CN115626937A - Continuous production process of hexamethyldisilazane - Google Patents
Continuous production process of hexamethyldisilazane Download PDFInfo
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- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 238000000034 method Methods 0.000 title claims abstract description 45
- 238000010924 continuous production Methods 0.000 title claims abstract description 19
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 130
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 64
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 64
- 238000004140 cleaning Methods 0.000 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- 238000000926 separation method Methods 0.000 claims abstract description 24
- 239000007787 solid Substances 0.000 claims abstract description 22
- TWJVNKMWXNTSAP-UHFFFAOYSA-N azanium;hydroxide;hydrochloride Chemical compound [NH4+].O.[Cl-] TWJVNKMWXNTSAP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 claims abstract description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 14
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 50
- 239000007788 liquid Substances 0.000 claims description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 229910021529 ammonia Inorganic materials 0.000 claims description 27
- 239000005051 trimethylchlorosilane Substances 0.000 claims description 25
- 238000005406 washing Methods 0.000 claims description 22
- 238000002425 crystallisation Methods 0.000 claims description 18
- 230000008025 crystallization Effects 0.000 claims description 18
- 150000003839 salts Chemical class 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 11
- 239000006227 byproduct Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 7
- 239000012459 cleaning agent Substances 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 6
- 238000006386 neutralization reaction Methods 0.000 claims description 6
- 239000008399 tap water Substances 0.000 claims description 6
- 235000020679 tap water Nutrition 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000005191 phase separation Methods 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 238000010926 purge Methods 0.000 claims 1
- 238000009834 vaporization Methods 0.000 claims 1
- 230000008016 vaporization Effects 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 abstract description 6
- 238000000354 decomposition reaction Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract 1
- 238000011084 recovery Methods 0.000 abstract 1
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 description 6
- 238000011437 continuous method Methods 0.000 description 4
- VZEXJUAYWWLSEP-UHFFFAOYSA-N N.[Cl].Cl Chemical compound N.[Cl].Cl VZEXJUAYWWLSEP-UHFFFAOYSA-N 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- 239000006200 vaporizer Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229930186147 Cephalosporin Natural products 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 229930182555 Penicillin Natural products 0.000 description 1
- JGSARLDLIJGVTE-MBNYWOFBSA-N Penicillin G Chemical compound N([C@H]1[C@H]2SC([C@@H](N2C1=O)C(O)=O)(C)C)C(=O)CC1=CC=CC=C1 JGSARLDLIJGVTE-MBNYWOFBSA-N 0.000 description 1
- DRMLKDKBOXSZBE-UHFFFAOYSA-N [SiH3]N[SiH3].C[Si](N[Si](C)(C)C)(C)C Chemical compound [SiH3]N[SiH3].C[Si](N[Si](C)(C)C)(C)C DRMLKDKBOXSZBE-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- LKCWBDHBTVXHDL-RMDFUYIESA-N amikacin Chemical compound O([C@@H]1[C@@H](N)C[C@H]([C@@H]([C@H]1O)O[C@@H]1[C@@H]([C@@H](N)[C@H](O)[C@@H](CO)O1)O)NC(=O)[C@@H](O)CCN)[C@H]1O[C@H](CN)[C@@H](O)[C@H](O)[C@H]1O LKCWBDHBTVXHDL-RMDFUYIESA-N 0.000 description 1
- 229960004821 amikacin Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 229940124587 cephalosporin Drugs 0.000 description 1
- 150000001780 cephalosporins Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 229940049954 penicillin Drugs 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/16—Halides of ammonium
- C01C1/164—Ammonium chloride
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Chemical & Material Sciences (AREA)
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- Inorganic Chemistry (AREA)
Abstract
Description
技术领域technical field
本发明涉及化工技术领域，尤其涉及一种六甲基二硅氮烷的连续生产工艺。The invention relates to the technical field of chemical industry, in particular to a continuous production process of hexamethyldisilazane.
