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CN-116272746-B - Recovery device and recovery method for aminosilane by-product

CN116272746BCN 116272746 BCN116272746 BCN 116272746BCN-116272746-B

Abstract

The application provides a recycling device and recycling method for aminosilane byproducts. The recovery device comprises a liquid ammonia reactor, a flash tank and a filter, wherein the liquid ammonia reactor is provided with an inlet and an outlet, the inlet of the liquid ammonia reactor is respectively connected with a liquid ammonia source and an amino hydrochloride source, the liquid ammonia reactor is used for carrying out neutralization reaction on raw materials comprising liquid ammonia and amino hydrochloride to obtain a product system, the flash tank is provided with an inlet, a flash ammonia outlet and a flash liquid outlet, the inlet of the flash tank is connected with the outlet of the liquid ammonia reactor, the flash tank is used for carrying out flash evaporation treatment on the product system to obtain ammonia and flash liquid, the filter is provided with an inlet and an outlet, the inlet of the filter is connected with the flash liquid outlet, and the filter is used for carrying out solid-liquid separation on the flash liquid to obtain an ammonium chloride solid filter cake and an amine product. Compared with the prior art, the technical scheme of the application reduces environmental pollution from the source, simplifies equipment, reduces equipment investment and energy consumption, and is suitable for large-scale production.

Inventors

  • WAN YE
  • LI YUANXIAO
  • CHANG XIN
  • ZHAO XIZHE
  • LIU JIANHUA
  • ZHANG JIE
  • ZHOU ZHIPENG
  • YUAN ZHENJUN

Assignees

  • 洛阳中硅高科技有限公司
  • 中国恩菲工程技术有限公司
  • 中国有色工程有限公司

Dates

Publication Date
20260508
Application Date
20230414

Claims (20)

  1. 1. An amino silane byproduct recovery device, the recycling device is characterized by comprising: The liquid ammonia reactor (1) is provided with an inlet and an outlet, the inlet of the liquid ammonia reactor is respectively connected with a liquid ammonia source and an amino hydrochloride source, and the liquid ammonia reactor (1) is used for carrying out neutralization reaction on raw materials comprising liquid ammonia and amino hydrochloride to obtain a product system; A flash tank (2) with an inlet, a flash ammonia outlet and a flash liquid outlet, wherein the inlet is connected with the outlet of the liquid ammonia reactor (1), the flash tank (2) is used for carrying out flash evaporation treatment on the product system to obtain flash ammonia and flash liquid, and And the filter (3) is provided with an inlet and an outlet, the inlet of the filter is connected with the flash liquid outlet, and the filter (3) is used for carrying out solid-liquid separation on the flash liquid to obtain an ammonium chloride solid filter cake and an amine product.
  2. 2. The recycling apparatus according to claim 1, the recycling device is characterized by further comprising: and the condenser (4) is provided with an inlet and an outlet, and the inlet of the condenser is connected with the flash ammonia outlet and is used for condensing the flash ammonia.
  3. 3. Recovery device according to claim 2, characterized in that the outlet of the condenser (4) is connected to the inlet of the liquid ammonia reactor (1).
  4. 4. A method for recovering an aminosilane by-product, said method comprising: step S1, carrying out a neutralization reaction on raw materials comprising liquid ammonia and amino hydrochloride to obtain a product system; Step S2, carrying out flash evaporation treatment on the product system to obtain flash evaporation ammonia gas and flash evaporation liquid, and And S3, carrying out solid-liquid separation on the flash evaporation liquid to obtain an ammonium chloride solid filter cake and an amine product.
  5. 5. The recycling method according to claim 4, characterized in that the recycling method further comprises: and S4, condensing the flash ammonia gas to obtain condensed flash ammonia gas.
  6. 6. The recovery method according to claim 5, wherein the condensed flash ammonia gas is returned to the step S1.
  7. 7. The recovery method according to claim 5, wherein the condensing treatment is carried out at a temperature of-60 to-30 ℃.
  8. 8. The recycling method according to any one of claims 4 to 7, characterized in that the recycling method further comprises: The amine product is returned to the step S1.
  9. 9. The recovery method according to any one of claims 4 to 7, wherein the purity of the amine product is 93-99%.
  10. 10. The recovery method of claim 9, wherein the purity of the amine product is 97-99%.
  11. 11. The recovery method according to any one of claims 4 to 7, wherein the amine product is selected from any one or more of primary amine, secondary amine, tertiary amine.
  12. 12. The method according to any one of claims 4 to 7, wherein in step S1, the molar ratio of the liquid ammonia to the amine-based hydrochloride is 1 to 35:1.
  13. 13. The recovery method according to any one of claims 4 to 7, wherein the pressure of the neutralization reaction is 0.01 to 0.6mpa.
  14. 14. The recovery method according to any one of claims 4 to 7, wherein the temperature of the neutralization reaction is-60 to 10 ℃.
  15. 15. The recovery method according to any one of claims 4 to 7, wherein the neutralization reaction time is 1 to 3 hours.
  16. 16. The recovery method according to any one of claims 4 to 7, wherein the amine hydrochloride is selected from any one or more of primary amine hydrochloride, secondary amine hydrochloride, tertiary amine hydrochloride.
  17. 17. The recovery method according to any one of claims 4 to 7, characterized in that the liquid ammonia is added to the neutralization reaction system in a stirred state.
  18. 18. The recycling method according to any one of claims 17, characterized in that the rotational speed of the stirring is 5 to 300r/min.
  19. 19. The method according to claim 17, wherein the liquid ammonia is added to the neutralization reaction system at a temperature of-60 to-30 ℃.
  20. 20. The recovery method according to any one of claims 4 to 7, wherein in the step S2, the pressure of the flash evaporation treatment is 10kpa to 0.3mpa.

