WO2021075618A1 - Alkylene carbonate production system, and production method using same - Google Patents

Alkylene carbonate production system, and production method using same Download PDF

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Publication number
WO2021075618A1
WO2021075618A1 PCT/KR2019/014132 KR2019014132W WO2021075618A1 WO 2021075618 A1 WO2021075618 A1 WO 2021075618A1 KR 2019014132 W KR2019014132 W KR 2019014132W WO 2021075618 A1 WO2021075618 A1 WO 2021075618A1
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reactor
alkylene carbonate
reaction product
distillation column
steam
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PCT/KR2019/014132
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French (fr)
Korean (ko)
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양준화
백제범
조진수
신동희
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그린케미칼 주식회사
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Priority to JP2019565434A priority Critical patent/JP2022551354A/en
Publication of WO2021075618A1 publication Critical patent/WO2021075618A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
    • C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D317/34—Oxygen atoms
    • C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0239—Quaternary ammonium compounds
    • 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
    • Y02P20/141—Feedstock

Definitions

  • the present invention relates to the production of alkylene carbonate, and more particularly, in the presence of a phenolic organic catalyst, carbon dioxide and alkylene oxide are reacted in an integrated heat exchanger reactor, and the thermal energy generated during the reaction is reused in an integrated distillation column to reboil alkylene carbonate. It relates to the production of alkylene carbonate to purify.
  • Exhaust gases emitted from various industries such as thermal power plants contain large amounts of air pollutants such as acid gases such as carbon dioxide and fine dust.
  • the technology for separating and treating harmful substances in exhaust gas is increasing in importance not only in the industrial aspect, but also for the sustainable development of civilization.
  • fossil fuels such as coal, oil, and natural gas are used, the need for economical carbon dioxide treatment technology development is urgent.
  • alkylene carbonate is an intermediate of various synthetic raw materials, raw materials of polycarbonate, intermediates in pharmaceutical processes, oxyalkylation agents in the synthesis process of dyestuffs, protective agents for process facilities, and solvents in the textile production process. It is used as a polymer electrolyte solvent for secondary batteries, and its use range is expanding.
  • a conventional method of reacting ethylene glycol and phosgene (COCl 2 ) was used.
  • the reaction for producing alkylene carbonate by reacting an alkylene oxide with carbon dioxide in the presence of a catalyst is a supercritical reaction and generates a very large heat of reaction of 125.5 KJ/mol. Accordingly, it is particularly important for the safety of the process to stably remove the reaction heat during the production of alkylene carbonate, and typically, a heat exchanger is used to remove the reaction heat generated. However, the addition of a heat exchanger not only complicates the process, but also increases the energy required.
  • the prepared alkylene carbonate is commercialized through a purification process, and a general purification process of alkylene carbonate uses a distillation process, specifically, impurities are removed in a distillation column to obtain purified alkylene carbonate.
  • the high temperature heat applied in the purification process through distillation has a problem in that a large amount of energy is consumed in the production of alkylene carbonate.
  • carbon dioxide used in the reaction process is released as a by-product, and efficient recovery of the carbon dioxide used in the reaction process may also be a problem with reduction of thermal energy.
  • Korean Patent Application Publication No. 2006-0026034 discloses a method for producing alkylene carbonate including a reactor and a heat exchanger. However, this has a problem that the process becomes complicated by providing a separate heat exchanger.
  • Korean Patent Application Publication No. 2007-0016666 relates to the production of alkylene carbonate, and discloses a catalytic addition reaction method using a membrane separator to synthesize high purity alkylene carbonate. A simple filter is used to separate the catalyst and alkylene carbonate by supplying the reactant to a membrane separator, which takes a long time and still has a problem that impurities are included in addition to the alkylene carbonate in the liquid phase of the reactant.
  • the present invention provides a system and method for producing alkylene carbonate in which alkylene oxide and carbon dioxide are reacted in a heat exchanger-integrated reactor in the presence of a phenolic organic catalyst, and the thermal energy generated during the reaction is reused in a reboiler integrated distillation column to purify alkylene carbonate. I want to.
  • the present inventors produce carbon dioxide and alkylene oxide as alkylene carbonate in a heat exchanger-integrated reactor in the presence of a phenolic organic catalyst, and purify it in an integrated reboiler distillation column, but an energy-saving type that can be purified by reusing the heat energy generated during the reaction.
  • the present invention was completed by discovering a production system and method with alkylene carbonate.
  • the present invention is a system for the production and purification of alkylene carbonate, the system comprising: a first reactor for synthesizing a first reaction product containing alkylene carbonate by reacting an alkylene oxide and carbon dioxide in the presence of a phenolic organic catalyst; A second reactor connected to the first reactor and supplying the first reaction product to react unreacted reactants to synthesize a second reaction product containing alkylene carbonate; A gas-liquid separation drum connected to the second reactor and supplied with the second reaction product to separate carbon dioxide and a final reaction product; And a distillation column connected to the gas-liquid separation drum and into which a final reaction product separated from carbon dioxide in the gas-liquid separation drum is added to purify alkylene carbonate, and the first reactor is a heat exchanger integrated reactor.
  • a reaction retention portion positioned at the top of the first reactor and having carbon dioxide, alkylene oxide and catalyst injection portions, respectively, and having an open lower surface thereof;
  • a shell & tube type heat exchanger having a steam condensate injection part and a first steam discharge part connected to the open lower surface of the reaction holding part and the open upper surface through a flange coupling;
  • a first reaction product discharge unit connected to the open bottom surface of the shell and tube heat exchange unit through a flange connection and located at the bottom of the first reactor, and the second reactor includes water for controlling reaction temperature on an outer circumferential surface.
  • a jacket is provided, and a second steam outlet is provided at the top, the distillation column is a reboiler integrated distillation column having a reboiler at the bottom, and the steam from the first and second steam discharges is supplied to the reboiler of the distillation column. It provides a system for producing alkylene carbonate, which is used as a heat source.
  • the operating temperature of the first reactor is 150 °C to 185 °C
  • the pressure is 4.9 to 9.8 MpaG
  • the operating temperature of the second reactor is 150 °C to 170 °C
  • the pressure is 3.5 to 5.0 MpaG.
  • the present invention also provides a system for producing an alkylene carbonate in which 70° C. to 133° C. steam condensed water is injected into the steam condensed water injection unit of the first reactor and the water jacket of the second reactor.
  • the present invention also provides a system for producing an alkylene carbonate, wherein the phenolic organic catalyst is an organic catalyst represented by the following formula (1).
  • R is hydrogen, a C 1 to C 10 alkyl group, I, Br, Cl, F, OMe, NO 2 or NMe 2
  • X is I, Br, Cl, or NO 3 .
  • the reboiling integrated distillation column has a packing part, and the packing material is a structured packing in which a corrugated wire gauze plate in the form of a corrugated plate is regularly arranged is stacked in multiple stages. It provides a structure, a system for producing alkylene carbonate.
  • the present invention is also a method for producing an alkylene carbonate, the method comprising: injecting carbon dioxide, an alkylene oxide, and a phenol-based organic catalyst into a first reactor to synthesize a first reaction product containing an alkylene carbonate; Injecting the first reaction product into a second reactor to react the unreacted product to synthesize a second reaction product containing alkylene carbonate; Supplying the secondary reaction product to a gas-liquid separation drum to separate carbon dioxide and a final reaction product; And supplying the final reaction product to a distillation column connected to a gas-liquid separation drum to purify the alkylene carbonate, wherein the first reactor is a heat exchanger integrated reactor, located at the top of the first reactor, and carbon dioxide , An alkylene oxide and a catalyst injection portion, respectively, and a reaction retention portion having an open lower surface thereof; A shell & tube type heat exchanger having a steam condensate injection part and a first steam discharge part connected to the open lower surface of the reaction holding part and the open upper
  • a jacket is provided, and a second steam discharge unit is provided at the top, and the distillation column is an integrated reboiler distillation column having a reboiler at the bottom, and the steam from the steam discharge units of the first and second reactors is supplied from the distillation column. It provides a method for producing alkylene carbonate, which is supplied to the reboiler and used as a heat source.
  • the operating temperature of the first reactor is 150 °C to 185 °C
  • the pressure is 4.9 to 9.8 MpaG
  • the operating temperature of the second reactor is 150 °C to 170 °C
  • the pressure is 3.5 to 5.0.
  • the reboiling integrated distillation column has a packing unit, and the packing material is It is a structure in which structured packing in which a corrugated wire gauze plate in the form of a corrugated plate is regularly arranged is stacked in multiple stages, and the phenolic organic catalyst is made of alkylene carbonate, an organic catalyst represented by the following formula (1). Provides a manufacturing method.
  • R is hydrogen, a C 1 to C 10 alkyl group, I, Br, Cl, F, OMe, NO 2 or NMe 2
  • X is I, Br, Cl, or NO 3 .
  • the system and method for producing alkylene carbonate of the present invention can simplify the device used in the process by using a heat exchanger-integrated reactor and a reboiler-integrated distillation column, and the generated steam is reused as thermal energy in the alkylene carbonate purification process.
  • Carbon dioxide can be efficiently commercialized while reducing the energy and cost required.
  • FIG. 1 is a schematic diagram of an alkylene carbonate production system according to an embodiment of the present invention.
  • FIG. 2 is a cross-sectional view of the first reactor of the system for producing alkylene carbonate according to an embodiment of the present invention.
  • FIG 3 is a cross-sectional view of a second reactor of the system for producing alkylene carbonate according to an embodiment of the present invention.
  • FIG. 4 is a cross-sectional view of a reboiling integrated distillation column of an alkylene carbonate production system according to an embodiment of the present invention.
  • the system of the present invention can synthesize alkylene carbonate by reacting alkylene oxide and carbon dioxide at high temperature and high pressure in the presence of a catalyst.