背景技术Background technique
六甲基二硅氮烷是一种应用广泛的有机硅化合物，在医药领域应用于青霉素、阿米卡星、头孢菌素等合成过程中，在有机合成领域用作甲硅烷化试剂，在半导体领域用作光致刻蚀剂的粘剂助剂，在表面处理领域用作硅藻土、白炭黑和钛白粉等材料的表面处理。Hexamethyldisilazane is a widely used organosilicon compound. It is used in the synthesis of penicillin, amikacin and cephalosporin in the field of medicine, as a silylating agent in the field of organic synthesis, and in the field of semiconductors. It is used as an adhesive agent for photoresist in the field, and used as a surface treatment for materials such as diatomaceous earth, white carbon black and titanium dioxide in the field of surface treatment.
六甲基二硅氮烷的生产工艺主要是通过三甲基氯硅烷和氨气反应来进行制备，在反应过程中不可避免的会产生氯化铵的副产物，为了获得高纯度的六甲基二硅氮烷产品，需要通过各种方式除去氯化铵副产物。六甲基二硅氮烷生产中氯化铵的脱除是决定生产周期以及生产成本的重要因素，而根据除去副产物的方法不同，六甲基二硅氮烷的生产工艺一般分为连续法和间歇法。The production process of hexamethyldisilazane is mainly prepared by the reaction of trimethylchlorosilane and ammonia. During the reaction process, the by-product of ammonium chloride will inevitably be produced. In order to obtain high-purity hexamethyldisilazane Disilazane products require removal of the ammonium chloride by-product by various means. The removal of ammonium chloride in the production of hexamethyldisilazane is an important factor determining the production cycle and production cost, and according to the different methods of removing by-products, the production process of hexamethyldisilazane is generally divided into continuous method and batch method.
间歇法为一定配比的三甲基氯硅烷和氨气(有些工艺还需加入惰性溶剂)在反应釜中反应一定时间后加入溶盐清洗剂(水)，洗涤反应中产生的氯化铵固体。搅拌一定时间后静置分层，下层氯化铵水溶液再经蒸发结晶分离出氯化铵。这种方法效率低，氨气损耗大，能耗大，氯化铵蒸发结晶对设备耐腐蚀性要求高。The batch method is a certain ratio of trimethylchlorosilane and ammonia (some processes need to add an inert solvent) in the reactor for a certain period of time and then add a dissolved salt cleaning agent (water) to wash the solid ammonium chloride produced in the reaction. . After stirring for a certain period of time, let it stand for stratification, and the ammonium chloride aqueous solution in the lower layer is evaporated and crystallized to separate ammonium chloride. This method has low efficiency, large loss of ammonia gas, and high energy consumption, and the evaporation and crystallization of ammonium chloride requires high corrosion resistance of equipment.
连续法为三甲基氯硅烷和氨气连续通入反应塔或反应釜，通过过滤器除去氯化铵固体后继续打入反应釜或反应塔内循环反应以提高转化率，并通过排料阀采出六甲基二硅氮烷。由于氨气和三甲基氯硅烷为气液两相反应，接触效果差，反应效率低。The continuous method is that trimethylchlorosilane and ammonia are continuously fed into the reaction tower or reactor, and the solid ammonium chloride is removed through the filter and then continuously injected into the reactor or reaction tower to improve the conversion rate and pass through the discharge valve. Production of hexamethyldisilazane. Because ammonia and trimethylchlorosilane are gas-liquid two-phase reaction, the contact effect is poor and the reaction efficiency is low.
连续法中先采用过滤器除去六甲基二硅氮烷中的氯化铵固体，待过滤压力升高到一定压力后切换至其它过滤器。用水或氯化铵水循环清洗过滤器，以溶解滤饼上的氯化铵。滤液经过降温后析出氯化铵固体，经过离心分离得到副产物氯化铵，滤液再加热循环使用。此方法未能除去六甲基二硅氮烷中的氨气，以至其进入精馏系统后，进入尾气和污水系统，大大增加了污水处理难度。而氯化铵水溶液在碱性条件下很容易分解和再结合，会影响生产周期。In the continuous method, the filter is used to remove the ammonium chloride solid in the hexamethyldisilazane, and the filter pressure is increased to a certain pressure before switching to other filters. Wash the filter with water or ammonium chloride water circulation to dissolve the ammonium chloride on the filter cake. After the filtrate is cooled, ammonium chloride solid is precipitated, and the by-product ammonium chloride is obtained through centrifugation, and the filtrate is heated and recycled. This method fails to remove the ammonia in hexamethyldisilazane, so that after it enters the rectification system, it enters the tail gas and sewage system, which greatly increases the difficulty of sewage treatment. However, ammonium chloride aqueous solution is easy to decompose and recombine under alkaline conditions, which will affect the production cycle.
