TWI658001B - Catalyst for promoting silane reaction generation and full process byproduct recovery system - Google Patents
Catalyst for promoting silane reaction generation and full process byproduct recovery system Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
一種觸媒提升矽烷反應生成及其製程副產物全回收的系統,其中:本創作以新開發設計之分離純化系統和技術進行反應生成之矽烷混氣與參與反應之固體原物料的分離,再將矽甲烷由混氣中依其物理特性進行低溫氣液分離,並使用該矽甲烷分餾系統進行矽甲烷中氨原料的回收及矽甲烷的純化和其不純物的移除,而經氣液分離的矽乙烷和氨原料亦以矽乙烷蒸餾系統進行分餾純化,配合已開發的獨特觸媒使用技術進行矽乙烷轉化率的提升,及實施新的投料方式和開發的設備,並將氨回收以再次做為反應原料使用,藉此使矽甲烷及矽乙烷的產能和純化過程穩定。 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
本發明係有關於一種矽烷製程系統,尤指一種以觸媒提升矽烷反應生成及其製程副產物全回收的系統 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
按,矽鎂合金法為其中一種已知工業化製程,用於生產矽甲烷及矽乙烷等半導體特殊氣體原料的合成方法,習知使用矽鎂合金法進行矽烷的生產,其矽乙烷的反應選擇率過低、且隨高純度矽甲烷生產技術的精進及和成本降低,及反應渣料存置所造成之環境影響的問題和繁複且能源耗損大的處理程序,因此以矽鎂合金法生產矽烷的製程難以符合經濟效益。由此不足之處,改良的矽鎂合金法漸而發展,並提升矽乙烷反應生產上的選擇率、產量及純度,但其反應渣料的處置問題仍然為此矽烷生產方法之阻礙,且生產製程上依然有許多技術相關問題的衍生,如矽烷因製程過程的操作條件及環境而氧化反應生成二氧化矽粉粒或結晶,導致設備效能和生產效率的降低及拆清保養頻率增加。因此本創作欲設計開發的進階生產技術及設備系統,彌補及完善採用改良的矽鎂合金法用於生產矽烷技術及製程上的缺陷,進而發展為完善的高純度矽烷生產方法及系統。 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.
有鑑於此,本發明人於多年從事相關產品之製造開發與設計經驗,針對上述之目標,詳加設計與審慎評估後,終得一確具實用性之本發明。 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.
本發明所欲解決之技術問題在於針對現有技術存在的上述缺失,提供一種觸媒提升矽烷反應生成及其製程副產物全回收的系統。 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.
一矽烷反應系統包括有一矽化鎂吸粉桶、一矽化鎂自動進料裝置、一夾套式反應槽、一冷凝器及一氣動泵,該矽化鎂吸粉桶以無氧狀態存置矽化鎂與觸媒,且該觸媒的混合比例為矽化鎂的15%至30%,而該觸媒由20~50wt%的矽粉與50~80wt%的金屬粉末構成雙金屬複合物,又該矽化鎂自動進料裝置連接於該矽化鎂吸粉桶與該夾套式反應槽之間,且該夾套式反應槽裝設有一攪拌機,而該夾套式反應槽的頂端連接該冷凝器與底端連接該氣動泵,又該夾套式反應槽先投入氯化銨粉料,並進行密閉氮氣置換及真空除氧作業,再導入純氨後控制-30℃冷媒的冷凝形成液態氨,並啟動該攪拌機進行氯化銨與液態氨的預溶,且由該矽化鎂自動進料裝置以固定速率投入矽化鎂與觸媒進入該夾套式反應槽,藉此觸發反應生成矽甲烷與氫氣混氣並經由該冷凝器產出,另以90℃熱媒輔助反應後的液氨與矽乙烷進行蒸煮而經由該冷凝器回收,而反應後的渣料由該氣動泵排出存放於一渣料緩衝槽,一氣液分離槽連接於該冷凝器,並由該氣液分離槽的上端連接一用於存放汽化矽甲烷之矽甲烷暫存槽,且該氣液分離槽連接一用於存放液化矽乙烷與液氨之矽乙烷暫存槽,一矽乙烷蒸餾系統包括有一脫矽乙烷塔、一氨純化塔及一矽乙烷純化塔,該矽乙烷暫存槽連接該脫矽乙烷塔,該脫矽乙烷塔上端連接該氨純化塔,且該脫矽乙烷塔下端連接該矽乙烷純化塔,該脫矽乙烷塔以壓力18~24kg/cm2與溫度25℃至70℃條件將氨分離至該氨純化塔,以及矽乙烷分離至該矽乙烷純化塔,又該氨純化塔以溫度差分離少量矽甲烷回流至該矽甲烷暫存槽,且該矽乙烷純化塔以溫度 30℃至100℃進一步純化該矽乙烷,並將純化矽乙烷儲存於一液化矽乙烷緩衝桶,藉此使矽乙烷的反應選擇率能達到5~25vol%,而該氨純化塔與該矽乙烷純化塔所分離的氨儲存於一液氨緩衝槽。 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.