  • the system comprises: a first reactor 10 for reacting alkylene oxide and carbon dioxide in the presence of a phenol-based organic catalyst to synthesize a first reaction product containing alkylene carbonate; A second reactor (20) connected to the first reactor, wherein the first reaction product is supplied to react unreacted reactants to synthesize a second reaction product containing alkylene carbonate; A gas-liquid separation drum 30 connected to the second reactor and supplying the second reaction product to separate carbon dioxide and a final reaction product; And a distillation column 40 connected to the gas-liquid separation drum and into which a final reaction product separated from carbon dioxide in the gas-liquid separation drum is added to purify the alkylene carbonate.
  • An alkylene oxide, carbon dioxide, and a phenol-based organic catalyst are supplied to the first reactor 10 of the system of the present invention to prepare a first reaction product including alkylene carbonate.
  • the operating temperature of the first reactor 10 is 150°C to 185°C and the pressure is 4.9 to 9.8 MpaG. If it is carried out under too low temperature conditions, the reaction time is lengthened, and if the temperature is increased, the reaction time is shortened, but it is unnecessary because the reaction time is no longer shortened compared to the additional cost for this.
  • the alkylene oxide is from the group consisting of ethylene oxide, propylene oxide, butylene oxide, hexylene oxide, and styrene oxide. It may be selected. Ethylene carbonate can be produced preferably by using ethylene oxide.
  • the phenolic organic catalyst may be added and used in an amount of 0.01 to 10 mol% relative to the alkylene oxide, but is not limited thereto. If it is used in less than 0.01 mol%, the reaction time becomes too long, and if the concentration is increased, the reaction time is shortened, but if it is used in more than 10 mol%, there is no economic benefit due to an increase in the catalyst unit cost.
  • the catalyst used in the reaction for preparing the alkylene carbonate of the present invention is a phenolic organic catalyst, which is an organic catalyst represented by the following formula (1).
  • R is hydrogen, a C 1 to C 10 alkyl group, I, Br, Cl, F, OMe, NO 2 or NMe 2
  • X is I, Br, Cl, or NO 3
  • R is a C 4 alkyl group or NMe 2 It is possible to use a phenolic organic catalyst.
  • the first reactor 10 of the present invention is a heat exchanger-integrated reactor as shown in FIG. 2(a), located at the top of the first reactor, and having carbon dioxide, alkylene oxide, and catalyst injection portions, respectively, and the lower surface thereof is opened.
  • a first reaction product discharge part 13 that is connected to an open lower surface of the shell and tube heat exchange part and an open upper surface through a flange coupling, and is located at a lower end of the first reactor.
  • the retention portion may secure the reaction retention time to improve the reaction efficiency of the synthesis of alkylene carbonate, and the shell and tube heat exchange portion connected to the retention portion may be provided to simplify the apparatus compared to a conventional system having a separate heat exchanger.
  • Steam condensed water is injected into the shell-and-tube heat exchange unit to control the reaction heat generated during the reaction and produce steam. For example, steam condensed water from 70°C to 133°C is injected into the steam condensed water injection unit below the heat exchange unit and the reaction temperature is adjusted, and then the generated steam may be discharged to the primary steam discharge unit 101 located above the heat exchange unit. .
  • the generated steam is supplied to the reboiler of distillation in the purification process described later of the present invention and can be used as thermal energy, thereby saving required thermal energy.
  • the first reaction product synthesized in the first reactor of the present invention may be supplied to the second reactor to perform an additional reaction.
  • 3 (a) is a cross-sectional view of the second reactor of the present invention in one embodiment, and (b) is a cross-sectional view at each position.
  • the second reactor for example, a continuous stirred tank reactor may be used, and an unreacted product not reacted in the first reactor is reacted to increase the yield of alkylene carbonate.
  • the operating temperature of the second reactor is 150°C to 170°C and the pressure is 3.5 to 5.0 MpaG.
  • the second reactor may be provided with a water jacket for controlling the reaction temperature on the outer circumferential surface, and may be provided with a second steam discharge unit 201 at the top. In one embodiment, 70°C to 133°C steam condensed water may be injected into the water jacket to control the reaction temperature of the second reactor.
  • the final reaction product is supplied to the gas-liquid separation drum 30 to separate gas and liquid, and carbon dioxide is contained in the gas phase and the synthesized alkylene carbonate is contained in the liquid phase.
  • the gas-liquid separator may be equipped with a level instrument and a flow instrument, and a stable supply is possible through mutual control.
  • the alkylene carbonate present in the liquid phase it may be purified using a distillation method, and in the present invention, the alkylene carbonate present in the liquid product is purified using a distillation column.
  • the distillation column purifies the alkylene carbonate using high-temperature steam supplied from the reboiler
  • the integrated reboiler distillation column 40 of the present invention comprises: a packing part 41 having an open bottom surface; A gas-liquid separator 42 to which the open lower surface of the filling part is connected to the open upper surface through a flange coupling; And a reboiler 43 that is connected to an open bottom surface of the gas-liquid separation unit and an open top surface through a flange coupling, and is located under the gas-liquid separation unit.
  • the distillation column of the present invention may include a packing part 41 in the distillation column.
  • the filler is a structure in which structured packing in which corrugated wire gauze plates are regularly arranged is stacked in multiple stages.
  • the filler may be formed of a corrugated sheet of porous metal, plastic (including PTFE), or wire gauze depending on the application.
  • the ribs formed after processing a wire guaze in which a metal wire is woven with a blade and a transverse thread to have a structure similar to a fabric is processed into a serrated corrugated form are oblique lines. It is possible to use repetitive structural fillers so as to make the shape of the oblique line opposite to each other.
  • the distillation using the structural filler of the present invention causes vaporization of the liquid on the surface of the liquid thin film formed on the structural filler.
  • the vaporized alkylene carbonate goes to the top of the distillation column, and the solution flows down to the bottom.
  • the vaporized alkylene carbonate is discharged to the top of the distillation column and supplied to a condenser.
  • the thickness of the liquid thin film formed on the surface of the wire gauze is 0.1 to 0.5 mm thick, which can be controlled using a flow controller.
  • the solution passing through the filling part flows down to the gas-liquid separation part.
  • the gas-liquid separation unit is a space that facilitates the flow of the alkylene carbonate evaporated from the final reaction product upward and the other solutions downward.
  • the gas-liquid separation unit of the present invention is provided with a storage tank 421 and a solution discharge line 422 below the storage tank, so that the accumulated liquid can be immediately supplied to the reboiler 43.
  • the reboiler located at the bottom of the distillation column of the present invention can simultaneously secure a wide liquid evaporation area of the kettle-type reboiler of the existing process and the energy efficiency excellence of the thermosiphon-type reboiler.
  • the reboil can be purified by heating the final reaction product and evaporating ethylene carbonate.
  • the reboiler uses a tube-type heat exchanger, and a fluid such as steam or hot oil heated externally can be injected and circulated to the heat exchanger.
  • the carbonate is purified.
  • the steam 101 and 201 generated in the first and second reactors described above may be injected into the steam injection unit 401 of the reboiler.
  • the steam generated in the first reactor may be produced at 166.4 kg/hr, and the steam used in the distillation column may use 69.3 kg/hr.
  • the steam injected into the distillation column reuses thermal energy generated in the process, thereby reducing thermal energy required for ethylene carbonate purification.
  • the alkylene carbonate production system of the present invention has a spatial advantage by using a heat exchanger-integrated reactor and a reboiler-integrated distillation column, and by reusing the thermal energy generated in the reactor for product purification, it is possible to reduce energy and cost required for the process. .
  • the present invention is a method for producing an alkylene carbonate using the alkylene carbonate production system, wherein the method includes an alkylene carbonate by injecting carbon dioxide, an alkylene oxide, and a phenol-based organic catalyst into the first reactor. Synthesizing the primary reaction product; Injecting the first reaction product into a second reactor to react the unreacted product to synthesize a second reaction product containing alkylene carbonate; Supplying the secondary reaction product to a gas-liquid separation drum to separate carbon dioxide and a final reaction product; And supplying the final reaction product to a distillation column connected to a gas-liquid separation drum to purify the alkylene carbonate.
  • the phenolic organic catalyst, the first reactor, the second reactor, and the distillation column may use the same configuration and operating conditions as the above-described alkylene carbonate system, and the steam discharge portion of the first reactor and the second reactor Is supplied to the reboiler of the distillation column and used as a heat source to reduce thermal energy.

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Abstract

The present invention relates to the production of an alkylene carbonate via the synthesis of an alkylene oxide and carbon dioxide, and more specifically, to the production and purification of an alkylene carbonate via the use of a heat exchanger-integrated reactor and a reboiler-integrated distillation column. A system and method for producing an alkylene carbonate according to the present invention uses a heat exchanger-integrated reactor, thus making it possible to simplify the equipment used in the process, and uses generated steam as heat energy by injecting the same into a reboiler-integrated distillation column for performing purification of alkylene carbonate, thus making it possible to reduce the energy and cost required by the process.

Description

알킬렌카보네이트 제조 시스템 및 그를 이용한 제조방법Alkylene carbonate manufacturing system and manufacturing method using the same
본 발명은 알킬렌카보네이트 제조에 관한 것으로, 보다 상세하게는 페놀계 유기촉매 존재 하에 이산화탄소와 알킬렌옥사이드를 열교환기 일체형 반응기에서 반응시키고, 반응 시 발생한 열에너지를 재비기 일체형 증류탑에서 재사용하여 알킬렌카보네이트를 정제하는 알킬렌카보네이트 제조에 관한 것이다.The present invention relates to the production of alkylene carbonate, and more particularly, in the presence of a phenolic organic catalyst, carbon dioxide and alkylene oxide are reacted in an integrated heat exchanger reactor, and the thermal energy generated during the reaction is reused in an integrated distillation column to reboil alkylene carbonate. It relates to the production of alkylene carbonate to purify.