综上可知现有技术中六甲基二硅氮烷的生产工艺的连续法和间歇法均存在一定的问题，因此需要一种更好的生产方法。In summary, it can be seen that both the continuous method and the batch method of the production process of hexamethyldisilazane in the prior art have certain problems, so a better production method is needed.
发明内容Contents of the invention
针对现有技术中所存在的不足，本发明提供了一种六甲基二硅氮烷的连续生产工艺，其解决了现有技术中存在的或是效率低，氨气损耗大，能耗大，氯化铵蒸发结晶对设备耐腐蚀性要求高的问题，或是遗留氨气增加了污水处理难度的问题。Aiming at the deficiencies in the prior art, the present invention provides a continuous production process for hexamethyldisilazane, which solves the existing problems in the prior art such as low efficiency, large ammonia loss, and large energy consumption. , Ammonium chloride evaporation crystallization requires high corrosion resistance of equipment, or the problem of residual ammonia increases the difficulty of sewage treatment.
根据本发明的实施例，一种六甲基二硅氮烷的连续生产工艺，包括如下步骤：According to an embodiment of the present invention, a continuous production process of hexamethyldisilazane comprises the following steps:
六甲基二硅氮烷的生产：Production of Hexamethyldisilazane:
S1、先用氮气置换整套生产装置内的空气，为了氨气和三甲基氯硅烷有充分的接触效果以提高反应效率，将三甲基氯硅烷气化后与氨气通过文丘里混合器充分混合后进入管氏反应器中反应，实现均相反应，氨气与三甲基氯硅烷的配料比为3.01～3.2(摩尔比)；氨气的压力控制为700～1200kPa，三甲基氯硅烷的气化温度控制在57～80℃，反应温度控制在40～100℃。S1. First replace the air in the whole set of production equipment with nitrogen. In order to have a sufficient contact effect between ammonia and trimethylchlorosilane to improve the reaction efficiency, trimethylchlorosilane is vaporized and mixed with ammonia through a Venturi mixer. After mixing, it enters the tube reactor for reaction to achieve a homogeneous reaction. The ratio of ammonia gas to trimethylchlorosilane is 3.01-3.2 (molar ratio); the pressure of ammonia gas is controlled at 700-1200kPa, and trimethylchlorosilane The gasification temperature is controlled at 57-80°C, and the reaction temperature is controlled at 40-100°C.
S1.1、三甲基氯硅烷与氨气反应生成氯化铵固体，虽大部分被六甲基二硅氮烷液体带走，但仍会有部分积聚在反应器和管道的内壁上，经过长时间积累后容易堵塞。为了能连续反应，本发明包括两套反应装置进行轮换使用，并配合对应的生产装置清洗方法：S1.1. Trimethylchlorosilane reacts with ammonia to form ammonium chloride solid. Although most of it is taken away by the hexamethyldisilazane liquid, some of it will still accumulate on the inner wall of the reactor and the pipeline. It is easy to clog after accumulating for a long time. In order to be able to react continuously, the present invention includes two sets of reaction devices for alternate use, and cooperates with the corresponding production device cleaning method:
一套反应装置需要清理时，先关闭三甲基氯硅烷进料阀、氨气进料阀和反应产物出口阀，然后加入清洗剂，循环溶解管壁上的氯化铵固体，循环清洗1～3h。关闭清洗水进口和出口阀门，打开自来水进水阀和回用水罐进口阀，用自来水清洗不少于15min，回用水打入清洗液缓冲罐用于补充氯化铵清洗损耗的水。关闭自来水进水阀和清洗完毕后用氮气吹扫反应系统至几无水流出。When a set of reaction device needs to be cleaned, first close the trimethylchlorosilane feed valve, ammonia gas feed valve and reaction product outlet valve, then add cleaning agent, circulate and dissolve the ammonium chloride solid on the pipe wall, and cycle clean for 1~ 3h. Close the cleaning water inlet and outlet valves, open the tap water inlet valve and the inlet valve of the reuse water tank, wash with tap water for no less than 15 minutes, and pour the reuse water into the cleaning solution buffer tank to supplement the water lost in ammonium chloride cleaning. After closing the tap water inlet valve and cleaning, the reaction system was purged with nitrogen until almost no water flowed out.