其中,該冷凝器依序連接有一第二冷凝器與一第三冷凝器,利用各物質沸點溫度不同之物理特性進行初步的矽烷分離,以2~7kg/cm2之定壓依序導入該第二冷凝器以-30℃冷凝進行與該第三冷凝器以-75℃進行冷凝,形成液態矽乙烷及液化氨,以及氣態的矽甲烷和氫氣,並於該氣液分離槽進行分離。 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.
其中,該冷凝器與該第二冷凝器之間裝設有一過濾器,由於該夾套式反應槽於反應過程生成的矽甲烷混氣及反應結束後蒸煮出的氨和矽乙烷,會伴隨少量經壓差氣流所載帶的原物料或渣料粉體,利用該過濾器攔截大於3~100μm的粉粒。 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.
其中,該液化矽乙烷緩衝桶所儲存的矽乙烷可達4N8(99.998%)之純度,於矽乙烷灌充需求時,藉由真空低溫-75℃冷凝使矽乙烷能由該液化矽乙烷緩衝桶充填入至少一鋼瓶中,亦能以相同真空冷凝技術進行小量矽乙烷的純化及微量不純的氣體脫除。 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.
其中,該矽甲烷暫存槽連接有一矽甲烷分餾系統,該矽甲烷分餾系統包括有一矽甲烷回收塔、一矽甲烷分子篩及一矽甲烷純化塔,該矽甲烷回收塔上端連接該矽甲烷分子篩,並由該矽甲烷分子篩連接該矽甲烷純化塔,該矽甲烷回收塔以壓力8~15kg/cm2與變化溫度-60℃~40℃將大部分的氨分餾儲存至該液氨緩衝槽,而分餾出的矽甲烷氣體與少量的氨再由該3A~5A的矽甲烷分子篩吸附去除氨及其它不純物之氣體,再將矽甲烷導 入矽甲烷純化塔並以-160℃至-50℃的低溫將所含的氫氣脫除分離,讓純化矽甲烷儲存於一液化矽甲烷緩衝桶。 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.
其中,該液化矽甲烷緩衝桶所儲存的矽甲烷可達6N(99.9999%)之純度,且該液化矽甲烷緩衝桶採用內外雙層結構,由該內層存放液化矽甲烷,而該外層呈真空狀並繞設有一環體盤管,利用該環體盤管流通冷媒達-50℃的溫控和壓控,並於需要使用時使用冷媒做為矽甲烷之冷凝,又該液化矽甲烷緩衝桶連接有一汽化器,於矽甲烷灌充需求時,讓矽甲烷導入該汽化器並以-30℃冷媒進行穩定流量之控制輸送至一成品加壓機,並藉由該成品加壓機加壓至100~160kg/cm2的壓力將矽甲烷充填入至少一鋼瓶或至少一槽車中。 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 .