화력발전소 등 다양한 산업체에서 배출되는 배가스에는 이산화탄소 등의 산성가스와 미세먼지 등 대기오염물질이 다량 포함되어 있다. 이러한 배기가스 내 유해물질의 분리 및 처리 기술은 산업적 측면에서 뿐 아니라 인류의 지속 가능한 발전을 위해 중요성이 날로 증가하고 있다. 석탄, 석유, 천연가스 등 화석연료가 사용되는 상황에서 경제적인 이산화탄소 처리 기술 개발의 필요성은 절실하다.Exhaust gases emitted from various industries such as thermal power plants contain large amounts of air pollutants such as acid gases such as carbon dioxide and fine dust. The technology for separating and treating harmful substances in exhaust gas is increasing in importance not only in the industrial aspect, but also for the sustainable development of mankind. In the situation where fossil fuels such as coal, oil, and natural gas are used, the need for economical carbon dioxide treatment technology development is urgent.
한편, 알킬렌카보네이트(Alkylene carbonate)는 다양한 합성 원료의 중간체, 폴리카보네이트의 원료, 제약공정의 중간체, 염료(dyestuff) 합성 과정의 옥시알킬화 시약(oxyalkylation agent), 공정설비 보호제, 섬유 생산 공정의 용매로 사용되고, 이차전지의 고분자 전해질 용매로 그 사용 범위가 확대되고 있다. 알킬렌카보네이트의 제조에는 종래 에틸렌 글리콜(ethylene glycol)과 포스젠(COCl2)을 반응시키는 방법이 이용되었다. 그러나 원료물질인 포스젠의 맹독성과 환경오염 물질인 염화수소의 부생문제 등으로 인해 최근에는 하기 반응식 1과 같이 주로 알킬렌옥사이드와 이산화탄소를 촉매 및 가압조건에서 반응시키는 공정이 사용되면서 이산화탄소의 저감 및 이의 실질적인 제품화가 이루어지고 있다.On the other hand, alkylene carbonate is an intermediate of various synthetic raw materials, raw materials of polycarbonate, intermediates in pharmaceutical processes, oxyalkylation agents in the synthesis process of dyestuffs, protective agents for process facilities, and solvents in the textile production process. It is used as a polymer electrolyte solvent for secondary batteries, and its use range is expanding. In the production of alkylene carbonate, a conventional method of reacting ethylene glycol and phosgene (COCl 2 ) was used. However, due to the severe toxicity of phosgene as a raw material and by-products of hydrogen chloride as an environmental pollutant, in recent years, a process of reacting mainly alkylene oxide and carbon dioxide under catalyst and pressurized conditions as shown in Scheme 1 below is used to reduce carbon dioxide and reduce its Substantial commercialization is taking place.
Figure PCTKR2019014132-appb-I000001
Figure PCTKR2019014132-appb-I000001
촉매의 존재하에 알킬렌옥사이드를 이산화탄소와 반응시켜 알킬렌카보네이트를 제조하기 위한 반응은, 초임계 반응으로 125.5 KJ/mol이라는 매우 큰 반응열을 발생시킨다. 이에 따라, 알킬렌카보네이트의 제조시 안정적으로 반응열을 제거하는 것이 공정의 안전을 위해 특히 중요하며, 통상적으로, 발생하는 반응열을 제거하는 데 열 교환기가 이용된다. 그러나, 열교환기의 추가는 공정을 복잡하게 할 뿐만 아니라, 필요한 에너지 또한 증가하게 된다.The reaction for producing alkylene carbonate by reacting an alkylene oxide with carbon dioxide in the presence of a catalyst is a supercritical reaction and generates a very large heat of reaction of 125.5 KJ/mol. Accordingly, it is particularly important for the safety of the process to stably remove the reaction heat during the production of alkylene carbonate, and typically, a heat exchanger is used to remove the reaction heat generated. However, the addition of a heat exchanger not only complicates the process, but also increases the energy required.
제조된 알킬렌카보네이트는 정제 공정을 거쳐 제품화되는데, 일반적인 알킬렌카보네이트의 정제 공정은 증류공정을 이용하며, 구체적으로는 증류탑에서 불순물을 제거해서 정제된 알킬렌카보네이트를 얻게 된다. 증류를 통한 정제공정에서 가해지는 고온의 열은 알킬렌카보네이트 제조에 많은 양의 에너지를 소모하도록 하는 문제가 있다. 또한, 반응공정에서 사용된 이산화탄소가 부산물로 방출되는데 이의 효율적인 회수도 열에너지 저감과 함께 문제될 수 있다.The prepared alkylene carbonate is commercialized through a purification process, and a general purification process of alkylene carbonate uses a distillation process, specifically, impurities are removed in a distillation column to obtain purified alkylene carbonate. The high temperature heat applied in the purification process through distillation has a problem in that a large amount of energy is consumed in the production of alkylene carbonate. In addition, carbon dioxide used in the reaction process is released as a by-product, and efficient recovery of the carbon dioxide used in the reaction process may also be a problem with reduction of thermal energy.
대한민국 공개특허 2006-0026034호는 반응기와 열교환기를 포함하는 알킬렌카보네이트 제조방법을 개시한다. 그러나 이는 별도의 열교환기를 구비함으로써 공정이 복잡해지는 문제점이 있다. 대한민국 공개특허 2007-0016666호는 알킬렌카보네이트 제조에 관한 것으로, 고순도 알킬렌카보네이트를 합성하기 위해 막분리기를 이용한 촉매부가반응공법을 개시한다. 반응물을 막분리기로 공급하여 촉매와 알킬렌카보네이트를 분리하는 것으로 단순 필터를 이용하는 것이며, 이는 시간이 오래 걸리고 반응물 액상내의 알킬렌카보네이트 외에도 불순물이 포함되는 문제점을 여전히 가진다.Korean Patent Application Publication No. 2006-0026034 discloses a method for producing alkylene carbonate including a reactor and a heat exchanger. However, this has a problem that the process becomes complicated by providing a separate heat exchanger. Korean Patent Application Publication No. 2007-0016666 relates to the production of alkylene carbonate, and discloses a catalytic addition reaction method using a membrane separator to synthesize high purity alkylene carbonate. A simple filter is used to separate the catalyst and alkylene carbonate by supplying the reactant to a membrane separator, which takes a long time and still has a problem that impurities are included in addition to the alkylene carbonate in the liquid phase of the reactant.
따라서 효율적이면서도 경제적으로 알킬렌카보네이트를 제조할 수 있는 장치의 필요성이 제기되고 있다.Accordingly, there is a need for an apparatus capable of efficiently and economically producing alkylene carbonate.
[선행기술문헌][Prior technical literature]
[특허문헌][Patent Literature]
대한민국 공개특허 2006-0026034Republic of Korea Patent Publication 2006-0026034
대한민국 공개특허 2007-0016666Republic of Korea Patent Publication 2007-0016666
본 발명은 알킬렌옥사이드와 이산화탄소를 페놀계 유기촉매 존재 하에 열교환기 일체형 반응기에서 반응시키고, 반응 시 발생한 열에너지를 재비기 일체형 증류탑에서 재사용하여 알킬렌카보네이트를 정제하는 알킬렌카보네이트 제조 시스템 및 방법을 제공하고자 한다.The present invention provides a system and method for producing alkylene carbonate in which alkylene oxide and carbon dioxide are reacted in a heat exchanger-integrated reactor in the presence of a phenolic organic catalyst, and the thermal energy generated during the reaction is reused in a reboiler integrated distillation column to purify alkylene carbonate. I want to.
본 발명자들은 페놀계 유기촉매 존재하에 이산화탄소 및 알킬렌옥사이드를 열교환기 일체형 반응기에서 알킬렌카보네이트로 제조하고, 이를 재비기 일체형 증류탑에서 정제하되 반응시 발생하는 열에너지를 재사용하여 정제할 수 있는 에너지 절감형 알킬렌카보네이트로 제조 시스템 및 방법을 발견하여 본 발명을 완성하였다. The present inventors produce carbon dioxide and alkylene oxide as alkylene carbonate in a heat exchanger-integrated reactor in the presence of a phenolic organic catalyst, and purify it in an integrated reboiler distillation column, but an energy-saving type that can be purified by reusing the heat energy generated during the reaction. The present invention was completed by discovering a production system and method with alkylene carbonate.
본 발명은 알킬렌카보네이트의 제조 및 정제를 위한 시스템으로, 상기 시스템은 알킬렌옥사이드와 이산화탄소를 페놀계 유기촉매 존재하에 반응시켜 알킬렌카보네이트가 포함된 1차 반응 생성물을 합성하는 제 1차 반응기; 상기 제 1차 반응기와 연결되고, 상기 1차 반응 생성물이 공급되어 미반응 반응물을 반응시켜 알킬렌카보네이트가 포함된 2차 반응 생성물을 합성하는 제 2차 반응기; 상기 제 2차 반응기와 연결되고, 상기 2차 반응 생성물이 공급되어 이산화탄소와 최종 반응 생성물을 분리하는 기-액분리 드럼; 및 상기 기-액분리 드럼과 연결되고, 상기 기-액분리 드럼에서 이산화탄소와 분리된 최종 반응 생성물이 투입되어 알킬렌카보네이트가 정제되는 증류탑을 포함하고, 상기 제 1차 반응기는 열교환기 일체형 반응기로, 상기 제 1차 반응기 상단에 위치하며 이산화탄소, 알킬렌옥사이드 및 촉매 주입부를 각각 구비하며 하면이 개방된 반응 체류부; 상기 반응 체류부의 개방된 하면과 플랜지(Flange) 결합을 통해 개방된 상면이 연결되고 스팀응축수 주입부 및 제 1차 스팀배출부를 구비하는 쉘앤튜브(shell & tube)형 열교환부; 및 상기 쉘앤튜브 열교환부의 개방된 하면과 플랜지 결합을 통해 개방된 상면이 연결되며 상기 제 1차 반응기 하단에 위치하는 1차 반응 생성물 배출부를 포함하고, 상기 제 2차 반응기는 외주면에 반응 온도 조절용 워터자켓을 구비하고, 상부에는 제 2차 스팀 배출부를 구비하며, 상기 증류탑은 재비기가 하단에 구비된 재비기 일체형 증류탑이고, 상기 제 1차 및 제 2차 스팀 배출부의 스팀은 상기 증류탑의 재비기에 공급되어 열원으로 사용되는, 알킬렌카보네이트의 제조 시스템을 제공한다.The present invention is a system for the production and purification of alkylene carbonate, the system comprising: a first reactor for synthesizing a first reaction product containing alkylene carbonate by reacting an alkylene oxide and carbon dioxide in the presence of a phenolic organic catalyst; A second reactor connected to the first reactor and supplying the first reaction product to react unreacted reactants to synthesize a second reaction product containing alkylene carbonate; A gas-liquid separation drum connected to the second reactor and supplied with the second reaction product to separate carbon dioxide and a final reaction product; And a distillation column connected to the gas-liquid separation drum and into which a final reaction product separated from carbon dioxide in the gas-liquid separation drum is added to purify alkylene carbonate, and the first reactor is a heat exchanger integrated reactor. , A reaction retention portion positioned at the top of the first reactor and having carbon dioxide, alkylene oxide and catalyst injection portions, respectively, and having an open lower surface thereof; A shell & tube type heat exchanger having a steam condensate injection part and a first steam discharge part connected to the open lower surface of the reaction holding part and the open upper surface through a flange coupling; And a first reaction product discharge unit connected to the open bottom surface of the shell and tube heat exchange unit through a flange connection and located at the bottom of the first reactor, and the second reactor includes water for controlling reaction temperature on an outer circumferential surface. A jacket is provided, and a second steam outlet is provided at the top, the distillation column is a reboiler integrated distillation column having a reboiler at the bottom, and the steam from the first and second steam discharges is supplied to the reboiler of the distillation column. It provides a system for producing alkylene carbonate, which is used as a heat source.