S2、生成的六甲基二硅氮烷液体流入循环槽，待循环槽积蓄一定液位后打开循环泵，将六甲基二硅氮烷连续通入用于回流的文丘里混合器与循环槽气相混合后送入管氏反应器进口；在循环反应过程中确保循环槽有一定的液位保持液封以防止气相进入循环泵中，循环流量控制在30～80m3/h，待反应系统稳定后，从循环泵出口采出粗六甲基氯化铵进入氯化铵清洗工序。S2. The generated hexamethyldisilazane liquid flows into the circulation tank. After a certain liquid level is accumulated in the circulation tank, the circulation pump is turned on, and the hexamethyldisilazane is continuously passed into the Venturi mixer and the circulation tank for reflux. The gas phase is mixed and sent to the inlet of the tube reactor; during the circulation reaction process, ensure that the circulation tank has a certain liquid level to maintain a liquid seal to prevent the gas phase from entering the circulation pump. The circulation flow rate is controlled at 30-80m 3 /h, and the reaction system is stable. Finally, the crude hexamethylammonium chloride is extracted from the outlet of the circulating pump and enters the ammonium chloride cleaning process.
氯化铵的去除：Ammonium chloride removal:
S3、来自反应工序的粗六甲基二硅氮烷连续进入洗盐釜中，在搅拌下连续通入清洗水(氯化铵水溶液)，清洗水与粗六甲基二硅氮烷的配比为2.5～3.5(质量比)，反应釜内温度保持60～90℃。在清洗过程中，不断用循环泵给洗盐釜打循环以增加洗涤效果，流量为60～120m3/h。油相的六甲基二硅氮烷从洗盐釜的上部溢流进入分液槽，经分液槽再分层溢流进入集油槽，集油槽的粗六甲基二硅氮烷打入精馏系统提纯。水相中的氯化铵水用循环泵不断打入隔油槽分离少量的油相，分出的油相再溢流进入分液槽二次分相后进入集油槽。水相流入结晶釜内，同时来自分液槽和集油槽的少量水相也流入结晶釜中。S3, the crude hexamethyldisilazane from the reaction process continuously enters the salt washing tank, and continuously feeds cleaning water (ammonium chloride aqueous solution) under stirring, and the ratio of cleaning water to crude hexamethyldisilazane It is 2.5～3.5 (mass ratio), and the temperature in the reactor is maintained at 60～90°C. During the cleaning process, the circulation pump is used to continuously circulate the salt washing kettle to increase the washing effect, and the flow rate is 60-120m 3 /h. The hexamethyldisilazane in the oil phase overflows from the upper part of the salt washing kettle into the liquid separation tank, and then overflows into the oil collection tank through the liquid separation tank, and the crude hexamethyldisilazane in the oil collection tank is injected into the refined Distillation system purification. The ammonium chloride water in the water phase is continuously pumped into the oil separation tank to separate a small amount of oil phase with a circulation pump, and the separated oil phase overflows into the liquid separation tank for secondary phase separation and then enters the oil collection tank. The water phase flows into the crystallization tank, and a small amount of water phase from the liquid separation tank and the oil collection tank also flows into the crystallization tank.
S4、来自隔油槽、分液槽、反应器清洗和集油槽的氯化铵水，连续进入结晶釜，用-15℃的冷冻水降温，保持釜内温度5～8℃，在不断的搅拌下结晶出氯化铵固体。氯化铵水经过二级结晶工艺后连续进入离心机，分离出氯化铵固体，作为副产物出售。滤液流入中和釜，用浓盐酸中和至pH为5～7。中和后的氯化铵稀溶液经清洗液缓冲罐后通过清洗液加热器，用蒸汽加热至60～95℃后用再进入洗盐釜和反应器。S4. The ammonium chloride water from the oil separation tank, liquid separation tank, reactor cleaning and oil collection tank continuously enters the crystallization tank, cools down with -15°C chilled water, keeps the temperature in the tank at 5-8°C, and keeps stirring Ammonium chloride solid crystallized out. After the ammonium chloride water goes through the secondary crystallization process, it continuously enters the centrifuge, and the ammonium chloride solid is separated and sold as a by-product. The filtrate flows into the neutralization tank and is neutralized with concentrated hydrochloric acid until the pH is 5-7. The neutralized dilute ammonium chloride solution passes through the cleaning liquid buffer tank, then passes through the cleaning liquid heater, is heated to 60-95°C with steam, and then enters the salt washing tank and reactor.