其中,該渣料緩衝槽依順序串接有一離心過濾器、一氨水溶液緩衝槽、一氫氧化鎂過濾器及一氨水緩衝桶,且該離心過濾器與該氫氧化鎂過濾器同時連接有一乾燥磨粉裝置,並以該乾燥磨粉裝置連接有一高壓成型製磚系統,排入該渣料緩衝槽之渣料先於該夾套式反應槽內加水攪拌,使部分轉化為難溶之氫氧化鎂固態粉粒及溶於其中之鹽類產物,並在該渣料緩衝槽的不間斷攪拌下將漿狀渣料流入該離心過濾器,利用該離心過濾器的轉旋脫液,使渣料的液態部分流至該氨水溶液緩術槽,而該固態部分排洩至該乾燥磨粉裝置,又該乾燥磨粉裝置以電加熱配合螺旋攪拌進行固態渣料的加熱乾燥及氨的脫離,並排至該高壓成型製磚系統做為製磚的原料,又該氨水溶液緩衝槽加入氨水,並使溶液中之氯化鎂能反應生成轉化為氯化銨和氫氧化鎂粉粒,再經由該氫氧化鎂過濾器以1~30μm精度過濾氫氧化鎂粉粒並排洩至該乾燥磨粉裝置,避免固態粉粒進入該氨水緩 衝桶,僅將氨水存入該氨水緩衝桶。 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.
其中,該氨水緩衝桶連接有一氨分離回收系統,該氨分離回收系統以一氨回收塔連接該氨水緩衝桶,並由該氨回收塔上端連接有一氨精餾塔,又該氨回收塔以0~5kg/cm2的壓力和50℃~145℃的溫度進行氯化銨溶液和氨水溶液的分離,使氨水溶液由該氨回收塔的塔頂排放至該氨精餾塔,並於該氨精餾塔中以-30℃~130℃的溫度進行氨和水的純化分離,且該氨精餾塔於塔頂的純化氨儲入一氨原料桶進行回收利用,而該氨精餾塔於塔底分離的水和微量的氨回流至該氨水緩衝桶,另該氨回收塔由塔底分離出的氯化銨溶液輸送至一多效蒸發系統,透過該多效蒸發系統以120℃~160℃的蒸汽進行加熱,使氯化銨溶液將所含之水分汽化而脫離氯化銨,氯化銨的含水率能低於1wt%,並由一乾燥機回收做為該夾套式反應槽的反應原料使用,而該水汽以一回收水緩衝槽回收提供該夾套式反應槽於反應後的渣料溶劑使用。 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.
其中,該夾套式反應槽於渣料排空後,以氮氣沖吹、抽真空及90℃熱媒的升溫進行該夾套式反應槽之槽內的清理及有效的除水分,以避免水分影響下個反應過程中生成的矽烷與水在鹼性環境氧化反應而形成二氧化矽,藉此提高矽烷反應率。 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.
其中,矽烷反應全製程之製程設備皆由複數個尾氣排放管線進行匯集連接一尾氣處理系統,該尾氣處理系統包括有一洗滌塔、一高溫氧化器及一過濾設備,且該尾(廢)氣依含有氨及矽烷氣體之組成分流至該尾氣處理系統的各個階段,該洗滌塔以水進行氨氣的吸附脫除,再將所形成之氨水導入該氨水溶液緩衝槽做回收,並做為氯化銨鹽類轉化之添加劑, 而微量的尾氣則由塔頂排放至該高溫氧化器進行矽烷氣體的破壞,使其轉化為二氧化矽之非危險性物質,再由該尾氣處理系統之過濾設備進行攔截收集。 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.
本發明的第一主要目的在於,矽烷生產方式採用改良的矽鎂合金法,配合已開發的獨特觸媒使用技術進行矽乙烷轉化率的提升,及實施新的投料方式和開發的設備,以提升原物料的反應率且降低反應系統受固體粉料阻塞問題的影響,並以改良的生產操作技術有效控制及優化矽烷反應生成的環境,以提升矽乙烷的產能。 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.
本發明的第二主要目的在於,藉由新開發設計之分離純化系統和技術進行反應生成之矽烷混氣與參與反應之固體原物料的分離,再將矽甲烷由混氣中依其物理特性進行低溫氣液分離,並使用該矽甲烷分餾系統進行矽甲烷中氨原料的回收及矽甲烷的純化和其不純物的移除,再以低溫真空方式做為矽甲烷之儲存,而經氣液分離的矽乙烷和氨原料亦以矽乙烷蒸餾系統進行分餾純化,並將氨回收以再次做為反應原料使用,藉此使矽甲烷及矽乙烷的產能和純化過程穩定,且能有效降低生產成本。 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.