본 발명은 또한, 상기 제 1차 반응기의 운전온도는 150℃ 내지 185℃ 이고 압력은 4.9 내지 9.8 MpaG 이고, 상기 제 2차 반응기의 운전온도는 150℃ 내지 170℃ 이고 압력은 3.5 내지 5.0 MpaG 인, 알킬렌카보네이트의 제조 시스템을 제공한다.In the present invention, the operating temperature of the first reactor is 150 °C to 185 °C, the pressure is 4.9 to 9.8 MpaG, the operating temperature of the second reactor is 150 °C to 170 °C, and the pressure is 3.5 to 5.0 MpaG. , It provides a system for producing an alkylene carbonate.
본 발명은 또한, 상기 제 1차 반응기의 스팀응축수 주입부와 제 2차 반응기의 워터자켓에는 70℃ 내지 133℃ 스팀 응축수가 주입되는, 알킬렌카보네이트의 제조 시스템을 제공한다.The present invention also provides a system for producing an alkylene carbonate in which 70° C. to 133° C. steam condensed water is injected into the steam condensed water injection unit of the first reactor and the water jacket of the second reactor.
본 발명은 또한, 상기 페놀계 유기촉매는 하기 화학식 1로 표시되는 유기촉매인, 알킬렌카보네이트의 제조 시스템을 제공한다.The present invention also provides a system for producing an alkylene carbonate, wherein the phenolic organic catalyst is an organic catalyst represented by the following formula (1).
[화학식 1][Formula 1]
Figure PCTKR2019014132-appb-I000002
Figure PCTKR2019014132-appb-I000002
상기 화학식 1에서, R은 수소, 탄소수 C1 내지 C10의 알킬기, I, Br, Cl, F, OMe, NO2 또는 NMe2 이고, X는 I, Br, Cl, 또는 NO3임. In Formula 1, R is hydrogen, a C 1 to C 10 alkyl group, I, Br, Cl, F, OMe, NO 2 or NMe 2 , and X is I, Br, Cl, or NO 3 .
본 발명은 또한, 상기 재비기 일체형 증류탑은 충진물(packing)부를 구비하고, 상기 충진물은 골판 형태의 와이어거즈판(corrugated wire gauze plate)이 규칙적으로 배열된 구조형 충전물(structured packing)이 다단으로 적층된 구조물인,알킬렌카보네이트의 제조 시스템을 제공한다.In the present invention, the reboiling integrated distillation column has a packing part, and the packing material is a structured packing in which a corrugated wire gauze plate in the form of a corrugated plate is regularly arranged is stacked in multiple stages. It provides a structure, a system for producing alkylene carbonate.
본 발명은 또한, 알킬렌카보네이트의 제조방법으로, 상기 방법은, 이산화탄소, 알킬렌옥사이드 및 페놀계 유기촉매를 제 1차 반응기로 주입하여 알킬렌카보네이트가 포함된 1차 반응 생성물을 합성하는 단계; 상기 제 1차 반응생성물을 제 2차 반응기로 주입하여 미반응물을 반응시켜 알킬렌카보네이트가 포함된 2차 반응 생성물을 합성하는 단계; 상기 2차 반응 생성물을 기-액분리 드럼으로 공급하여 이산화탄소와 최종 반응 생성물을 분리하는 단계; 및 상기 최종 반응 생성물을 기-액분리 드럼과 연결된 증류탑으로 공급하여 알킬렌카보네이트를 정제하는 단계를 포함하고, 상기 제 1차 반응기는 열교환기 일체형 반응기로, 상기 제 1차 반응기 상단에 위치하며 이산화탄소, 알킬렌옥사이드 및 촉매 주입부를 각각 구비하며 하면이 개방된 반응 체류부; 상기 반응 체류부의 개방된 하면과 플랜지(Flange) 결합을 통해 개방된 상면이 연결되고 스팀응축수 주입부 및 제 1차 스팀배출부를 구비하는 쉘앤튜브(shell & tube)형 열교환부; 및 상기 쉘앤튜브 열교환부의 개방된 하면과 플랜지 결합을 통해 개방된 상면이 연결되며 상기 제 1차 반응기 하단에 위치하는 1차 반응 생성물 배출부를 포함하고, 상기 제 2차 반응기는 외주면에 반응 온도 조절용 워터자켓을 구비하고, 상부에는 제 2차 스팀배출부를 구비하며, 상기 증류탑은 재비기가 하단에 구비된 재비기 일체형 증류탑이고, 상기 제 1차 반응기 및 제 2차 반응기의 스팀 배출부의 스팀은 상기 증류탑의 재비기에 공급되어 열원으로 사용되는, 알킬렌카보네이트의 제조방법을 제공한다.The present invention is also a method for producing an alkylene carbonate, the method comprising: injecting carbon dioxide, an alkylene oxide, and a phenol-based organic catalyst into a first reactor to synthesize a first reaction product containing an alkylene carbonate; Injecting the first reaction product into a second reactor to react the unreacted product to synthesize a second reaction product containing alkylene carbonate; Supplying the secondary reaction product to a gas-liquid separation drum to separate carbon dioxide and a final reaction product; And supplying the final reaction product to a distillation column connected to a gas-liquid separation drum to purify the alkylene carbonate, wherein the first reactor is a heat exchanger integrated reactor, located at the top of the first reactor, and carbon dioxide , An alkylene oxide and a catalyst injection portion, respectively, and a reaction retention portion having an open lower surface thereof; A shell & tube type heat exchanger having a steam condensate injection part and a first steam discharge part connected to the open lower surface of the reaction holding part and the open upper surface through a flange coupling; And a first reaction product discharge unit connected to the open bottom surface of the shell and tube heat exchange unit through a flange connection and located at the bottom of the first reactor, and the second reactor includes water for controlling reaction temperature on an outer circumferential surface. A jacket is provided, and a second steam discharge unit is provided at the top, and the distillation column is an integrated reboiler distillation column having a reboiler at the bottom, and the steam from the steam discharge units of the first and second reactors is supplied from the distillation column. It provides a method for producing alkylene carbonate, which is supplied to the reboiler and used as a heat source.
본 발명은 또한, 상기 제 1차 반응기의 운전온도는 150℃ 내지 185℃ 이고 압력은 압력은 4.9 내지 9.8 MpaG 이고, 상기 제 2차 반응기의 운전온도는 150℃ 내지 170℃ 이고 압력은 3.5 내지 5.0 MpaG 이며, 상기 제 1차 반응기의 스팀응축수 주입부와 제 2차 반응기의 워터자켓에는 70℃ 내지 133℃ 스팀 응축수가 주입되고, 상기 재비기 일체형 증류탑은 충진물(packing)부를 구비하고, 상기 충진물은 골판 형태의 와이어거즈판(corrugated wire gauze plate)이 규칙적으로 배열된 구조형 충전물(structured packing)이 다단으로 적층된 구조물이며, 상기 페놀계 유기촉매는 하기 화학식 1로 표시되는 유기촉매인 알킬렌카보네이트의 제조 방법을 제공한다.In the present invention, the operating temperature of the first reactor is 150 °C to 185 °C, the pressure is 4.9 to 9.8 MpaG, the operating temperature of the second reactor is 150 °C to 170 °C, and the pressure is 3.5 to 5.0. MpaG, and 70°C to 133°C steam condensed water is injected into the steam condensed water injection unit of the first reactor and the water jacket of the second reactor, and the reboiling integrated distillation column has a packing unit, and the packing material is It is a structure in which structured packing in which a corrugated wire gauze plate in the form of a corrugated plate is regularly arranged is stacked in multiple stages, and the phenolic organic catalyst is made of alkylene carbonate, an organic catalyst represented by the following formula (1). Provides a manufacturing method.
[화학식 1][Formula 1]
Figure PCTKR2019014132-appb-I000003
Figure PCTKR2019014132-appb-I000003
상기 화학식 1에서, R은 수소, 탄소수 C1 내지 C10의 알킬기, I, Br, Cl, F, OMe, NO2 또는 NMe2 이고, X는 I, Br, Cl, 또는 NO3임.In Formula 1, R is hydrogen, a C 1 to C 10 alkyl group, I, Br, Cl, F, OMe, NO 2 or NMe 2 , and X is I, Br, Cl, or NO 3 .