Description

Recovery device and recovery method for aminosilane by-product Technical Field The invention relates to the technical field of aminosilane byproduct recovery, in particular to a device and a method for recovering aminosilane byproducts. Background The aminosilane precursor is used for various deposition processes, mainly for preparing novel precursors of silicon oxide and silicon nitride by a low-temperature atomic layer vapor deposition (ALD) technology, is used for preparing novel materials of silicon-based high dielectric constant (high-k) films, and is used for advanced integrated circuit processes (nodes of 28nm and below). In recent years, with the rapid development of economy, aminosilane raw materials and production cost are higher and higher, and requirements on environmental protection and energy consumption are also stricter and stricter. The treatment of the byproduct amino hydrochloride generated by the amino silane is urgent, and the recycling of the amino hydrochloride not only can recycle the raw materials required by production, reduce the production cost and the energy consumption, but also can reduce the environmental pollution, thereby having high economic and environmental benefits. Yangping et al mention in the study of the direct amination of isobutene to tert-butylamine that the more 4% of the primary yield of tert-butylamine is obtained by the post-treatment of the conversion of tert-butylamine to the hydrochloride. 67g (1.2 mol) of isobutene and 45g (2.65 mol) of ammonia were introduced into a high-pressure reactor equipped with an H-Y catalyst, and the reaction was carried out at a temperature of 256℃and a pressure of 50 kg for 8 hours. The product tert-butylamine is absorbed by hydrochloric acid, the absorption liquid is concentrated, suction filtered, the filtrate is adjusted to alkalinity by sodium hydroxide, and extracted by dichloromethane. Adding 1:1 hydrochloric acid into the extract to make the extract strong in acidity, separating the solution, and evaporating the aqueous phase to obtain tert-butylamine hydrochloride (m.p.278-280 ℃ and 291 ℃ for decomposition). Then mixing the hydrochloride, 6g of sodium hydroxide and 1mol of water, fractionating, collecting 40-50 ℃ fractions to obtain 3.59 of tert-butylamine with a yield of about 4% (one-time conversion rate), and introducing an alkaline aqueous solution into the process, wherein the alkaline aqueous solution has a high water content, so that an aminosilane product is hydrolyzed, polymerized and deteriorated, and cannot be reused as a production raw material. Hu Jianghua et al in the chinese patent application CN 102898460A disclose a process for preparing diaminosilane and treating by-products thereof, wherein it is mentioned that a certain temperature and pressure are controlled to prepare diaminosilane, the by-product of the lower layer is ethylenediamine hydrochloride, calcium oxide with an effective content of 99% is added into ethylenediamine hydrochloride of the lower layer, ethylenediamine is obtained by distillation under vacuum of-0.08 MPa under stirring at 100 rpm, the ethylenediamine content recovered by reaction and salt recovery is above 98%, the water content is about 0.002%, the process requires solid-solid reaction, a small amount of water is generated during the reaction, and then diethylamine is treated by vacuum purification, the process has many treatment facilities and complex process routes. Disclosure of Invention The invention mainly aims to provide a recovery device and a recovery method for an aminosilane byproduct, which are used for solving the problems of complex processing equipment, complex process route and easy partial deterioration of a product of the aminosilane byproduct in the prior art. In order to achieve the above object, according to one aspect of the present invention, there is provided an aminosilane by-product recovery apparatus comprising a liquid ammonia reactor having an inlet and an outlet, the inlet of which is connected to a liquid ammonia source and an aminochloride source, respectively, a liquid ammonia reactor for neutralizing a raw material comprising liquid ammonia and aminochloride to obtain a product system, a flash tank having an inlet, a flash ammonia outlet and a flash liquid outlet, the inlet of which is connected to the outlet of the liquid ammonia reactor, a flash tank for flash-evaporating the product system to obtain flash ammonia and a flash liquid, and a filter having an inlet and an outlet, the inlet of which is connected to the flash liquid outlet, the filter for solid-liquid separating the flash liquid to obtain an ammonium chloride solid cake and an amine product. Further, the recovery device further comprises a condenser, wherein the condenser is provided with an inlet and an outlet, and the inlet is connected with the flash ammonia outlet and is used for condensing the flash ammonia. Further, the outlet of the condenser is connected with the inlet