm precision of magnesium hydroxide particles and excreted into the mill drying apparatus to prevent solid particles from entering the ammonia buffer Flush the bucket and store only ammonia water in the ammonia buffer bucket.

The ammonia buffer tank is connected to an ammonia separation and recovery system. The ammonia separation recovery system is connected to the ammonia buffer tank by an ammonia recovery tower, and an ammonia rectification tower is connected to the upper end of the ammonia recovery tower. Separation of ammonium chloride solution and ammonia solution from a pressure of ~ 5kg / cm ² and a temperature of 50 ° C to 145 ° C, so that the ammonia solution is discharged from the top of the ammonia recovery tower to the ammonia rectification tower, and Purification and separation of ammonia and water in the distillation column at a temperature of -30 ° C to 130 ° C, and the purified ammonia at the top of the ammonia rectification tower is stored in an ammonia raw material barrel for recycling, and the ammonia rectification tower is in the tower The bottom separated water and a small amount of ammonia are returned to the ammonia buffer tank, and the ammonia recovery tower is sent from the ammonium chloride solution separated from the bottom of the tower to a multi-effect evaporation system, and passes through the multi-effect evaporation system at 120 ° C to 160 ° C. The steam is heated to vaporize the ammonium chloride solution to remove the ammonium chloride. The moisture content of the ammonium chloride can be lower than 1% by weight, and it is recovered by a dryer as a reaction in the jacketed reaction tank. The raw material is used, and the water vapor is recovered in a recycled water buffer tank to provide the jacket The reaction tank is used as a residue solvent after the reaction.

Wherein, after the slag is evacuated, the jacketed reaction tank is purged with nitrogen, evacuated, and heated at a temperature of 90 ° C to perform cleaning and effective moisture removal in the jacketed reaction tank to avoid moisture. Affect the oxidation reaction of silane generated in the next reaction process with water in alkaline environment to form silicon dioxide, thereby improving the silane reaction rate.

Among them, the process equipment of the full silane reaction process is assembled by a plurality of exhaust gas exhaust lines to connect an exhaust gas treatment system. The exhaust gas treatment system includes a washing tower, a high-temperature oxidizer, and a filtering device. The composition containing ammonia and silane gas is shunted to each stage of the tail gas treatment system. The scrubbing tower removes ammonia gas with water, and then introduces the formed ammonia water into the ammonia solution buffer tank for recovery and chlorination. Additives for the conversion of ammonium salts, A small amount of tail gas is discharged from the top of the tower to the high-temperature oxidizer to destroy the silane gas, so that it is converted into a non-hazardous substance of silicon dioxide, which is then intercepted and collected by the filtering equipment of the tail gas treatment system.

The first main objective of the present invention is to use an improved silicon-magnesium alloy method for the silane production method, cooperate with the developed unique catalyst use technology to improve the conversion rate of siloxane, and implement a new feeding method and developed equipment to Promote the reaction rate of raw materials and reduce the impact of the reaction system on the problem of blockage of solid powders, and effectively control and optimize the environment for silane reaction production with improved production operation technology to increase the production capacity of silane.

The second main object of the present invention is to separate the silane gas mixture generated from the reaction and the solid raw materials participating in the reaction through a newly developed and designed separation and purification system and technology, and then carry out the silanol from the gas mixture according to its physical characteristics. Low-temperature gas-liquid separation, and use the silicic acid fractionation system to recover ammonia raw materials in silicic acid, and to purify silicic acid and remove its impurities, and then use low-temperature vacuum as storage of silicic acid. The silicon and ammonia raw materials are also fractionally purified by a silicon distillation system, and the ammonia is recovered for reuse as a reaction raw material, thereby stabilizing the production capacity and purification process of silicon methane and silicon, and can effectively reduce production. cost.

The third main object of the present invention is that after the silane reaction is completed, water is added as a solvent, so that a part of the content of the slag can be converted into a salt substance and dissolved in ammonia water, and can be pulped. The solid fluid is used for subsequent separation and recovery, and a newly designed separation method is adopted. The solid-liquid separation of the slurry residue is performed by centrifugal separation technology, and the separated solid product is dried as a raw material for making bricks. The liquid fluid is converted into a recoverable salt ammonia solution by adding ammonia, and then a distillation system is used to separate, purify and recover the ammonium chloride salt solution, ammonia and water. The ammonium chloride solution is then removed by a high-efficiency evaporation system. And drying, and recycling as raw materials for silane production reaction. This can effectively reduce the impact of slag storage on the environment and the cost of production costs.