相比于现有技术，本发明具有如下有益效果：Compared with the prior art, the present invention has the following beneficial effects:
1、三甲基氯硅烷气化后通过文丘里混合器与氨气混合，使得氨气和三甲基氯硅烷能够充分接触，能够有效地改变氨气和液态三甲基氯硅烷气液两相接触不好而导致反应效率低的问题；1. After trimethylchlorosilane is gasified, it is mixed with ammonia gas through a Venturi mixer, so that ammonia gas and trimethylchlorosilane can fully contact, and can effectively change the gas-liquid two-phase of ammonia gas and liquid trimethylchlorosilane The problem of low reaction efficiency due to poor contact;
2、本发明既能通过在生产中不断切换两套反应装置，同时停产装置用清洗液(氯化铵水溶液)清除反应器和管道中的氯化铵固体的方式，以实现整个生产工艺的连续性，又能有效地利用60～95℃下不饱和的氯化铵水溶液回收其中的氯化铵；2. The present invention can continuously switch two sets of reaction devices in production, and simultaneously stop the production device to remove the ammonium chloride solids in the reactor and pipelines with cleaning solution (ammonium chloride aqueous solution), so as to realize the continuous operation of the whole production process. It can effectively utilize the unsaturated ammonium chloride aqueous solution at 60-95°C to recover the ammonium chloride;
4、在循环管回路上装文丘里混合器，利用循环液的高流速将循环槽气相吸入，使未反应的氨气溶解于粗六甲基硅氮烷中或由其夹带回到管氏反应器中继续与三甲基氯硅烷反应，可以有效降低氨气的单耗，以及排放氨气造成的环境污染；4. Install a Venturi mixer on the circulation pipe circuit, use the high flow rate of the circulation liquid to suck the gas phase of the circulation tank, so that the unreacted ammonia gas is dissolved in the crude hexamethylsilazane or carried back to the tube reactor by it Continue to react with trimethylchlorosilane, which can effectively reduce the unit consumption of ammonia and the environmental pollution caused by the discharge of ammonia;
5、本发明的氯化铵去除工艺中使用的装置为一套釜式连续洗涤装置，由于六甲基二硅氮烷不溶于水的特性，在洗盐釜中上部油相处连续采出六甲基二硅氮烷，并通过静置分液将少量氯化铵水分离，而氯化铵水中带有的少量六甲基二硅氮烷则通过隔油槽回收夹带的六甲基二硅氮烷。同时为了增加洗涤效果设计了氯化铵水循环洗涤装置，连续不断地将釜底的氯化铵水打回洗盐釜内以增加与氯化铵的接触效果。本发明相较间歇洗涤效率更高，无需操作人员反复操作。相较于利用过滤器过滤氯化铵固体后再用水溶解过滤器上氯化氨固体的连续工艺，能大幅减少操作人员的工作量和操作风险；5. The device used in the ammonium chloride removal process of the present invention is a kettle-type continuous washing device. Due to the insoluble characteristics of hexamethyldisilazane in water, hexamethyldisilazane is continuously extracted from the upper oil phase of the salt washing kettle. Disilazane, and a small amount of ammonium chloride water is separated by static liquid separation, and a small amount of hexamethyldisilazane contained in the ammonium chloride water is recovered through the oil separation tank to recover the entrained hexamethyldisilazane . At the same time, in order to increase the washing effect, an ammonium chloride water circulation washing device is designed, and the ammonium chloride water at the bottom of the kettle is continuously returned to the salt washing kettle to increase the contact effect with ammonium chloride. Compared with intermittent washing, the present invention has higher efficiency and does not require repeated operations by operators. Compared with the continuous process of using a filter to filter the ammonium chloride solid and then dissolving the ammonium chloride solid on the filter with water, it can greatly reduce the workload and operational risk of the operator;