본 발명의 알킬렌카보네이트 제조 시스템 및 방법은 열교환기 일체형 반응기 및 재비기 일체형 증류탑을 사용하여 공정에 사용되는 장치를 간소화할 수 있으며, 발생하는 스팀을 알킬렌카보네이트 정제 과정에서 열에너지로 재사용함으로써 공정에 필요한 에너지 및 비용을 절감하면서 이산화탄소를 효율적으로 제품화할 수 있다.The system and method for producing alkylene carbonate of the present invention can simplify the device used in the process by using a heat exchanger-integrated reactor and a reboiler-integrated distillation column, and the generated steam is reused as thermal energy in the alkylene carbonate purification process. Carbon dioxide can be efficiently commercialized while reducing the energy and cost required.
도 1은 본 발명의 한 구현예에 따른 알킬렌카보네이트 제조 시스템의 개략도이다. 1 is a schematic diagram of an alkylene carbonate production system according to an embodiment of the present invention.
도 2는 본 발명의 한 구현예에 따른 알킬렌카보네이트 제조 시스템의 제 1차 반응기의 단면도이다. 2 is a cross-sectional view of the first reactor of the system for producing alkylene carbonate according to an embodiment of the present invention.
도 3은 본 발명의 한 구현예에 따른 알킬렌카보네이트 제조 시스템의 제 2차 반응기의 단면도이다. 3 is a cross-sectional view of a second reactor of the system for producing alkylene carbonate according to an embodiment of the present invention.
도 4는 본 발명의 한 구현예에 따른 알킬렌카보네이트 제조 시스템의 재비기 일체형 증류탑의 단면도이다.4 is a cross-sectional view of a reboiling integrated distillation column of an alkylene carbonate production system according to an embodiment of the present invention.
본 발명의 상세한 설명에 앞서, 이하에서 설명되는 본 명세서 및 청구범위에 사용된 용어나 단어는 통상적이거나 사전적인 의미로 한정해서 해석되어서는 아니 된다. 따라서, 본 명세서에 기재된 실시예와 도면에 도시된 구성은 본 발명의 가장 바람직한 일실시예에 불과할 뿐이고 본 발명의 기술적 사상을 모두 대변하는 것은 아니므로, 본 출원시점에 있어서 이들을 대체할 수 있는 다양한 균등물과 변형예들이 있을 수 있음을 이해하여야 한다. Prior to the detailed description of the present invention, terms or words used in the present specification and claims described below should not be construed as being limited to their conventional or dictionary meanings. Accordingly, the embodiments described in the present specification and the configurations shown in the drawings are only the most preferred embodiments of the present invention, and do not represent all the technical spirit of the present invention. It should be understood that there may be equivalents and variations.
여기서, 본 발명의 실시 형태를 설명하기 위한 전체 도면에 있어서, 동일한 기능을 갖는 것은 동일한 부호를 붙이고, 그에 대한 상세한 설명은 생략하기로 한다. 이하, 첨부된 도면을 참조하여 본 발명의 알킬렌카보네이트의 제조 시스템에 대하여 설명하면 다음과 같다.Here, in all the drawings for explaining the embodiment of the present invention, those having the same function are denoted by the same reference numerals, and detailed description thereof will be omitted. Hereinafter, a system for producing an alkylene carbonate of the present invention will be described with reference to the accompanying drawings.
도 1은 본 발명의 한 구현예에 따른 알킬렌카보네이트 제조 시스템의 개략도이다. 본 발명의 시스템은 알킬렌옥사이드와 이산화탄소를 촉매 존재하에 고온 고압에서 반응시켜 알킬렌카보네이트를 합성할 수 있다. 상기 시스템은 알킬렌옥사이드와 이산화탄소를 페놀계 유기촉매 존재하에 반응시켜 알킬렌카보네이트가 포함된 1차 반응 생성물을 합성하는 제 1차 반응기(10); 상기 제 1차 반응기와 연결되고, 상기 1차 반응 생성물이 공급되어 미반응 반응물을 반응시켜 알킬렌카보네이트가 포함된 2차 반응 생성물을 합성하는 제 2차 반응기(20); 상기 제 2차 반응기와 연결되고, 상기 2차 반응 생성물이 공급되어 이산화탄소와 최종 반응 생성물을 분리하는 기-액분리 드럼(30); 및 상기 기-액분리 드럼과 연결되고, 상기 기-액분리 드럼에서 이산화탄소와 분리된 최종 반응 생성물이 투입되어 알킬렌카보네이트가 정제되는 증류탑(40)을 포함한다. 1 is a schematic diagram of an alkylene carbonate production system according to an embodiment of the present invention. The system of the present invention can synthesize alkylene carbonate by reacting alkylene oxide and carbon dioxide at high temperature and high pressure in the presence of a catalyst. The system comprises: a first reactor 10 for reacting alkylene oxide and carbon dioxide in the presence of a phenol-based organic catalyst to synthesize a first reaction product containing alkylene carbonate; A second reactor (20) connected to the first reactor, wherein the first reaction product is supplied to react unreacted reactants to synthesize a second reaction product containing alkylene carbonate; A gas-liquid separation drum 30 connected to the second reactor and supplying the second reaction product to separate carbon dioxide and a final reaction product; And a distillation column 40 connected to the gas-liquid separation drum and into which a final reaction product separated from carbon dioxide in the gas-liquid separation drum is added to purify the alkylene carbonate.
본 발명의 시스템의 제 1차 반응기(10)로 알킬렌옥사이드, 이산화탄소 및 페놀계 유기촉매가 공급되어 알킬렌카보네이트를 포함하는 1차 반응 생성물을 제조할 수 있다. 상기 제 1차 반응기(10)의 운전온도는 150℃ 내지 185℃ 이고 압력은 4.9 내지 9.8 MpaG 이다. 너무 낮은 온도 조건에서 수행할 경우 반응 시간이 길어지고, 온도를 증가시키면 반응 시간이 단축되는 효과가 있으나, 이를 위해 추가적으로 소요되는 비용에 비하여 더 이상 반응 시간이 단축되지 않으므로 불필요하다. An alkylene oxide, carbon dioxide, and a phenol-based organic catalyst are supplied to the first reactor 10 of the system of the present invention to prepare a first reaction product including alkylene carbonate. The operating temperature of the first reactor 10 is 150°C to 185°C and the pressure is 4.9 to 9.8 MpaG. If it is carried out under too low temperature conditions, the reaction time is lengthened, and if the temperature is increased, the reaction time is shortened, but it is unnecessary because the reaction time is no longer shortened compared to the additional cost for this.
한 구현예에서 상기 알킬렌옥사이드는 에틸렌 옥사이드(ethylene oxide), 프로필렌 옥사이드(propylene oxide), 부틸렌 옥사이드(butylene oxide), 헥실렌 옥사이드(hexylene oxide) 및 스타이렌 옥사이드(styrene oxide)로 이루어진 군으로부터 선택되는 것일 수 있다. 바람직하게 에틸렌옥사이드를 사용하여 에틸렌카보네이트를 제조할 수 있다. 상기 페놀계 유기촉매는 알킬렌옥사이드 대비 0.01 내지 10 mol%로 투입되어 사용될 수 있으나 이로 한정하는 것은 아니다. 0.01 mol% 미만으로 사용할 경우 반응 시간이 너무 길어지고, 농도를 증가시키면 반응시간이 단축되는 효과가 있으나, 10 mol% 이상으로 사용할 경우 촉매 단가의 증가로 인해 경제적 이득이 없다.In one embodiment, the alkylene oxide is from the group consisting of ethylene oxide, propylene oxide, butylene oxide, hexylene oxide, and styrene oxide. It may be selected. Ethylene carbonate can be produced preferably by using ethylene oxide. The phenolic organic catalyst may be added and used in an amount of 0.01 to 10 mol% relative to the alkylene oxide, but is not limited thereto. If it is used in less than 0.01 mol%, the reaction time becomes too long, and if the concentration is increased, the reaction time is shortened, but if it is used in more than 10 mol%, there is no economic benefit due to an increase in the catalyst unit cost.
본 발명의 알킬렌카보네이트 제조 반응에 사용되는 촉매는 페놀계 유기촉매로 하기 화학식 1로 표시되는 유기촉매이다.The catalyst used in the reaction for preparing the alkylene carbonate of the present invention is a phenolic organic catalyst, which is an organic catalyst represented by the following formula (1).
[화학식 1][Formula 1]
Figure PCTKR2019014132-appb-I000004
Figure PCTKR2019014132-appb-I000004
상기 화학식 1에서, R은 수소, 탄소수 C1 내지 C10의 알킬기, I, Br, Cl, F, OMe, NO2 또는 NMe2 이고, X는 I, Br, Cl, 또는 NO3이다. 바람직하게 상기 R은 C4의 알킬기 또는 NMe2인 것인 페놀계 유기촉매를 사용할 수 있다.In Formula 1, R is hydrogen, a C 1 to C 10 alkyl group, I, Br, Cl, F, OMe, NO 2 or NMe 2 , and X is I, Br, Cl, or NO 3 . Preferably, R is a C 4 alkyl group or NMe 2 It is possible to use a phenolic organic catalyst.