The fourth main objective of the present invention is that the tail gas (waste) generated during the process is uniformly collected into the tail gas treatment system through the tail gas discharge pipeline, and the ammonia gas in the tail gas is removed by ammonia adsorption removal technology and recovered as a salt solution. The additive liquid is used, and other silane waste gas is treated by oxidation reaction in the tail gas treatment system to be converted into non-hazardous gas or slag for disposal to reduce environmental pollution and harm.

Other objects, advantages, and novel features of the present invention will become more apparent from the following detailed description and the accompanying drawings.

[This creation]

11‧‧‧ Silane reaction system

111‧‧‧Magnesium silicide powder bucket

112‧‧‧Magnesium silicide automatic feeding device

113‧‧‧ Jacketed reaction tank

114‧‧‧ condenser

115‧‧‧Pneumatic pump

116‧‧‧Blender

117‧‧‧Second condenser

118‧‧‧Third condenser

119‧‧‧Filter

12‧‧‧Gas-liquid separation tank

13‧‧‧Silicon distillation system

131‧‧‧Silicon tower

132‧‧‧Ammonia purification tower

133‧‧‧Silica purification tower

134‧‧‧Liquid ammonia buffer tank

14‧‧‧Slag buffer tank

15‧‧‧ Silane temporary storage tank

16‧‧‧ Liquefied Silicone Buffer Bucket

17‧‧‧ steel cylinder

21‧‧‧ Silane temporary storage tank

22‧‧‧Silicon methane fractionation system

221‧‧‧Silicon Methane Recovery Tower

222‧‧‧ Silane molecular sieve

223‧‧‧Silicon methane purification tower

23‧‧‧ Liquefied Silica Buffer Tank

231‧‧‧Vaporizer

232‧‧‧Ring body coil

24‧‧‧ Finished Press

25‧‧‧ Cylinder

26‧‧‧ Tank truck

31‧‧‧ Centrifugal Filter

32‧‧‧ ammonia buffer tank

33‧‧‧Magnesium hydroxide filter

34‧‧‧Ammonia buffer bucket

35‧‧‧Drying and grinding device

351‧‧‧High pressure forming brick making system

36‧‧‧Ammonia separation and recovery system

361‧‧‧Ammonia Recovery Tower

362‧‧‧Ammonia distillation column

37‧‧‧Ammonia raw material barrel

38‧‧‧Multi-effect evaporation system

381‧‧‧ dryer

39‧‧‧Recycled water buffer tank

41‧‧‧ tail gas exhaust pipeline

42‧‧‧Exhaust gas treatment system

421‧‧‧washing tower

422‧‧‧High temperature oxidizer

423‧‧‧filtration equipment

FIG. 1 is a structure and a flowchart of a process for producing silicon in accordance with the present invention.

Figure 2 is the structure and flow chart of the process of silicon methane of the present invention.

FIG. 3 is a schematic structural diagram of a liquefied silicon methane buffer tank of the present invention.

FIG. 4 is a structure and flowchart of the slag recovery process of the present invention.

Figure 5 is the structure and flowchart of the exhaust gas recovery process of the present invention.