6、本发明利用氯化铵在不同温度下溶解度的差别，将5～8℃饱和氯化铵溶液加热至60～95℃，再溶解粗六甲基二硅氮烷中的氯化铵，然后降温至5～8℃后在结晶釜中析出氯化铵固体，反复循环。相较蒸发结晶氯化铵大大降低了能耗(无水的气化过程，此过程消耗大量的能量)，以及极大地减少了含氨废水和废气的排放。此外，本发明增加了中和工序，用浓盐酸来中和母液中的氨，以降低氯化铵水溶液在加热过程中氯化铵的分解。6. The present invention utilizes the difference in the solubility of ammonium chloride at different temperatures to heat the saturated ammonium chloride solution at 5 to 8°C to 60 to 95°C, then dissolve the ammonium chloride in the crude hexamethyldisilazane, and then After cooling down to 5-8°C, solid ammonium chloride is precipitated in the crystallization kettle, and the cycle is repeated. Compared with evaporating crystalline ammonium chloride, the energy consumption is greatly reduced (anhydrous gasification process, which consumes a lot of energy), and the discharge of ammonia-containing wastewater and waste gas is greatly reduced. In addition, the present invention adds a neutralization process, using concentrated hydrochloric acid to neutralize the ammonia in the mother liquor, so as to reduce the decomposition of ammonium chloride in the heating process of the ammonium chloride aqueous solution.
附图说明Description of drawings
图1为本发明实施例中六甲基二硅氮烷的生产部分工艺流程图。Fig. 1 is the process flow chart of the production part of hexamethyldisilazane in the embodiment of the present invention.
图2为本发明实施例中氯化铵的去除部分工艺流程图。Fig. 2 is the process flowchart of the removal part of ammonium chloride in the embodiment of the present invention.
具体实施方式Detailed ways
下面结合附图及实施例对本发明中的技术方案进一步说明。The technical solutions in the present invention will be further described below in conjunction with the accompanying drawings and embodiments.
实施例1：Example 1:
(1)三甲基氯硅烷打入三甲汽化器，打开蒸汽加热至57℃，打开氨气进料阀和三甲进料阀，开始反应，氨气和三甲基氯硅烷的投料比为3.01(摩尔比)。通过反应器的蒸汽加热和循环管路上的冷凝器控制反应温度为40℃。硅氮烷的收率为96.2％。(1) Trimethylchlorosilane is injected into the trimethylsilane vaporizer, the steam is turned on and heated to 57° C., the ammonia feed valve and the trimethylsilane feed valve are opened, and the reaction is started. The feed ratio of ammonia and trimethylchlorosilane is 3.01 (mol Compare). The reaction temperature was controlled at 40°C by the steam heating of the reactor and the condenser on the circulation line. The yield of silazane was 96.2%.
(2)循环槽液位达到20％打开循环泵，控制循环流量为30m3/h，控制循环槽液位在10％～80％之间，连续采出粗六甲基二硅氮烷进入氯化铵清洗工序。(2) When the liquid level of the circulation tank reaches 20%, turn on the circulation pump, control the circulation flow rate to 30m 3 /h, control the liquid level of the circulation tank between 10% and 80%, and continuously extract the crude hexamethyldisilazane into the chlorine Ammonium chloride cleaning process.
(3)清洗水和粗六甲基二硅氮烷连续通入洗盐釜，比例为2.5(质量比)，在搅拌和循环下溶解粗六甲基二硅氮烷中的氯化铵和氨，控制釜内温度在60～90℃，循环流量60m3/h。通过氯化铵水和六甲基二硅氮烷采出量控制釜内液位在60～80％之间。(3) Cleaning water and crude hexamethyldisilazane are continuously passed into the salt washing tank, the ratio is 2.5 (mass ratio), and the ammonium chloride and ammonia in the crude hexamethyldisilazane are dissolved under stirring and circulation , control the temperature in the kettle at 60-90°C, and the circulating flow rate at 60m 3 /h. The liquid level in the kettle is controlled between 60% and 80% by the output of ammonium chloride water and hexamethyldisilazane.