본 발명의 제 1차 반응기(10)는 도 2(a)와 같이 열교환기 일체형 반응기로, 상기 제 1차 반응기 상단에 위치하며 이산화탄소, 알킬렌옥사이드 및 촉매 주입부를 각각 구비하며 하면이 개방된 반응 체류부(11); 상기 반응 체류부의 개방된 하면과 플랜지(Flange) 결합을 통해 개방된 상면이 연결되고 스팀응축수 주입부 및 제 1차 스팀배출부를 구비하는 쉘앤튜브(shell & tube)형 열교환부(12); 및 상기 쉘앤튜브 열교환부의 개방된 하면과 플랜지 결합을 통해 개방된 상면이 연결되며 상기 제 1차 반응기 하단에 위치하는 1차 반응 생성물 배출부(13)를 포함한다. 도 2(b)는 제 1차 반응기의 A, B, C 각 위치에서의 단면을 나타낸다. 상기 체류부는 반응 체류시간을 확보하여 알킬렌카보네이트 합성 반응 효율을 향상시킬 수 있으며, 체류부와 연결되는 쉘앤튜브 열교환부를 구비하여 종래 별도 열교환기를 구비하는 시스템보다 장치를 간소화할 수 있다. 상기 쉘앤튜브 열교환부에는 스팀응축수를 투입함으로써 반응 시 발생되는 반응열을 조절하며 스팀을 생산할 수 있다. 예를 들면 70℃ 내지 133℃ 스팀응축수를 열교환부의 하부의 스팀응축수 주입부로 주입하고 반응온도를 조절한 후 생성된 스팀은 열교환부의 상부에 위치하는 1차 스팀배출부(101)로 배출될 수 있다. 상기 생성된 스팀은 본 발명의 후술되는 정제공정에서 증류의 재비기로 공급되어 열에너지로 사용될 수 있어 필요한 열에너지를 절약할 수 있다. The first reactor 10 of the present invention is a heat exchanger-integrated reactor as shown in FIG. 2(a), located at the top of the first reactor, and having carbon dioxide, alkylene oxide, and catalyst injection portions, respectively, and the lower surface thereof is opened. A staying part 11; A shell & tube type heat exchange unit (12) connected to the open lower surface of the reaction retention unit and the open upper surface through a flange coupling and having a steam condensate injection unit and a first steam discharge unit; And a first reaction product discharge part 13 that is connected to an open lower surface of the shell and tube heat exchange part and an open upper surface through a flange coupling, and is located at a lower end of the first reactor. 2(b) shows a cross section of the first reactor at positions A, B, and C. The retention portion may secure the reaction retention time to improve the reaction efficiency of the synthesis of alkylene carbonate, and the shell and tube heat exchange portion connected to the retention portion may be provided to simplify the apparatus compared to a conventional system having a separate heat exchanger. Steam condensed water is injected into the shell-and-tube heat exchange unit to control the reaction heat generated during the reaction and produce steam. For example, steam condensed water from 70°C to 133°C is injected into the steam condensed water injection unit below the heat exchange unit and the reaction temperature is adjusted, and then the generated steam may be discharged to the primary steam discharge unit 101 located above the heat exchange unit. . The generated steam is supplied to the reboiler of distillation in the purification process described later of the present invention and can be used as thermal energy, thereby saving required thermal energy.
본 발명의 제 1차 반응기에서 합성된 1차 반응 생성물은 제 2차 반응기로 공급되어 추가적인 반응을 수행할 수 있다. 도 3 (a)는 한 구현예에서 본 발명의 제 2차 반응기의 단면도이며, (b)는 각 위치에서의 절단면도이다. 제2 반응기는 예를 들면 연속 교반 탱크 반응기를 사용할 수 있고, 제 1차 반응기에서 반응되지 못한 미반응물을 반응시켜 알킬렌카보네이트 수율을 높이기 위한 것이다. 한 구현예에서 상기 제 2차 반응기의 운전 온도는 150℃ 내지 170℃ 이고 압력은 3.5 내지 5.0 MpaG 이다. 제 2차 반응기는 외주면에 반응 온도 조절용 워터자켓을 구비하고, 상부에는 2차 스팀 배출부(201)를 구비할 수 있다. 한 구현예에서 상기 제 워터자켓에는 70℃ 내지 133℃ 스팀응축수가 주입되어 제 2차 반응기의 반응온도를 조절할 수 있다.The first reaction product synthesized in the first reactor of the present invention may be supplied to the second reactor to perform an additional reaction. 3 (a) is a cross-sectional view of the second reactor of the present invention in one embodiment, and (b) is a cross-sectional view at each position. As the second reactor, for example, a continuous stirred tank reactor may be used, and an unreacted product not reacted in the first reactor is reacted to increase the yield of alkylene carbonate. In one embodiment, the operating temperature of the second reactor is 150°C to 170°C and the pressure is 3.5 to 5.0 MpaG. The second reactor may be provided with a water jacket for controlling the reaction temperature on the outer circumferential surface, and may be provided with a second steam discharge unit 201 at the top. In one embodiment, 70°C to 133°C steam condensed water may be injected into the water jacket to control the reaction temperature of the second reactor.
제 2차 반응기에서 반응이 끝난 후 최종 반응 생성물은 기-액 분리 드럼(30)으로 공급되어 기체와 액체가 분리되며, 기체상에는 이산화탄소가 포함되고 액체상에는 합성된 알킬렌카보네이트가 포함된다. 최종 반응 생성물의 안정적인 공급을 위해 기-액 분리기는 수위 측정기(level instrument)와 유량 측정기(flow instrument)를 구비할 수 있으며, 상호제어에 의해 안정적 공급이 가능하도록 한다. 액체상에 존재하는 알킬렌카보네이트를 정제하기 위해 증류법을 이용하여 정제할 수 있으며, 본 발명에서는 증류탑을 사용하여 액체 생성물 내에 존재하는 알킬렌카보네이트를 정제한다. After the reaction in the second reactor is completed, the final reaction product is supplied to the gas-liquid separation drum 30 to separate gas and liquid, and carbon dioxide is contained in the gas phase and the synthesized alkylene carbonate is contained in the liquid phase. For a stable supply of the final reaction product, the gas-liquid separator may be equipped with a level instrument and a flow instrument, and a stable supply is possible through mutual control. In order to purify the alkylene carbonate present in the liquid phase, it may be purified using a distillation method, and in the present invention, the alkylene carbonate present in the liquid product is purified using a distillation column.
도 4는 본 발명의 한 구현예에서 알킬렌카보네이트의 고순도 정제에 사용할 수 있는 재비기 일체형 증류탑(40)이다. 상기 증류탑은 재비기로부터 공급되는 고온의 증기를 사용하여 알킬렌카보네이트를 정제하는 것으로, 본 발명의 재비기 일체형 증류탑(40)은 하면이 개방된 충진물(packing)부(41); 상기 충진물부의 개방된 하면과 플랜지(Flange) 결합을 통해 개방된 상면이 연결되는 기-액분리부(separator)(42); 및 상기 기-액 분리부의 개방된 하면과 플랜지 결합을 통해 개방된 상면이 연결되며 상기 기-액 분리부의 하부에 위치하는 재비기(43)를 포함한다.4 is a reboiling integrated distillation column 40 that can be used for high purity purification of alkylene carbonate in one embodiment of the present invention. The distillation column purifies the alkylene carbonate using high-temperature steam supplied from the reboiler, and the integrated reboiler distillation column 40 of the present invention comprises: a packing part 41 having an open bottom surface; A gas-liquid separator 42 to which the open lower surface of the filling part is connected to the open upper surface through a flange coupling; And a reboiler 43 that is connected to an open bottom surface of the gas-liquid separation unit and an open top surface through a flange coupling, and is located under the gas-liquid separation unit.
본 발명의 증류탑은 증류탑 내에 충진물(packing)부(41)를 구비할 수 있다. 상기 충진물은 골판 형태의 와이어거즈판(corrugated wire gauze plate)이 규칙적으로 배열된 구조형 충진물(structured packing)이 다단으로 적층된 구조물이다. 상기 충진물은 용도에 따라 다공성 금속, 플라스틱(PTFE 포함) 또는 와이어 거즈의 골판 형태 시트로 형성될 수 있다. 한 구현예에서 본 발명에서는 바람직하게 직물과 유사한 구조를 가지도록 금속선(wire)을 날줄과 씨줄로 직조한 와이어거즈(wire guaze)를 톱니 모양의 골판(corrugated) 형태로 가공 후 형성된 골이 사선이 되도록 하고 서로 반대되는 사선 형상을 구성하도록 반복적인 구조형 충진물을 사용할 수 있다.The distillation column of the present invention may include a packing part 41 in the distillation column. The filler is a structure in which structured packing in which corrugated wire gauze plates are regularly arranged is stacked in multiple stages. The filler may be formed of a corrugated sheet of porous metal, plastic (including PTFE), or wire gauze depending on the application. In one embodiment, in the present invention, the ribs formed after processing a wire guaze in which a metal wire is woven with a blade and a transverse thread to have a structure similar to a fabric is processed into a serrated corrugated form are oblique lines. It is possible to use repetitive structural fillers so as to make the shape of the oblique line opposite to each other.
상기 제 2차 반응기로부터 공급되는 최종 반응 생성물이 증류탑 상부로 주입되면 상기 구조형 충진재 표면을 흐르며 액상 박막(liquid film)을 형성하며 충진재의 사선 형태의 골을 따라 충진제 하부로 흘러내려간다. 증발에 의한 액체의 기화는 액체의 표면에서 발생하기 때문에, 본 발명의 구조형 충진재를 이용한 증류는 구조형 충진재에 형성된 액체 박막 표면에서 액체의 기화가 발생하게 된다. 기화된 알킬렌카보네이트는 증류탑 상부로 향하고, 용액은 하부로 흘러내려간다. 기화된 알킬렌카보네이트는 증류탑 상부로 배출되어 응축기로 공급된다. 한 구현예에서 상기 와이어거즈 표면에 형성되는 액상박막의 두께를 0.1 내지 0.5mm 두께이며, 이는 유량제어기를 이용하여 제어할 수 있다. When the final reaction product supplied from the second reactor is injected into the top of the distillation column, it flows on the surface of the structural filler, forms a liquid film, and flows down the filler along the diagonal valleys of the filler. Since vaporization of the liquid by evaporation occurs on the surface of the liquid, the distillation using the structural filler of the present invention causes vaporization of the liquid on the surface of the liquid thin film formed on the structural filler. The vaporized alkylene carbonate goes to the top of the distillation column, and the solution flows down to the bottom. The vaporized alkylene carbonate is discharged to the top of the distillation column and supplied to a condenser. In one embodiment, the thickness of the liquid thin film formed on the surface of the wire gauze is 0.1 to 0.5 mm thick, which can be controlled using a flow controller.