In order for your reviewers to have a better understanding and understanding of the purpose, features and effects of the present invention, the following is to be accompanied by the [Simplified Description of the Drawings], as detailed below: Please first observe from Figure 1, a touch The system promotes silane reaction generation and full recovery of process by-products, including: a silane reaction system 11, a gas-liquid separation tank 12, and a silane distillation system 13. The silane reaction system 11 includes a magnesium silicide powder A barrel 111, an automatic magnesium silicide feeding device 112, a jacketed reaction tank 113, a condenser 114, and a pneumatic pump 115. The magnesium silicide suction barrel 111 stores magnesium silicide (Mg ₂ Si) and oxygen in an oxygen-free state. The catalyst is anaerobic and is evacuated and replaced with nitrogen after filling and sealing. The mixing ratio of the catalyst is 15% to 30% of magnesium silicide, and the catalyst is composed of 20-50% by weight of silicon powder ( Si) and 50 ~ 80wt% of metal powder to form a bimetal composite. The metal powder can use alkali metal group and alkaline earth metal group metal elements, and can also use metal elements in transition metals, such as iron (Fe), Or alloys such as elements in the IIIA ~ ⅥA group, and the magnesium silicide An automatic feeding device 112 is connected between the magnesium silicide powder suction barrel 111 and the jacketed reaction tank 113, and the jacketed reaction tank 113 is provided with a mixer 116, and the top of the jacketed reaction tank 113 is connected The condenser 114 is connected to the bottom end of the pneumatic pump 115, and the jacketed reaction tank 113 is first charged with ammonium chloride (NH ₄ Cl) powder, and performs closed nitrogen replacement and vacuum deoxidation, and then introduces pure ammonia ( NH ₃ ), then control the condensation of -30 ° C refrigerant to form liquid ammonia, and start the mixer 116 to pre-dissolve ammonium chloride and liquid ammonia, dissolve ammonium chloride in liquid ammonia to form ammonia and chloride salt ions, and maintain The agitator 116 is continuously operated until the clearance of the tank after the reaction is completed, to avoid uneven dispersion of the powder during the reaction or to block due to solidification and agglomeration due to the reaction, and the magnesium silicide automatic feeding device 112 is used at a fixed rate. Magnesium silicide and catalyst are put into the jacketed reaction tank 113, that is, magnesium silicide and catalyst powder are fed at a fixed rate of 0 ~ 150kg / h, and a little liquid ammonia with stable flow control is used as the carrier fluid. Reaction with ammonium chloride in jacketed reaction tank 113 Therefore, it can prevent the magnesium silicide powder from splashing when it comes into contact with the liquid ammonia in the tank, and the powder adheres to the pipeline or the tank wall gradually causes the pipeline to be blocked. The process of generating silane is an exothermic reaction, so it is a reaction process. The thermal energy must be continuously removed with a -30 ° C refrigerant in order to maintain the reaction temperature. During the reaction, liquid ammonia will also be vaporized by the thermal energy generated by the reaction and will flow out of the jacketed reaction with the generated silane. The tank 113 causes the reaction rate to decrease or terminates the reaction. In order to maintain the amount of liquid ammonia during the reaction, ammonia will be condensed through the condenser 114 at a -30 ° C refrigerant to liquefy and flow back to the jacket. The reaction tank 113 is used to trigger the reaction to generate a mixture of silicon methane (SiH4) and hydrogen (H ₂ ) and produce it through the condenser 114. Most of the produced silicon is similar to ammonia in terms of its physical characteristics. Therefore, it will be condensed by the condenser 114 and liquefied and returned to the jacketed reaction tank 113 again. Therefore, after the silane reaction ends, the liquid ammonia participating in the reaction and the silane contained therein must be recovered as much as possible. So conversion The refrigerant in the condenser 114 is heated to 90 ° C, so that the liquid ammonia and siloxane in the jacketed reaction tank 113 can be stably cooked and heated up and vaporized, thereby assisting the reaction liquid with the 90 ° C heating medium. Ammonia and silane (Si ₂ H ₆ ) are cooked and recovered through the condenser 114, wherein the proportion of the reaction raw materials is usually based on the weight of magnesium silicide, and is based on magnesium silicide 1: ammonium chloride 3 ~ 6: liquid The amount of ammonia is 9 ~ 12, and the reaction formula is as follows: The reaction formula of silicon dioxide is as follows (main reaction): Mg ₂ Si _(s) + 4NH ₄ Cl _(s) + 8NH _{3 (l)} → SiH _{4 (g)} +2 (MgCl ₂ ‧6NH ₃ ) _(s)

The silane reaction equation is as follows (side reaction): 2Mg ₂ Si _(s) + 8NH ₄ Cl _(s) + 16NH _{3 (l)} → Si ₂ H _{6 (g)} +4 (MgCl ₂ ‧6NH ₃ ) _(s) + H _{2 (g)}