本發明的第三主要目的在於,反應所產生的渣料於矽烷反應結束後,以添加入水做為溶劑,使部分渣料內含物能轉化為鹽類物質並溶於氨水中,且得以漿狀流體做後續分離回收處置,又採新設計的分離方法,以離心分離技術進行漿狀渣料的固液分離,並使分離後之固態產物經乾燥後做為製磚原料之開發。而液態之流體藉由添加氨,使其轉化反應為可回收之鹽類氨水溶液,再使用蒸餾系統進行氯化銨鹽類溶液、氨和水的分離純化及回收。氯化銨鹽類溶液則再使用高效蒸發系統進行水分移除的處理 和乾燥,而做為矽烷生產反應原料回收使用。藉使得以有效降低渣料存置對於環境的影響和生產成本的耗費。 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.
本發明的第四主要目的在於,製程產生之尾(廢)氣經尾氣排放管線統一匯集導入尾氣處理系統,藉由氨吸附移除技術將尾氣中之氨氣吸收移除並回收做鹽類溶液添加液使用,而其它矽烷廢氣則由尾氣處理系統進行氧化反應處理,以轉化為非危險性氣體或渣料做處置,以降低環境之汙染和危害。 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.
其他目的、優點和本發明的新穎特性將從以下詳細的描述與相關的附圖更加顯明。 Other objects, advantages, and novel features of the present invention will become more apparent from the following detailed description and the accompanying drawings.
〔本創作〕 [This creation]
11‧‧‧矽烷反應系統 11‧‧‧ Silane reaction system
111‧‧‧矽化鎂吸粉桶 111‧‧‧Magnesium silicide powder bucket
112‧‧‧矽化鎂自動進料裝置 112‧‧‧Magnesium silicide automatic feeding device
113‧‧‧夾套式反應槽 113‧‧‧ Jacketed reaction tank
114‧‧‧冷凝器 114‧‧‧ condenser
115‧‧‧氣動泵 115‧‧‧Pneumatic pump
116‧‧‧攪拌機 116‧‧‧Blender
117‧‧‧第二冷凝器 117‧‧‧Second condenser
118‧‧‧第三冷凝器 118‧‧‧Third condenser
119‧‧‧過濾器 119‧‧‧Filter
12‧‧‧氣液分離槽 12‧‧‧Gas-liquid separation tank
13‧‧‧矽乙烷蒸餾系統 13‧‧‧Silicon distillation system
131‧‧‧脫矽乙烷塔 131‧‧‧Silicon tower
132‧‧‧氨純化塔 132‧‧‧Ammonia purification tower
133‧‧‧矽乙烷純化塔 133‧‧‧Silica purification tower
134‧‧‧液氨緩衝槽 134‧‧‧Liquid ammonia buffer tank
14‧‧‧渣料緩衝槽 14‧‧‧Slag buffer tank
15‧‧‧矽乙烷暫存槽 15‧‧‧ Silane temporary storage tank
16‧‧‧液化矽乙烷緩衝桶 16‧‧‧ Liquefied Silicone Buffer Bucket
17‧‧‧鋼瓶 17‧‧‧ steel cylinder
21‧‧‧矽甲烷暫存槽 21‧‧‧ Silane temporary storage tank
22‧‧‧矽甲烷分餾系統 22‧‧‧Silicon methane fractionation system
221‧‧‧矽甲烷回收塔 221‧‧‧Silicon Methane Recovery Tower
222‧‧‧矽甲烷分子篩 222‧‧‧ Silane molecular sieve
223‧‧‧矽甲烷純化塔 223‧‧‧Silicon methane purification tower
23‧‧‧液化矽甲烷緩衝桶 23‧‧‧ Liquefied Silica Buffer Tank
231‧‧‧汽化器 231‧‧‧Vaporizer
232‧‧‧環體盤管 232‧‧‧Ring body coil
24‧‧‧成品加壓機 24‧‧‧ Finished Press
25‧‧‧鋼瓶 25‧‧‧ Cylinder
26‧‧‧槽車 26‧‧‧ Tank truck
31‧‧‧離心過濾器 31‧‧‧ Centrifugal Filter