상기 충진물부를 거친 용액은 기-액 분리부로 흘러 내려온다. 상기 기-액 분리부는 최종 반응 생성물로부터 증발된 알킬렌카보네이트는 상방으로, 그 외 용액은 하방으로의 흐름을 용이하게 하는 공간이다. 본 발명의 기-액 분리부는 저장조(421)를 구비하고 저장조 하부에 용액 배출라인(422)을 구비하여 쌓이는 액체를 즉시 재비기(43)로 공급할 수 있다. 본 발명의 증류탑 하단에 위치하는 재비기는 기존 공정의 케틀 타입의 재기비가 가지는 넓은 액체 증발 면적과 써모사이펀 타입의 재비기가 가지는 에너지 효율 우수성을 동시에 확보할 수 있다. 상기 재비기는 최종 반응 생성물을 가열하고 에틸렌카보네이트를 증발 시켜 정제 할 수 있다. 본 발명의 한 구현예에서 상기 재비기는 튜브형 열교환기를 사용하며 상기 열교환기에는 외부에서 가열된 스팀 또는 열매유(hot oil) 등의 유체를 주입하고 순환시킬 수 있으며, 주입되는 유체의 열에 의해 알킬렌카보네이트가 정제된다. 한 구현예에서 상기 재비기에는 전술한 제 1차 반응기 및 제 2차 반응기에서 발생되는 스팀(101, 201)을 재비기의 스팀 주입부(401)로 주입하여 사용할 수 있다. 예를 들면, 상기 제 1차 반응기에서 발생되는 스팀은 166.4kg/hr으로 생산되고, 증류탑에서 사용되는 스팀은 69.3kg/hr을 사용할 수 있다. 상기 증류탑으로 주입되는 스팀은 공정 내에서 발생되는 열에너지를 재사용하는 것으로, 에틸렌카보네이트 정제에 필요한 열에너지를 절감할 수 있다. The solution passing through the filling part flows down to the gas-liquid separation part. The gas-liquid separation unit is a space that facilitates the flow of the alkylene carbonate evaporated from the final reaction product upward and the other solutions downward. The gas-liquid separation unit of the present invention is provided with a storage tank 421 and a solution discharge line 422 below the storage tank, so that the accumulated liquid can be immediately supplied to the reboiler 43. The reboiler located at the bottom of the distillation column of the present invention can simultaneously secure a wide liquid evaporation area of the kettle-type reboiler of the existing process and the energy efficiency excellence of the thermosiphon-type reboiler. The reboil can be purified by heating the final reaction product and evaporating ethylene carbonate. In one embodiment of the present invention, the reboiler uses a tube-type heat exchanger, and a fluid such as steam or hot oil heated externally can be injected and circulated to the heat exchanger. The carbonate is purified. In one embodiment, in the reboiler, the steam 101 and 201 generated in the first and second reactors described above may be injected into the steam injection unit 401 of the reboiler. For example, the steam generated in the first reactor may be produced at 166.4 kg/hr, and the steam used in the distillation column may use 69.3 kg/hr. The steam injected into the distillation column reuses thermal energy generated in the process, thereby reducing thermal energy required for ethylene carbonate purification.
본 발명의 알킬렌카보네이트 제조 시스템은 열교환기 일체형 반응기 및 재비기 일체형 증류탑을 사용함에 따라 공간적 이점이 있으며, 반응기에서 발생하는 열에너지를 생성물 정제에 재사용 함에 따라 공정에 필요한 에너지 및 비용을 절감할 수 있다.The alkylene carbonate production system of the present invention has a spatial advantage by using a heat exchanger-integrated reactor and a reboiler-integrated distillation column, and by reusing the thermal energy generated in the reactor for product purification, it is possible to reduce energy and cost required for the process. .
또 다른 측면에서 본 발명은 상기 알킬렌카보네이트 제조 시스템을 사용한 알킬렌카보네이트의 제조방법으로, 상기 방법은, 이산화탄소, 알킬렌옥사이드 및 페놀계 유기촉매를 제 1차 반응기로 주입하여 알킬렌카보네이트가 포함된 1차 반응 생성물을 합성하는 단계; 상기 제 1차 반응생성물을 제 2차 반응기로 주입하여 미반응물을 반응시켜 알킬렌카보네이트가 포함된 2차 반응 생성물을 합성하는 단계; 상기 2차 반응 생성물을 기-액분리 드럼으로 공급하여 이산화탄소와 최종 반응 생성물을 분리하는 단계; 및 상기 최종 반응 생성물을 기-액분리 드럼과 연결된 증류탑으로 공급하여 알킬렌카보네이트를 정제하는 단계를 포함한다. 상기 페놀계 유기촉매, 제 1차 반응기, 제 2차 반응기 및 증류탑은 전술한 알킬렌카보네이트 시스템과 동일한 구성 및 운전 조건을 사용할 수 있으며, 상기 제 1차 반응기 및 제 2차 반응기의 스팀 배출부의 스팀은 상기 증류탑의 재비기로 공급되어 열원으로 사용하여 열에너지를 절감할 수 있다.In another aspect, the present invention is a method for producing an alkylene carbonate using the alkylene carbonate production system, wherein the method includes an alkylene carbonate by injecting carbon dioxide, an alkylene oxide, and a phenol-based organic catalyst into the first reactor. Synthesizing the primary reaction product; Injecting the first reaction product into a second reactor to react the unreacted product to synthesize a second reaction product containing alkylene carbonate; Supplying the secondary reaction product to a gas-liquid separation drum to separate carbon dioxide and a final reaction product; And supplying the final reaction product to a distillation column connected to a gas-liquid separation drum to purify the alkylene carbonate. The phenolic organic catalyst, the first reactor, the second reactor, and the distillation column may use the same configuration and operating conditions as the above-described alkylene carbonate system, and the steam discharge portion of the first reactor and the second reactor Is supplied to the reboiler of the distillation column and used as a heat source to reduce thermal energy.
이상에서 본원의 예시적인 실시예에 대하여 상세하게 설명하였지만 본원의 권리범위는 이에 한정되는 것은 아니고 다음의 청구범위에서 정의하고 있는 본원의 기본 개념을 이용한 당업자의 여러 변형 및 개량 형태 또한 본원의 권리범위에 속하는 것이다.Although the exemplary embodiments of the present application have been described in detail above, the scope of the present application is not limited thereto, and various modifications and improvements of those skilled in the art using the basic concept of the present application defined in the following claims are also included in the scope of the present application. It belongs to.
본 발명에서 사용되는 모든 기술용어는, 달리 정의되지 않는 이상, 본 발명의 관련 분야에서 통상의 당업자가 일반적으로 이해하는 바와 같은 의미로 사용된다. 본 명세서에 참고문헌으로 기재되는 모든 간행물의 내용은 본 발명에 도입된다. All technical terms used in the present invention, unless otherwise defined, are used in the same meaning as those of ordinary skill in the art generally understand in the related field of the present invention. The contents of all publications referred to herein by reference are incorporated into the present invention.
[부호의 설명][Explanation of code]
10. 제 1차 반응기10. First reactor
11. 반응 체류부11. Reaction retention section
12. 열교환부12. Heat exchange part
13. 1차 반응 생성물 배출부13. First reaction product discharge
20. 제 2차 반응기20. Second reactor
30. 기-액 분리 드럼30. Gas-liquid separation drum
40. 재비기 일체형 증류탑40. Reboiling integrated distillation column
41. 충진물부41. Filling part
42. 기-액 분리부42. Gas-liquid separator
43. 재비기43. Rebiging
101. 1차 스팀 배출부101. Primary steam outlet
201. 2차 스팀 배출부201. Secondary steam outlet
401. 재비기 스팀 주입부401. Reboil steam inlet
421. 저장조421. Reservoir
422. 용액 배출라인422. Solution discharge line

Claims (7)

  1. 알킬렌카보네이트의 제조 및 정제를 위한 시스템으로,As a system for the production and purification of alkylene carbonate,
    상기 시스템은 알킬렌옥사이드와 이산화탄소를 페놀계 유기촉매 존재하에 반응시켜 알킬렌카보네이트가 포함된 1차 반응 생성물을 합성하는 제 1차 반응기;The system comprises: a first reactor for reacting alkylene oxide and carbon dioxide in the presence of a phenolic organic catalyst to synthesize a first reaction product containing alkylene carbonate;
    상기 제 1차 반응기와 연결되고, 상기 1차 반응 생성물이 공급되어 미반응 반응물을 반응시켜 알킬렌카보네이트가 포함된 2차 반응 생성물을 합성하는 제 2차 반응기;A second reactor connected to the first reactor and supplying the first reaction product to react unreacted reactants to synthesize a second reaction product containing alkylene carbonate;
    상기 제 2차 반응기와 연결되고, 상기 2차 반응 생성물이 공급되어 이산화탄소와 최종 반응 생성물을 분리하는 기-액분리 드럼; 및A gas-liquid separation drum connected to the second reactor and supplied with the second reaction product to separate carbon dioxide and a final reaction product; And
    상기 기-액분리 드럼과 연결되고, 상기 기-액분리 드럼에서 이산화탄소와 분리된 최종 반응 생성물이 투입되어 알킬렌카보네이트가 정제되는 증류탑을 포함하고,And a distillation column connected to the gas-liquid separation drum and into which a final reaction product separated from carbon dioxide in the gas-liquid separation drum is added to purify alkylene carbonate,
    상기 제 1차 반응기는 열교환기 일체형 반응기로, 상기 제 1차 반응기 상단에 위치하며 이산화탄소, 알킬렌옥사이드 및 촉매 주입부를 각각 구비하며 하면이 개방된 반응 체류부;The first reactor is a heat exchanger-integrated reactor, which is located at an upper end of the first reactor and has a reaction retention portion having carbon dioxide, an alkylene oxide, and a catalyst injection portion, respectively, and having an open lower surface thereof;
    상기 반응 체류부의 개방된 하면과 플랜지(Flange) 결합을 통해 개방된 상면이 연결되고 스팀응축수 주입부 및 제 1차 스팀배출부를 구비하는 쉘앤튜브(shell & tube)형 열교환부; 및A shell & tube type heat exchanger having a steam condensate injection part and a first steam discharge part connected to the open lower surface of the reaction holding part and the open upper surface through a flange coupling; And
    상기 쉘앤튜브 열교환부의 개방된 하면과 플랜지 결합을 통해 개방된 상면이 연결되며 상기 제 1차 반응기 하단에 위치하는 1차 반응 생성물 배출부를 포함하고,An open lower surface of the shell and tube heat exchange unit and an open upper surface are connected to each other through a flange coupling, and include a first reaction product discharge unit located at the lower end of the first reactor,
    상기 제 2차 반응기는 외주면에 반응 온도 조절용 워터자켓을 구비하고, 상부에는 제 2차 스팀 배출부를 구비하며,The second reactor has a water jacket for controlling the reaction temperature on the outer circumferential surface, and has a second steam discharge part on the upper side,
    상기 증류탑은 재비기가 하단에 구비된 재비기 일체형 증류탑이고,The distillation column is an integrated reboiler distillation column provided with a reboiler at the bottom,
    상기 제 1차 및 제 2차 스팀 배출부의 스팀은 상기 증류탑의 재비기에 공급되어 열원으로 사용되는,Steam from the first and second steam discharge units is supplied to the reboiler of the distillation column and used as a heat source,
    알킬렌카보네이트의 제조 시스템.Alkylene carbonate production system.