The slag after the reaction is discharged from the pneumatic pump 115 and stored in a slag buffer tank 14, and the slag discharged into the slag buffer tank 14 is stirred with water before the jacketed reaction tank 113, so that part of the slag is converted into insoluble The magnesium hydroxide solid powder and the salt products dissolved therein. After the slag is evacuated, the jacketed reaction tank 113 is purged with nitrogen, evacuated, and heated at 90 ° C to perform the jacket. The reaction tank 113 is cleaned in the tank and effectively removes water to prevent water from affecting the silane generated during the next reaction and the oxidation reaction of water in an alkaline environment to form silicon dioxide, thereby improving the silane reaction rate. The separation tank 12 is connected to the condenser 114. The condenser 114 is sequentially connected with a second condenser 117 and a third condenser 118. The preliminary silane separation is performed by using the physical characteristics of the boiling point and temperature of each substance. A constant pressure of 7kg / cm ² is sequentially introduced into the second condenser 117 to condense at -30 ° C and the third condenser 118 to condense at -75 ° C, so that the silane can be prevented from being scattered in the gas phase and then with the gaseous state. Of silicon dioxide and hydrogen mixed in this gas-liquid separation equipment It is separated into liquid silicon and liquefied ammonia, and gaseous silicon methane and hydrogen. A filter 119 is installed between the condenser 114 and the second condenser 117. Since the jacketed reaction tank 113 is in the reaction process, The generated silicon dioxide gas mixture and the ammonia and ethane distilled out after the reaction are accompanied by a small amount of raw material or slag powder carried by the pressure difference air stream, and the filter 119 is used to intercept the powder larger than 3 ~ 100 μm. The upper end of the gas-liquid separation tank 12 is connected to a silicic acid temporary storage tank 21 for storing vaporized silicon methane, and the gas-liquid separation tank 12 is connected to a silicon for storage of liquefied silicon and liquid ammonia. Temporary storage tank 15, a siloxane distillation system 13 includes a desiliconization column 131, an ammonia purification column 132, and a siloxane purification column 133. The silane temporary storage tank 15 is connected to the desiliconization column. 131, the upper end of the desiliconizer tower 131 is connected to the ammonia purification tower 132, and the lower end of the desiliconizer tower 131 is connected to the silicon purification tower 133. The desiliconizer tower 131 is at a pressure of 18 to 24 kg / cm ² Ammonia is separated into the ammonia purification tower 132 at a temperature of 25 ° C to 70 ° C, and the amount of liquid ammonia separated is 58 ~ 67 wt%, at the same time, the silicon is separated into the silicon purification tower 133, and the ammonia purification tower 132 separates a small amount of silicon methane with a temperature difference and returns to the silicon methane temporary storage tank 21, and the silicon purification tower 133 is The temperature was further purified at a temperature of 30 ° C to 100 ° C, and the purified silicon was stored in a liquefied silicon buffer tank 16 so that the reaction selectivity of the silicon could reach 5 to 25 vol%. The ethane stored in the ethane buffer bucket 16 can reach a purity of 4N8 (99.998%). When the ethane is filled with silicon, the ethane can be buffered by the liquefied siloxane by low-temperature vacuum condensation at -75 ° C. The barrel 16 is filled into at least one steel cylinder 17, and the same vacuum condensation technology can be used to purify a small amount of silicon and remove trace impurities. The ammonia purification tower 132 and the silicon purification tower 133 are separated. The ammonia is stored in a liquid ammonia buffer tank 134, and the recovered ammonia is introduced into the jacketed reaction tank 113 for reuse through the liquid ammonia buffer tank 134, thereby effectively reducing its production cost.