(4)来自隔油槽、分液槽、反应器清洗和集油槽的氯化铵水，连续进入结晶釜，用-15℃冷冻水降温，保持釜内温度5～8℃，在不断的搅拌下结晶出氯化铵固体。氯化铵水经过二级结晶工艺后连续进入离心机，分离出氯化铵固体，作为副产物出售。滤液流入中和釜，用浓盐酸中和至pH为5～7。中和后的氯化铵稀溶液经清洗液缓冲罐后通过清洗液加热器，用蒸汽加热至60～95℃后用再进入洗盐釜和反应器。(4) The ammonium chloride water from the oil separation tank, liquid separation tank, reactor cleaning and oil collection tank continuously enters the crystallization kettle, cools down with -15°C frozen water, keeps the temperature in the kettle at 5-8°C, and keeps stirring Ammonium chloride solid crystallized out. After the ammonium chloride water goes through the secondary crystallization process, it continuously enters the centrifuge, and the ammonium chloride solid is separated and sold as a by-product. The filtrate flows into the neutralization tank and is neutralized with concentrated hydrochloric acid until the pH is 5-7. The neutralized dilute ammonium chloride solution passes through the cleaning liquid buffer tank, then passes through the cleaning liquid heater, is heated to 60-95°C with steam, and then enters the salt washing tank and reactor.
实施例2：Example 2:
(1)三甲基氯硅烷打入三甲汽化器，打开蒸汽加热至70℃，打开氨气进料阀和三甲进料阀，开始反应，氨气和三甲基氯硅烷的投料比为3.08(摩尔比)。通过反应器的蒸汽加热和循环管路上的冷凝器控制反应温度为80℃。硅氮烷的收率为97.0％。(1) Trimethylchlorosilane is injected into the trimethylsilane vaporizer, the steam is turned on and heated to 70° C., the ammonia feed valve and the trimethylsilane feed valve are opened, and the reaction is started. The feed ratio of ammonia and trimethylchlorosilane is 3.08 (mol Compare). The reaction temperature was controlled at 80°C by the steam heating of the reactor and the condenser on the circulation line. The yield of silazane was 97.0%.
(2)循环槽液位达到20％打开循环泵，控制循环流量为60m3/h，控制循环槽液位在10％～80％之间，连续采出粗六甲基二硅氮烷进入氯化铵清洗工序。(2) When the liquid level of the circulation tank reaches 20%, turn on the circulation pump, control the circulation flow rate to 60m 3 /h, control the liquid level of the circulation tank between 10% and 80%, and continuously extract the crude hexamethyldisilazane into the chlorine Ammonium chloride cleaning process.
(3)清洗水和粗六甲基二硅氮烷连续通入洗盐釜，比例为2.7(质量比)，在搅拌和循环下溶解粗六甲基二硅氮烷中的氯化铵和氨，控制釜内温度在60～90℃，循环流量80m3/h。通过氯化铵水和六甲基二硅氮烷采出量控制釜内液位在60～80％之间。(3) Cleaning water and crude hexamethyldisilazane are continuously passed into the salt washing tank, the ratio is 2.7 (mass ratio), and the ammonium chloride and ammonia in the crude hexamethyldisilazane are dissolved under stirring and circulation , control the temperature in the kettle at 60-90°C, and the circulation flow rate is 80m 3 /h. The liquid level in the kettle is controlled between 60% and 80% by the output of ammonium chloride water and hexamethyldisilazane.
(4)来自隔油槽、分液槽、反应器清洗和集油槽的氯化铵水，连续进入结晶釜，用-15℃冷冻水降温，保持釜内温度5～8℃，在不断的搅拌下结晶出氯化铵固体。氯化铵水经过二级结晶工艺后连续进入离心机，分离出氯化铵固体，作为副产物出售。滤液流入中和釜，用浓盐酸中和至pH为5～7。中和后的氯化铵稀溶液经清洗液缓冲罐后通过清洗液加热器，用蒸汽加热至60～95℃后用再进入洗盐釜和反应器。(4) The ammonium chloride water from the oil separation tank, liquid separation tank, reactor cleaning and oil collection tank continuously enters the crystallization kettle, cools down with -15°C frozen water, keeps the temperature in the kettle at 5-8°C, and keeps stirring Ammonium chloride solid crystallized out. After the ammonium chloride water goes through the secondary crystallization process, it continuously enters the centrifuge, and the ammonium chloride solid is separated and sold as a by-product. The filtrate flows into the neutralization tank and is neutralized with concentrated hydrochloric acid until the pH is 5-7. The neutralized dilute ammonium chloride solution passes through the cleaning liquid buffer tank, then passes through the cleaning liquid heater, is heated to 60-95°C with steam, and then enters the salt washing tank and reactor.