  2. 제 1 항에 있어서,The method of claim 1,
    상기 제 1차 반응기의 운전온도는 150℃ 내지 185℃ 이고 압력은 4.9 내지 9.8 MpaG 이고, The operating temperature of the first reactor is 150 ℃ to 185 ℃, the pressure is 4.9 to 9.8 MpaG,
    상기 제 2차 반응기의 운전온도는 150℃ 내지 170℃ 이고 압력은 3.5 내지 5.0 MpaG 인,The operating temperature of the second reactor is 150 ℃ to 170 ℃ and the pressure is 3.5 to 5.0 MpaG,
    알킬렌카보네이트의 제조 시스템.Alkylene carbonate production system.
  3. 제 1 항에 있어서,The method of claim 1,
    상기 제 1차 반응기의 스팀응축수 주입부와 제 2차 반응기의 워터자켓에는 70℃ 내지 133℃ 스팀 응축수가 주입되는,70°C to 133°C steam condensed water is injected into the steam condensed water injection unit of the first reactor and the water jacket of the second reactor,
    알킬렌카보네이트의 제조 시스템.Alkylene carbonate production system.
  4. 제 1 항에 있어서,The method of claim 1,
    상기 페놀계 유기촉매는 하기 화학식 1로 표시되는 유기촉매인,The phenolic organic catalyst is an organic catalyst represented by the following formula (1),
    [화학식 1][Formula 1]
    Figure PCTKR2019014132-appb-I000005
    Figure PCTKR2019014132-appb-I000005
    상기 화학식 1에서, In Formula 1,
    R은 수소, 탄소수 C1 내지 C10의 알킬기, I, Br, Cl, F, OMe, NO2 또는 NMe2 이고,R is hydrogen, a C 1 to C 10 alkyl group, I, Br, Cl, F, OMe, NO 2 or NMe 2 ,
    X는 I, Br, Cl, 또는 NO3임. X is I, Br, Cl, or NO 3 .
    알킬렌카보네이트의 제조 시스템.Alkylene carbonate production system.
  5. 제 1 항에 있어서,The method of claim 1,
    상기 재비기 일체형 증류탑은 충진물(packing)부를 구비하고, The reboiling integrated distillation column has a packing unit,
    상기 충진물은 골판 형태의 와이어거즈판(corrugated wire gauze plate)이 규칙적으로 배열된 구조형 충전물(structured packing)이 다단으로 적층된 구조물인,The filler is a structure in which a structured packing in which a corrugated wire gauze plate in the form of a corrugated plate is regularly arranged is stacked in multiple stages,
    알킬렌카보네이트의 제조 시스템.Alkylene carbonate production system.
  6. 알킬렌카보네이트의 제조방법으로,As a method for producing alkylene carbonate,
    상기 방법은, 이산화탄소, 알킬렌옥사이드 및 페놀계 유기촉매를 제 1차 반응기로 주입하여 반응시켜 알킬렌카보네이트가 포함된 1차 반응 생성물을 합성하는 단계;The method comprises the steps of injecting carbon dioxide, an alkylene oxide, and a phenol-based organic catalyst into a first reactor and reacting to synthesize a first reaction product containing alkylene carbonate;
    상기 제 1차 반응생성물을 제 2차 반응기로 주입하여 미반응물을 반응시켜 알킬렌카보네이트가 포함된 2차 반응 생성물을 합성하는 단계;Injecting the first reaction product into a second reactor to react the unreacted product to synthesize a second reaction product containing alkylene carbonate;
    상기 2차 반응 생성물을 기-액분리 드럼으로 공급하여 이산화탄소와 최종 반응 생성물을 분리하는 단계; 및Supplying the secondary reaction product to a gas-liquid separation drum to separate carbon dioxide and a final reaction product; And
    상기 최종 반응 생성물을 기-액분리 드럼과 연결된 증류탑으로 공급하여 알킬렌카보네이트를 정제하는 단계를 포함하고,Supplying the final reaction product to a distillation column connected to a gas-liquid separation drum to purify the alkylene carbonate,
    상기 제 1차 반응기는 열교환기 일체형 반응기로, 상기 제 1차 반응기 상단에 위치하며 이산화탄소, 알킬렌옥사이드 및 촉매 주입부를 각각 구비하며 하면이 개방된 반응 체류부;The first reactor is a heat exchanger-integrated reactor, which is located at an upper end of the first reactor and has a reaction retention portion having carbon dioxide, an alkylene oxide, and a catalyst injection portion, respectively, and having an open lower surface thereof;
    상기 반응 체류부의 개방된 하면과 플랜지(Flange) 결합을 통해 개방된 상면이 연결되고 스팀응축수 주입부 및 제 1차 스팀배출부를 구비하는 쉘앤튜브(shell & tube)형 열교환부; 및A shell & tube type heat exchanger having a steam condensate injection part and a first steam discharge part connected to the open lower surface of the reaction holding part and the open upper surface through a flange coupling; And
    상기 쉘앤튜브 열교환부의 개방된 하면과 플랜지 결합을 통해 개방된 상면이 연결되며 상기 제 1차 반응기 하단에 위치하는 1차 반응 생성물 배출부를 포함하고,An open lower surface of the shell and tube heat exchange unit and an open upper surface are connected to each other through a flange coupling, and include a first reaction product discharge unit located at the lower end of the first reactor,
    상기 제 2차 반응기는 외주면에 반응 온도 조절용 워터자켓을 구비하고, 상부에는 제 2차 스팀배출부를 구비하며,The second reactor has a water jacket for controlling the reaction temperature on the outer circumferential surface, and has a second steam discharge part on the upper side,
    상기 증류탑은 재비기가 하단에 구비된 재비기 일체형 증류탑이고,The distillation column is an integrated reboiler distillation column provided with a reboiler at the bottom,
    상기 제 1차 반응기 및 제 2차 반응기의 스팀 배출부의 스팀은 상기 증류탑의 재비기에 공급되어 열원으로 사용되는,Steam from the steam outlet of the first reactor and the second reactor is supplied to the reboiler of the distillation column and used as a heat source,
    알킬렌카보네이트의 제조방법.Method for producing alkylene carbonate.
  7. 제 6 항에 있어서,The method of claim 6,
    상기 제 1차 반응기의 운전온도는 150℃ 내지 185℃ 이고 압력은 압력은 4.9 내지 9.8 MpaG 이고, The operating temperature of the first reactor is 150 ℃ to 185 ℃, the pressure is 4.9 to 9.8 MpaG,
    상기 제 2차 반응기의 운전온도는 150℃ 내지 170℃ 이고 압력은 3.5 내지 5.0 MpaG 이며,The operating temperature of the second reactor is 150 ℃ to 170 ℃, the pressure is 3.5 to 5.0 MpaG,
    상기 제 1차 반응기의 스팀응축수 주입부와 제 2차 반응기의 워터자켓에는 70℃ 내지 133℃ 스팀 응축수가 주입되고,70 ℃ to 133 ℃ steam condensed water is injected into the steam condensed water injection unit of the first reactor and the water jacket of the second reactor,
    상기 재비기 일체형 증류탑은 충진물(packing)부를 구비하고, The reboiling integrated distillation column has a packing unit,
    상기 충진물은 골판 형태의 와이어거즈판(corrugated wire gauze plate)이 규칙적으로 배열된 구조형 충전물(structured packing)이 다단으로 적층된 구조물이며,The filler is a structure in which a structured packing in which a corrugated wire gauze plate in the form of a corrugated plate is regularly arranged is stacked in multiple stages,
    상기 페놀계 유기촉매는 하기 화학식 1로 표시되는 유기촉매인,The phenolic organic catalyst is an organic catalyst represented by the following formula (1),
    [화학식 1][Formula 1]
    Figure PCTKR2019014132-appb-I000006
    Figure PCTKR2019014132-appb-I000006
    상기 화학식 1에서, In Formula 1,
    R은 수소, 탄소수 C1 내지 C10의 알킬기, I, Br, Cl, F, OMe, NO2 또는 NMe2 이고,R is hydrogen, a C 1 to C 10 alkyl group, I, Br, Cl, F, OMe, NO 2 or NMe 2 ,
    X는 I, Br, Cl, 또는 NO3임. X is I, Br, Cl, or NO 3 .
    알킬렌카보네이트의 제조 방법.Method for producing alkylene carbonate.
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