The other branch of this project is for the purification of silicic acid. Please observe from Figure 2. The silicic acid temporary storage tank 21 is connected with a silicic acid fractionation system 22, which includes a silicic acid recovery tower. 221. A silicic acid molecular sieve 222 and a silicic acid purification tower 223. The upper end of the silicic acid recovery tower 221 is connected to the silicic acid molecular sieve 222, and the silicic acid molecular sieve 222 is connected to the silicic acid purification tower 223. The silicic acid recovery tower 221 Most of the ammonia is fractionated and stored in the liquid ammonia buffer tank 134 at a pressure of 8 to 15 kg / cm ² and a varying temperature of -60 ° C to 40 ° C. That is, the characteristics of ammonia as a relatively heavy substance are used. The bottom of the recovery tower 221 is produced and sent to the ammonia buffer tank 134 for recovery, and the separated silicon dioxide gas still contains a small amount of ammonia component of about 2-10% by weight, and the fractionated silicon dioxide gas and a small amount of Ammonia is then adsorbed and removed by the 3A ~ 5A silicon sieve molecular sieve 222 to remove ammonia and other impurities. The silicon sieve molecular sieve 222 can be heated to provide a re-used vacuum after vacuum switching to remove adsorbed substances. Alkoxy purification column 223 and hydrogen at a low temperature of -160 deg.] C to -50 ℃ contained in the removed separation, purification of silicon so that the liquefied methane is stored in a buffer tub 23 silicon methane. The liquefied silicic acid buffer bucket 23 has a purity of 6N (99.9999%), and the liquefied silicic acid buffer bucket 23 has an inner and outer double-layer structure (coordinated with FIG. 3), and the liquefied silicon is stored in the inner layer. Silane, and the outer layer is vacuum-shaped and is provided with a ring body coil 232, and the ring body coil 232 is used to circulate the temperature control and pressure control of the refrigerant to -50 ° C, and use the refrigerant as the methane when needed Condensation, and the liquefied silicic acid buffer tank 23 is connected with a vaporizer 231. When the silicic acid is filled, the silicic acid is introduced into the vaporizer 231 and controlled to a stable flow of -30 ° C refrigerant to a finished product pressor 24. And by using the finished product presser 24 to pressurize to a pressure of 100-160 kg / cm ² , the silylmethane is filled into at least one steel cylinder 25 or at least one tanker 26, thereby facilitating the filling and transportation.

Another line of this creation is to carry out the slag recovery operation, and then please observe it as shown in Figure 4. The slag buffer tank 14 is connected in series with a centrifugal filter 31, an ammonia solution buffer tank 32, and a magnesium hydroxide. A filter 33 and an ammonia buffer bucket 34, and the centrifugal filter 31 and the magnesium hydroxide filter 33 are connected to a dry milling device 35 at the same time, and a high pressure forming brick making system 351 is connected to the dry milling device 35, During the operation, the slag discharged into the slag buffer tank 14 is added with water in the jacketed reaction tank 113 and stirred, so that part of the slag is converted into insoluble magnesium hydroxide solid particles and the salt products dissolved therein. The slurry slag flows into the centrifugal filter 31 under the uninterrupted stirring of the slag buffer tank 14, so that the slag can react with water more effectively to generate soluble salts, so that the generated solid powder can be evenly distributed and Avoid sedimentation, and then use the spin-off solution of the centrifugal filter 31, that is, the centrifugal filter 31 performs de-liquidation at a speed of 300 to 1000 rpm, and intercepts solid powder with a filter material of 200 to 400 mesh. Allow the liquid portion of the slag to flow to the ammonia solution. Tank 32, and when the solid slag is formed into an appropriate thickness in the centrifugal filter 31, it is discharged to the dry milling device 35 by scraping, and the dry milling device 35 performs solid slag by electric heating and spiral stirring The heating drying and ammonia desorption are discharged to the high pressure forming brick making system 351 as raw materials for making bricks, and can also be directly used as fume desulfurization agent, and the ammonia solution buffer tank 32 is added with the recovered ammonia water. The magnesium chloride in the solution can be reacted to form ammonium chloride and magnesium hydroxide particles, and then the magnesium hydroxide particles are filtered through the magnesium hydroxide filter 33 with a precision of 1 to 30 μm and discharged to the dry milling device 35. The excretion method is to use nitrogen to blow off the particles from the centrifugal filter 31 and discharge the particles to the dry milling device 35 by its gravity to prevent solid particles from entering the ammonia buffer bucket 34. The ammonia water is stored in the ammonia buffer tank 34. An ammonia separation and recovery system 36 is connected to the ammonia buffer tank 34. The ammonia separation and recovery system 36 is connected to the ammonia buffer tank 34 via an ammonia recovery tower 361, and an ammonia rectification tower 362 is connected to the upper end of the ammonia recovery tower 361. The ammonia recovery tower 361 separates the ammonium chloride solution and the ammonia solution at a pressure of 0 to 5 kg / cm ² and a temperature of 50 ° C to 145 ° C. The concentration of the separated ammonia water is 10 to 30% by weight, which is a relatively light substance. The aqueous solution is discharged from the top of the ammonia recovery tower 361 to the ammonia rectification tower 362, and the ammonia and water are purified and separated in the ammonia rectification tower 362 at a temperature of -30 ° C to 130 ° C. It reaches an industrial grade purity level of 98% ~ 99%, and the purified ammonia at the top of the ammonia rectification tower 362 is stored in an ammonia raw material barrel 37 for recycling, and the water and A trace amount of ammonia is returned to the ammonia buffer tank 34, and the ammonia recovery tower 361 is sent from the ammonium chloride solution separated from the bottom of the tower to a multi-effect evaporation system 38. The steam is heated to make the ammonium chloride solution vaporize the water contained in it, and the ammonium chloride solution is removed. The water rate can be lower than 1% by weight, and is recovered by a dryer 381 as the reaction raw material of the jacketed reaction tank 113, and the water vapor is recovered by a recovered water buffer tank 39 to provide the jacketed reaction tank 113 for reaction After the residue solvent is used.