32‧‧‧氨水溶液緩衝槽 32‧‧‧ ammonia buffer tank
33‧‧‧氫氧化鎂過濾器 33‧‧‧Magnesium hydroxide filter
34‧‧‧氨水緩衝桶 34‧‧‧Ammonia buffer bucket
35‧‧‧乾燥磨粉裝置 35‧‧‧Drying and grinding device
351‧‧‧高壓成型製磚系統 351‧‧‧High pressure forming brick making system
36‧‧‧氨分離回收系統 36‧‧‧Ammonia separation and recovery system
361‧‧‧氨回收塔 361‧‧‧Ammonia Recovery Tower
362‧‧‧氨精餾塔 362‧‧‧Ammonia distillation column
37‧‧‧氨原料桶 37‧‧‧Ammonia raw material barrel
38‧‧‧多效蒸發系統 38‧‧‧Multi-effect evaporation system
381‧‧‧乾燥機 381‧‧‧ dryer
39‧‧‧回收水緩衝槽 39‧‧‧Recycled water buffer tank
41‧‧‧尾氣排放管線 41‧‧‧ tail gas exhaust pipeline
42‧‧‧尾氣處理系統 42‧‧‧Exhaust gas treatment system
421‧‧‧洗滌塔 421‧‧‧washing tower
422‧‧‧高溫氧化器 422‧‧‧High temperature oxidizer
423‧‧‧過濾設備 423‧‧‧filtration equipment
第1圖係本發明矽乙烷製程之結構與流程圖。 FIG. 1 is a structure and a flowchart of a process for producing silicon in accordance with the present invention.
第2圖係本發明矽甲烷製程之結構與流程圖。 Figure 2 is the structure and flow chart of the process of silicon methane of the present invention.
第3圖係本發明液化矽甲烷緩衝槽之結構示意圖。 FIG. 3 is a schematic structural diagram of a liquefied silicon methane buffer tank of the present invention.
第4圖係本發明渣料回收製程之結構與流程圖。 FIG. 4 is a structure and flowchart of the slag recovery process of the present invention.
第5圖係本發明尾氣回收製程之結構與流程圖。 Figure 5 is the structure and flowchart of the exhaust gas recovery process of the present invention.
為使 貴審查委員對本發明之目的、特徵及功效能夠有更進一步之瞭解與認識,以下茲請配合【圖式簡單說明】詳述如後:先請由第1圖所示觀之,一種觸媒提升矽烷反應生成及其製程副產物全回收的系統,其包括有:一矽烷反應系統11、一氣液分離槽12及一矽乙烷蒸餾系統13,一矽烷反應系統11包括有一矽化鎂吸粉桶111、 一矽化鎂自動進料裝置112、一夾套式反應槽113、一冷凝器114及一氣動泵115,該矽化鎂吸粉桶111以無氧狀態存置矽化鎂(Mg2Si)與觸媒,其無氧狀態是於填裝密閉後進行抽真空與氮氣置換,且該觸媒的混合比例為矽化鎂的15%至30%,而該觸媒由20~50wt%的矽粉(Si)與50~80wt%的金屬粉末構成雙金屬複合物,其中的金屬粉料可使用鹼金屬族、鹼土金屬族之金屬元素,亦可採用過渡金屬中之金屬元素,如鐵(Fe),或ⅢA~ⅥA族群中之元素等合金,又該矽化鎂自動進料裝置112連接於該矽化鎂吸粉桶111與該夾套式反應槽113之間,且該夾套式反應槽113裝設有一攪拌機116,而該夾套式反應槽113的頂端連接該冷凝器114與底端連接該氣動泵115,又該夾套式反應槽113先投入氯化銨(NH4Cl)粉料,並進行密閉氮氣置換及真空除氧作業,再導入純氨(NH3)後控制-30℃冷媒的冷凝形成液態氨,並啟動該攪拌機116進行氯化銨與液態氨的預溶,使氯化銨溶解於液態氨中而形成氨及氯鹽離子,並維持該攪拌機116的持續運轉至反應結束後槽中的淨空,以避免粉料於反應過程中分散不均勻或因反應而凝固結塊造成阻滯,且由該矽化鎂自動進料裝置112以固定速率投入矽化鎂與觸媒進入該夾套式反應槽113,即矽化鎂和觸媒粉料以0~150kg/h的固定速率,配合流量穩定控制的少許液氨做為承載流體,平均地投入該夾套式反應槽113中與氯化銨進行反應,藉此,可避免矽化鎂粉料與槽中液氨接觸時造成飛濺,而使粉料附著於管線中或槽壁逐漸導致管線的阻塞,矽烷生成之過程屬於放熱反應,故於反應過程須持續以-30℃冷媒進行熱能的移除,以便使反應溫度得以維持,更於反應過程中,液態氨亦會受反應生成之熱能而汽化,並隨生成之矽烷飄流出該夾套式反應槽113,導致反應率的降低或終止反應的進 