实施例3：Example 3:
(1)三甲基氯硅烷打入三甲汽化器，打开蒸汽加热至80℃，打开氨气进料阀和三甲进料阀，开始反应，氨气和三甲基氯硅烷的投料比为3.8(摩尔比)。通过反应器的蒸汽加热和循环管路上的冷凝器控制反应温度为100℃。硅氮烷的收率为97.6％。(1) Trimethylchlorosilane is injected into the trimethylsilane vaporizer, the steam is turned on and heated to 80° C., the ammonia feed valve and the trimethylsilane feed valve are opened, and the reaction is started. The feed ratio of ammonia and trimethylchlorosilane is 3.8 (mole Compare). The reaction temperature is controlled at 100°C by the steam heating of the reactor and the condenser on the circulation line. The yield of silazane was 97.6%.
(2)循环槽液位达到20％打开循环泵，控制循环流量为60m3/h，控制循环槽液位在10％～80％之间，连续采出粗六甲基二硅氮烷进入氯化铵清洗工序。(2) When the liquid level of the circulation tank reaches 20%, turn on the circulation pump, control the circulation flow rate to 60m 3 /h, control the liquid level of the circulation tank between 10% and 80%, and continuously extract the crude hexamethyldisilazane into the chlorine Ammonium chloride cleaning process.
(3)清洗水和粗六甲基二硅氮烷连续通入洗盐釜，比例为3.5(质量比)，在搅拌和循环下溶解粗六甲基二硅氮烷中的氯化铵和氨，控制釜内温度在60～90℃，循环流量120m3/h。通过氯化铵水和六甲基二硅氮烷采出量控制釜内液位在60～80％之间。(3) Cleaning water and crude hexamethyldisilazane are continuously passed into the salt washing tank, the ratio is 3.5 (mass ratio), and the ammonium chloride and ammonia in the crude hexamethyldisilazane are dissolved under stirring and circulation , control the temperature in the kettle at 60-90°C, and the circulation flow rate is 120m 3 /h. The liquid level in the kettle is controlled between 60% and 80% by the output of ammonium chloride water and hexamethyldisilazane.
(4)来自隔油槽、分液槽、反应器清洗和集油槽的氯化铵水，连续进入结晶釜，用-15℃冷冻水降温，保持釜内温度5～8℃，在不断的搅拌下结晶出氯化铵固体。氯化铵水经过二级结晶工艺后连续进入离心机，分离出氯化铵固体，作为副产物出售。滤液流入中和釜，用浓盐酸中和至pH为5～7。中和后的氯化铵稀溶液经清洗液缓冲罐后通过清洗液加热器，用蒸汽加热至60～95℃后用再进入洗盐釜和反应器。(4) The ammonium chloride water from the oil separation tank, liquid separation tank, reactor cleaning and oil collection tank continuously enters the crystallization kettle, cools down with -15°C frozen water, keeps the temperature in the kettle at 5-8°C, and keeps stirring Ammonium chloride solid crystallized out. After the ammonium chloride water goes through the secondary crystallization process, it continuously enters the centrifuge, and the ammonium chloride solid is separated and sold as a by-product. The filtrate flows into the neutralization tank and is neutralized with concentrated hydrochloric acid until the pH is 5-7. The neutralized dilute ammonium chloride solution passes through the cleaning liquid buffer tank, then passes through the cleaning liquid heater, is heated to 60-95°C with steam, and then enters the salt washing tank and reactor.
最后说明的是，以上实施例仅用以说明本发明的技术方案而非限制，尽管参照较佳实施例对本发明进行了详细说明，本领域的普通技术人员应当理解，可以对本发明的技术方案进行修改或者等同替换，而不脱离本发明技术方案的宗旨和范围，其均应涵盖在本发明的权利要求范围当中。Finally, it is noted that the above embodiments are only used to illustrate the technical solutions of the present invention without limitation. Although the present invention has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that the technical solutions of the present invention can be carried out Modifications or equivalent replacements without departing from the spirit and scope of the technical solution of the present invention shall be covered by the claims of the present invention.
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