The tail (waste) gas recovery operation of this creation, and then please observe from Figure 5, the process equipment of the full silane reaction process is integrated by a plurality of tail gas discharge lines 41 to connect a tail gas treatment system 42, the tail gas treatment system 42 includes a washing tower 421, a high-temperature oxidizer 422, and a filtering device 423. The tail gas (waste gas) is divided into various stages of the tail gas treatment system 42 according to the composition containing ammonia and silane gas. The washing tower 421 uses water Adsorption and removal of ammonia gas, and then introducing the formed ammonia water into the ammonia solution buffer tank 32 for recovery and as an additive for the conversion of ammonium chloride salts, while a small amount of tail gas is discharged from the top of the tower to the high-temperature oxidizer 422 destroys silane gas and converts it into a non-hazardous substance of silicon dioxide. Then, it is intercepted and collected by the filtering equipment 423 of the exhaust gas treatment system 42 to effectively treat the exhaust gas and reduce the environmental pollution at low cost. .

To sum up, the present invention has indeed achieved a breakthrough structural design, with improved content of the invention, and at the same time, it can achieve industrial applicability and progress, and the present invention is not seen in any publications, and it is also novel. In accordance with the relevant provisions of the Patent Law, I filed an application for an invention patent in accordance with the law.

The above is only one of the preferred embodiments of the present invention. When it cannot be used to limit the scope of the present invention; that is, all equal changes and modifications made in accordance with the scope of the patent application for the present invention should still belong to the present invention. Within the scope of the patent.

Claims (9)