行,為維持反應過程中液態氨的量,將透過該冷凝器114以-30℃冷媒進行氨氣的冷凝,使其再次液化流回該夾套式反應槽113,藉此觸發反應生成矽甲烷(SiH4)與氫氣(H2)混氣並經由該冷凝器114產出,大部分所產出的矽乙烷因其物理特性與氨的特性相似,故會受該冷凝器114的冷凝而再次液化返回該夾套式反應槽113中,是故於矽烷反應結束後,須將參與反應的液態氨及含於其中的矽乙烷盡可能回收,因此轉換該冷凝器114內之冷媒至90℃的熱媒,使該夾套式反應槽113中的液態氨及矽乙烷能穩定的受蒸煮而升溫汽化,藉此以90℃熱媒輔助反應後的液氨與矽乙烷(Si2H6)進行蒸煮而經由該冷凝器114回收,其中,反應原料的使用比例通常由矽化鎂重量為標準,並以矽化鎂1:氯化銨3~6:液態氨9~12取量,且該反應式為:矽甲烷反應方程式如下(主反應):Mg2Si(s)+4NH4Cl(s)+8NH3(l)→SiH4(g)+2(MgCl2‧6NH3)(s) 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)
矽乙烷反應方程式如下(副反應):2Mg2Si(s)+8NH4Cl(s)+16NH3(l)→Si2H6(g)+4(MgCl2‧6NH3)(s)+H2(g) 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)
而反應後的渣料由該氣動泵115排出存放於一渣料緩衝槽14,排入該渣料緩衝槽14之渣料先於該夾套式反應槽113內加水攪拌,使部分轉化為難溶之氫氧化鎂固態粉粒及溶於其中之鹽類產物,其中,該夾套式反應槽113於渣料排空後,以氮氣沖吹、抽真空及90℃熱媒的升溫進行該夾套式反應槽113之槽內的清理及有效的除水分,以避免水分影響下個反應過程中生成的矽烷與水在鹼性環境氧化反應而形成二氧化矽,藉此提高矽烷反應率,一氣液分離槽12連接於該冷凝器114,該冷凝器114依序連接有一第二冷凝器117與一第三冷凝器118,利用各物質沸點溫度不同 之物理特性進行初步的矽烷分離,再以2~7kg/cm2之定壓依序導入該第二冷凝器117以-30℃冷凝進行與該第三冷凝器118以-75℃進行冷凝,即可避免矽乙烷飄散於氣相中再與氣態的矽甲烷和氫氣混合,於該氣液分離設備中進行分離形成液態矽乙烷及液化氨,以及氣態的矽甲烷和氫氣,該冷凝器114與該第二冷凝器117之間裝設有一過濾器119,由於該夾套式反應槽113於反應過程生成的矽甲烷混氣及反應結束後蒸煮出的氨和矽乙烷,會伴隨少量經壓差氣流所載帶的原物料或渣料粉體,利用該過濾器119攔截大於3~100μm的粉粒,由該氣液分離槽12的上端連接一用於存放汽化矽甲烷之矽甲烷暫存槽21,且該氣液分離槽12連接一用於存放液化矽乙烷與液氨之矽乙烷暫存槽15,一矽乙烷蒸餾系統13包括有一脫矽乙烷塔131、一氨純化塔132及一矽乙烷純化塔133,該矽乙烷暫存槽15連接該脫矽乙烷塔131,該脫矽乙烷塔131上端連接該氨純化塔132,且該脫矽乙烷塔131下端連接該矽乙烷純化塔133,該脫矽乙烷塔131以壓力18~24kg/cm2與溫度25°C至70℃條件將氨分離至該氨純化塔132,該分離的液態氨量為58~67wt%,同時將矽乙烷分離至該矽乙烷純化塔133,又該氨純化塔132以溫度差分離少量矽甲烷回流至該矽甲烷暫存槽21,且該矽乙烷純化塔133以溫度30℃至100℃進一步純化該矽乙烷,並將純化矽乙烷儲存於一液化矽乙烷緩衝桶16,藉此使矽乙烷的反應選擇率能達到5~25vol%,該液化矽乙烷緩衝桶16所儲存的矽乙烷可達4N8(99.998%)之純度,於矽乙烷灌充需求時,藉由真空低溫-75℃冷凝使矽乙烷能由該液化矽乙烷緩衝桶16充填入至少一鋼瓶17中,亦能以相同真空冷凝技術進行小量矽乙烷的純化及微量不純的氣體脫除,而該氨純化塔132與該矽乙烷純化塔133所分離的氨儲存於一液氨緩衝 槽134,再透過該液氨緩衝槽134將回收的氨導入該夾套式反應槽113重覆使用,進而有效降低其生產成本。 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.