A catalyst-enhancing system for silane reaction generation and full recovery of process by-products, including: a silane reaction system, the silane reaction system includes a magnesium silicide powder suction barrel, an magnesium silicide automatic feeding device, and a jacket type A reaction tank, a condenser, and an air pump. The magnesium silicide powder bucket stores magnesium silicide and a catalyst in an oxygen-free state, and the mixing ratio of the catalyst is 15% to 30% of the magnesium silicide. 20 ~ 50wt% silicon powder and 50 ~ 80wt% metal powder constitute a bimetal composite, and the magnesium silicide automatic feeding device is connected between the magnesium silicide powder suction barrel and the jacketed reaction tank, and the clamp The jacketed reaction tank is equipped with a stirrer, the top of the jacketed reaction tank is connected to the condenser and the bottom is connected to the pneumatic pump, and the jacketed reaction tank is first charged with ammonium chloride powder and closed with nitrogen. And vacuum deoxidation operation, after the introduction of pure ammonia, the condensation of -30 ° C refrigerant is controlled to form liquid ammonia, and the stirrer is started to pre-dissolve ammonium chloride and liquid ammonia, and is input by the magnesium silicide automatic feeding device at a fixed rate Magnesium silicide and catalyst enter the jacket This type of reaction tank is used to trigger the reaction to generate a mixture of silicon methane and hydrogen and produce it through the condenser. In addition, the liquid ammonia after the reaction is assisted by heating at 90 ° C and the silicon are cooked and recovered through the condenser. The remaining slag is discharged by the pneumatic pump and stored in a slag buffer tank. After the slag is emptied, the jacketed reaction is carried out by nitrogen purging, vacuuming and heating at 90 ° C. The inside of the tank is cleaned and the water is effectively removed to prevent the water from affecting the silane generated during the next reaction and the oxidation reaction of water in an alkaline environment to form silicon dioxide, thereby improving the silane reaction rate; a gas-liquid separation tank, The gas-liquid separation tank is connected to the condenser, and an upper end of the gas-liquid separation tank is connected to a temporary silanol tank for storing vaporized silicon methane, and the gas-liquid separation tank is connected to a tank for storing liquefied silicon. A ethane temporary storage tank with liquid ammonia; and a siloxane distillation system including a desiliconizer tower, an ammonia purification tower, and a silane purification tower, the silane temporarily The storage tank is connected to the desilication tower, and the desilication The upper end of the alkane tower is connected to the ammonia purification tower, and the lower end of the desiliconizer tower is connected to the silicon purification tower. The desiliconizer tower separates ammonia at a pressure of 18 to 24 kg / cm ² and a temperature of 25 ° C to 70 ° C. To the ammonia purification tower, and the ethane is separated into the siloxane purification tower, and the ammonia purification tower separates a small amount of silicon methane with a temperature difference and returns to the silane temporary storage tank, and the silicon purification tower is at a temperature of 30 ℃ to 100 ℃ to further purify the silicon, and store the purified silicon in a liquefied silicon buffer tank, so that the reaction selectivity of silicon can reach 5-25 vol%, and the ammonia purification tower and the The ammonia separated by the silicon purification tower is stored in a liquid ammonia buffer tank, and the recovered ammonia is introduced into the jacketed reaction tank for repeated use through the liquid ammonia buffer tank, thereby effectively reducing its production cost. The system for promoting the silane reaction generation and the full recovery of by-products of the process according to item 1 of the scope of the patent application, wherein the condenser is sequentially connected with a second condenser and a third condenser, and uses the boiling point of each substance The physical properties of different temperatures are used for preliminary silane separation. The second condenser is sequentially introduced at a constant pressure of 2 to 7 kg / cm ^{2 to} condense at -30 ° C and the third condenser is condensed at -75 ° C to form a liquid. Silicone, liquefied ammonia, and gaseous silicon methane and hydrogen are separated in the gas-liquid separation tank. The catalyst promotes the silane reaction generation and the full recovery of by-products of the process according to item 2 of the scope of the patent application, wherein a filter is installed between the condenser and the second condenser. The silicon dioxide gas mixture generated in the reaction tank during the reaction process, and the ammonia and ethane that are boiled out after the reaction are accompanied by a small amount of raw material or slag powder carried by the differential pressure air stream, and the filter is used to intercept more than 3 ~ 100μm powder. The system for improving the silane reaction generation and the full recovery of the by-products of the process according to the catalyst described in item 1 of the scope of the patent application, wherein the silane stored in the liquefied siloxane buffer tank can reach a purity of 4N8 (99.998%) At the time of silicon filling demand, silicon can be filled into the at least one steel cylinder from the liquefied silicon buffer tank by vacuum low-temperature-75 ° C condensation, and a small amount of silicon can also be used with the same vacuum condensation technology. Purification of alkane and removal of trace impurities. The catalyst promotes the silane reaction generation and the full recovery of by-products of the process according to item 1 of the scope of the patent application, wherein the silane temporary storage tank is connected to a silane fractionation system, and the silane fractionation system includes a silane A recovery tower, a silyl methion sieve and a silyl methion purification tower. The upper end of the sil meth recovery tower is connected to the sil meth sieve, and the sil meth sieve is connected to the sil meth purification tower. The sil meth recovery tower has a pressure of 8 to 15 kg / cm ² and varying temperature -60 ° C ~ 40 ° C, most of the ammonia is fractionated and stored in the liquid ammonia buffer tank, and the fractionated silicon dioxide gas and a small amount of ammonia are adsorbed and removed by the 3A ~ 5A silicon methane molecular sieve. Gases such as impurities and other impurities are then introduced into the silanol purification tower and the hydrogen contained is removed and separated at a low temperature of -160 ° C to -50 ° C, so that the purified silane is stored in a liquefied silanol buffer tank. According to the catalyst described in item 5 of the scope of the patent application, a system for improving the silane reaction generation and the full recovery of by-products of the process, wherein the liquefied silicic acid buffer tank has a purity of 6N (99.9999%), and The liquefied silicon methane buffer tank adopts an inner and outer double-layer structure, and the liquefied silicon methane is stored in the inner layer. The outer layer is vacuum-shaped and is surrounded by a ring body coil. The ring body coil is used to circulate refrigerant to a temperature of -50 ° C. Control and pressure control, and use refrigerant as the condensation of silicic acid when needed, and the liquefied silicic acid buffer tank is connected with a vaporizer, and when silicic acid is filled, let silicic acid be introduced into the vaporizer and use -30 ℃ refrigerant The controlled flow is controlled and conveyed to a finished press, and the silyl methane is filled into at least one steel bottle or at least one tanker by pressurizing the finished press to a pressure of 100 to 160 kg / cm ² . According to the system described in item 1 of the patent application, the catalyst promotes the silane reaction generation and the process by-products full recovery system, wherein the slag buffer tank is sequentially connected with a centrifugal filter, an ammonia solution buffer tank, a hydrogen A magnesium oxide filter and an ammonia buffer bucket, and the centrifugal filter and the magnesium hydroxide filter are connected to a dry grinding device at the same time, and a high pressure forming brick making system is connected to the dry grinding device to discharge the slag. The slag in the buffer tank is added with water and stirred in the jacketed reaction tank to partially convert it into insoluble magnesium hydroxide solid particles and salt products dissolved therein, and under the continuous stirring of the slag buffer tank The slurry residue is poured into the centrifugal filter, and the spin-off liquid of the centrifugal filter is used to make the liquid portion of the residue flow to the ammonia solution buffer tank, and the solid portion is discharged to the dry milling device. The drying and pulverizing device uses electric heating and spiral stirring to perform heating drying of solid slag and ammonia detachment, and discharges them to the high-pressure forming brick making system as raw materials for making bricks. Ammonia is added, and the magnesium chloride in the solution can be reacted to form ammonium chloride and magnesium hydroxide particles, and then the magnesium hydroxide particles are filtered through the magnesium hydroxide filter with a precision of 1 to 30 μm and discharged to the dry milled powder. The device prevents solid particles from entering the ammonia buffer bucket, and only stores ammonia water in the ammonia buffer bucket. The system for promoting the silane reaction generation and the full recovery of by-products of the process according to item 7 of the scope of the patent application, wherein the ammonia buffer tank is connected with an ammonia separation and recovery system, and the ammonia separation and recovery system is connected by an ammonia recovery tower The ammonia buffer tank is connected with an ammonia rectification tower from the upper end of the ammonia recovery tower, and the ammonia recovery tower performs the ammonium chloride solution and the ammonia solution at a pressure of 0 to 5 kg / cm ² and a temperature of 50 to 145 ° C. Separate, discharge the ammonia solution from the top of the ammonia recovery tower to the ammonia rectification tower, and perform purification and separation of ammonia and water in the ammonia rectification tower at a temperature of -30 ° C to 130 ° C. Purified ammonia at the top of the distillation tower is stored in an ammonia raw material barrel for recycling, and the water and ammonia in the ammonia distillation tower separated at the bottom of the tower are returned to the ammonia buffer tank, and the ammonia recovery tower is separated at the bottom of the tower. The produced ammonium chloride solution is sent to a multi-effect evaporation system, and the multi-effect evaporation system is used to heat the steam at 120 ° C to 160 ° C, so that the water contained in the ammonium chloride solution is vaporized and the ammonium chloride is separated from the chloride. The water content of ammonium can be less than 1wt%, and it is supplied by a dryer The reaction yield as a raw material of the jacket type reaction vessel, and the water vapor recovered to a buffer tank supplies the recovered solvent using a jacketed reaction vessel after the reaction of the slag. The catalyst promotes the silane reaction generation and the full recovery of the by-products of the process according to item 1 of the scope of the patent application. Among them, the process equipment of the full silane reaction process is assembled and connected to a tail gas treatment system by a plurality of tail gas discharge lines. The tail gas treatment system includes a washing tower, a high-temperature oxidizer, and a filtering device, and the tail (waste) gas is divided into various stages of the tail gas treatment system according to a composition containing ammonia and silane gas. The washing tower performs ammonia with water. The gas is removed by adsorption, and the formed ammonia water is introduced into the ammonia solution buffer tank for recovery and used as an additive for the conversion of ammonium chloride salts. A small amount of tail gas is discharged from the top of the tower to the high-temperature oxidizer for silane gas. The damage caused by it will be converted into non-hazardous substances of silicon dioxide, which will be intercepted and collected by the filtering equipment of the exhaust gas treatment system.