本創作另一支線進行矽甲烷的純化作業,再請由第2圖所示觀之,該矽甲烷暫存槽21連接有一矽甲烷分餾系統22,該矽甲烷分餾系統22包括有一矽甲烷回收塔221、一矽甲烷分子篩222及一矽甲烷純化塔223,該矽甲烷回收塔221上端連接該矽甲烷分子篩222,並由該矽甲烷分子篩222連接該矽甲烷純化塔223,該矽甲烷回收塔221以壓力8~15kg/cm2與變化溫度-60℃~40℃將大部分的氨分餾儲存至該液氨緩衝槽134,即利用氨為相對較重物質之特性,經分餾後由該矽甲烷回收塔221的塔底產出並輸送至該氨氣緩衝槽134進行回收,又該分離出的矽甲烷氣體仍含有約2~10wt%的少量氨成分,而分餾出的矽甲烷氣體與少量的氨再由該3A~5A的矽甲烷分子篩222吸附去除氨及其它不純物之氣體,其中該矽甲烷分子篩222能進行加熱以提供切換後的抽真空去除吸附物質的再生使用,再將矽甲烷導入矽甲烷純化塔223並以-160℃至-50℃的低溫將所含的氫氣脫除分離,讓純化矽甲烷儲存於一液化矽甲烷緩衝桶23。該液化矽甲烷緩衝桶23所儲存的矽甲烷可達6N(99.9999%)之純度,且該液化矽甲烷緩衝23桶採用內外雙層結構(配合第3圖所示),由該內層存放液化矽甲烷,而該外層呈真空狀並繞設有一環體盤管232,利用該環體盤管232流通冷媒達-50℃的溫控和壓控,並於需要使用時使用冷媒做為矽甲烷之冷凝,又該液化矽甲烷緩衝桶23連接有一汽化器231,於矽甲烷灌充需求時,讓矽甲烷導入該汽化器231並以-30℃冷媒進行穩定流量之控制輸送至一成品加壓機24,並藉由該成品加壓機24加壓至100~160kg/cm2的壓力將矽甲烷充填入至少一鋼瓶25或至少一槽 車26中,藉此有助於進行灌充運送。 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.
本創作另一支線進行渣料的回收作業,再請由第4圖所示觀之,該渣料緩衝槽14依順序串接有一離心過濾器31、一氨水溶液緩衝槽32、一氫氧化鎂過濾器33及一氨水緩衝桶34,且該離心過濾器31與該氫氧化鎂過濾器33同時連接有一乾燥磨粉裝置35,並以該乾燥磨粉裝置35連接有一高壓成型製磚系統351,作業時排入該渣料緩衝槽14之渣料先於該夾套式反應槽113內加水攪拌,使部分轉化為難溶之氫氧化鎂固態粉粒及溶於其中之鹽類產物,並在該渣料緩衝槽14的不間斷攪拌下將漿狀渣料流入該離心過濾器31,讓渣料能更有效的與水進行反應生成可溶之鹽類,令生成之固體粉粒能均勻分布且避免沉澱,再利用該離心過濾器31的轉旋脫液,即該離心過濾器31以300~1000rpm的轉速進行渣料的脫液,並以200~400目之濾材進行固態粉料的攔截,使渣料的液態部分流至該氨水溶液緩術槽32,而該固態渣料於該離心過濾器31形成一適當厚度時,以刮除方式排洩至該乾燥磨粉裝置35,又該乾燥磨粉裝置35以電加熱配合螺旋攪拌進行固態渣料的加熱乾燥及氨的脫離,並排至該高壓成型製磚系統351做為製磚的原料,亦能直接做為排煙脫硫之用劑,又該氨水溶液緩衝槽32加入回收取得的氨水,並使溶液中之氯化鎂能反應生成轉化為氯化銨和氫氧化鎂粉粒,再經由該氫氧化鎂過濾器33以1~30μm精度過濾氫氧化鎂粉粒並排洩至該乾燥磨粉裝置35,而該排洩方式是使用氮氣將粉粒由該離心過濾器31上吹落,並以其重力將粉粒排放至該乾燥磨粉裝置35,避免固態粉粒進入該氨水緩衝桶34,僅將氨水存入該氨水緩衝桶34。該氨水緩衝桶34連接有一氨分離回收系統36,該氨分離回收系統36以一氨回收塔361連接 該氨水緩衝桶34,並由該氨回收塔361上端連接有一氨精餾塔362,又該氨回收塔361以0~5kg/cm2的壓力和50℃~145℃的溫度進行氯化銨溶液和氨水溶液的分離,所分離的氨水濃度為10~30wt%屬於相對較輕物質,使氨水溶液由該氨回收塔361的塔頂排放至該氨精餾塔362,並於該氨精餾塔362中以-30℃~130℃的溫度進行氨和水的純化分離,所純化的氨能達工業級98%~99%的純度水準,且該氨精餾塔362於塔頂的純化氨儲入一氨原料桶37進行回收利用,而該氨精餾塔362於塔底分離的水和微量的氨回流至該氨水緩衝桶34,另該氨回收塔361由塔底分離出的氯化銨溶液輸送至一多效蒸發系統38,透過該多效蒸發系統38以120℃~160℃的蒸汽進行加熱,使氯化銨溶液將所含之水分汽化而脫離氯化銨,氯化銨的含水率能低於1wt%,並由一乾燥機381回收做為該夾套式反應槽113的反應原料使用,而該水汽以一回收水緩衝槽39回收提供該夾套式反應槽113於反應後的渣料溶劑使用。 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.
本創作之尾(廢)氣回收作業,再請由第5圖所示觀之,矽烷反應全製程之製程設備皆由複數個尾氣排放管線41進行匯集連接一尾氣處理系統42,該尾氣處理系統42包括有一洗滌塔421、一高溫氧化器422及一過濾設備423,且該尾(廢)氣依含有氨及矽烷氣體之組成分流至該尾氣處理系統42的各個階段,該洗滌塔421以水進行氨氣的吸附脫除,再將所形成之氨水導入該氨水溶液緩衝槽32做回收,並做為氯化銨鹽類轉化之添加劑,而微量的尾氣則由塔頂排放至該高溫氧化器422進行矽烷氣體的破壞,使其轉化為二氧化矽之非危險性物質,再由該尾氣處理系統42之過濾設備423進行攔截收集,藉此有效處理尾氣使其以低成本降低對環境的污染。 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. .
綜上所述,本發明確實已達突破性之結構設計,而具有改良之發明內容,同時又能夠達到產業上之利用性與進步性,且本發明未見於任何刊物,亦具新穎性,當符合專利法相關法條之規定,爰依法提出發明專利申請,懇請 鈞局審查委員授予合法專利權,至為感禱。 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.
唯以上所述者,僅為本發明之一較佳實施例而已,當不能以之限定本發明實施之範圍;即大凡依本發明申請專利範圍所作之均等變化與修飾,皆應仍屬本發明專利涵蓋之範圍內。 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.
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CN205709892U (en) * | 2016-06-25 | 2016-11-23 | 浙江迅鼎半导体材料科技有限公司 | A kind of Disilicoethane process units |
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CN205709892U (en) * | 2016-06-25 | 2016-11-23 | 浙江迅鼎半导体材料科技有限公司 | A kind of Disilicoethane process units |
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