WO2021047055A1 - 一种强化丙烯环氧化制备环氧丙烷的无醚化系统及工艺 - Google Patents

一种强化丙烯环氧化制备环氧丙烷的无醚化系统及工艺 Download PDF

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WO2021047055A1
WO2021047055A1 PCT/CN2019/120194 CN2019120194W WO2021047055A1 WO 2021047055 A1 WO2021047055 A1 WO 2021047055A1 CN 2019120194 W CN2019120194 W CN 2019120194W WO 2021047055 A1 WO2021047055 A1 WO 2021047055A1
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propylene
reaction
micro
reaction zone
epoxidation
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PCT/CN2019/120194
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English (en)
French (fr)
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张志炳
张锋
周政
李磊
孟为民
王宝荣
杨高东
罗华勋
杨国强
田洪舟
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南京延长反应技术研究院有限公司
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Publication of WO2021047055A1 publication Critical patent/WO2021047055A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
    • 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
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the invention relates to the technical field of preparing propylene oxide by epoxidation of propylene, and particularly relates to a non-etherification system and process for preparing propylene oxide by enhanced epoxidation of propylene.
  • Propylene oxide (PO) is the third largest organic chemical product in the production of propylene derivatives after polypropylene and acrylonitrile. Propylene oxide has a wide range of uses. At present, in addition to the production of polyether polyols and glycerol, it can also be used to produce propylene glycol, non-ionic surfactants, oil field demulsifiers, pesticide emulsifiers and wetting agents. Propylene oxide derivatives are also widely used in industries such as automobiles, construction, food, tobacco, medicine, and cosmetics. With the expansion of the use of propylene oxide and the continuous increase in the amount of downstream products, the market demand for propylene oxide is increasing year by year.
  • the main industrial methods for producing propylene oxide are the chlorohydrin method and the co-oxidation method (also called the indirect oxidation method, or the Halcon method). These two methods account for more than 99% of the world's total production capacity.
  • the chlorohydrin method propylene is reacted with chlorine and water to generate chloropropanol, which is then saponified under the action of lye to obtain propylene oxide.
  • This method has been the main method for the production of PO since it was developed and industrially produced by Union Carbon in the 1930s.
  • the co-oxidation method is divided into isobutane method and ethylbenzene method.
  • Isobutane (or ethylbenzene) undergoes oxidation to generate isobutane peroxide (or ethylbenzene peroxide), and then reacts with propylene to generate PO, and co-produce tert-butanol (or ⁇ -methyl phenethyl alcohol).
  • the present invention provides a non-etherification system and process for preparing propylene oxide by enhanced propylene epoxidation, so as to achieve the effect of not causing equipment corrosion and no ether products during the process of preparing propylene oxide.
  • a non-etherification system for preparing propylene oxide by enhanced propylene epoxidation including:
  • Propylene storage tank used to store and transport propylene
  • the gas-liquid separator is used to receive the propylene epoxidation product and perform gas-liquid separation of the epoxidation product to obtain propylene oxide and propylene;
  • the epoxidation reaction unit includes a first reaction zone, a second reaction zone and a third reaction zone.
  • the first reaction zone is arranged below the inside of the reaction tank for receiving the propylene into the inside of the reaction tank and serving as propylene
  • the main reaction place of the epoxidation reaction the first reaction zone is provided with a first micro-interface generator connected to the propylene storage tank; the second reaction zone is set above the inside of the reaction tank and is mixed with the mixed solvent
  • the storage tank is connected to receive the mixed liquid into the reaction tank and serve as a place for the epoxidation reaction of propylene in the first reaction zone and the third reaction zone where the epoxidation reaction has not sufficiently occurred.
  • a separation layer is arranged inside the second reaction zone to completely separate the second reaction zone and the third reaction zone, and a second micro-interface generator is arranged above the separation layer to separate the second reaction zone and the third reaction zone.
  • One-way communication; the third reaction zone is directly connected to the first reaction zone, and the third reaction zone is arranged in the middle of the reaction tank and connected to the inlet end of the gas-liquid separator, and is used to transport the epoxidation reaction product to the gas
  • the inside of the liquid separator is used as the epoxidation reaction site of propylene separated by the gas-liquid separator.
  • a third micro-interface generator connected to the outlet of the gas-liquid separator is provided inside, and a circulating pump is provided outside the reaction tank to circulate The inlet end of the pump is connected with the second reaction zone, and the outlet end is connected with the third micro-interface generator, and is used for transporting the mixed liquid received in the second reaction zone to the third reaction zone and the first reaction zone.
  • the first micro-interface generator adopts a pneumatic micro-interface generator, which is used before the epoxidation reaction of propylene in the first reaction zone occurs. , The propylene gas is broken into micron-sized bubbles, thereby increasing the contact area of propylene and hydrogen peroxide in the mixed solution, and making the epoxidation reaction of propylene more complete.
  • the second micro-interface generator adopts a pneumatic micro-interface generator, which is used as the first reaction zone and the third reaction inner zone.
  • the epoxidized propylene enters the channel of the second reaction zone, and the propylene that has not undergone the epoxidation reaction is broken into micron-sized bubbles.
  • the third micro-interface generator adopts a hydraulic micro-interface generator for separating the propylene roll separated by the gas-liquid separator. It is sucked into the inside of the third micro-interface generator, and the sucked propylene is broken into micron-sized bubbles and then released to the third reaction zone.
  • a buffer grid is arranged above the third micro-interface generator of the third reaction zone to prevent the solution inside the reaction tank from boiling violently.
  • a non-etherification process for preparing propylene oxide by enhanced propylene epoxidation which is characterized in that it comprises:
  • the propylene is transported to the first micro-interface generator, and then released to the first reaction zone.
  • the propylene gradually enters the third reaction zone and then enters the second reaction zone through the second micro-interface generator on the separation layer until the inside of the reaction tank Filled with acrylic.
  • the mixed solution is transported to the second reaction zone inside the reaction tank. Since the inside of the reaction tank is filled with propylene, the mixed solution will not flow into the third reaction zone from the second micro-interface generator under the action of air pressure, but can only pass through
  • the circulation pump enters the third micro-interface generator, and then is released to the third reaction zone and the first reaction zone;
  • the first micro-interface generator breaks the propylene into micro-sized bubbles and releases the micro-sized bubbles to the first reaction zone.
  • the mixed solution flows into the first reaction zone, the propylene micro-sized bubbles and the mixed solution Of hydrogen peroxide undergoes epoxidation reaction;
  • the incompletely reacted propylene in the first reaction zone enters the second micro-interface generator through the separation layer, and the second micro-interface generator breaks the incompletely reacted propylene into micro-sized bubbles and releases the micro-sized bubbles to the second micro-interface generator.
  • the second reaction zone undergoes an epoxidation reaction with the hydrogen peroxide in the mixed solution, and the epoxidation reaction product and the mixed solution are transported to the inside of the third micro-interface generator through a circulating pump, and then released to the third reaction zone;
  • the epoxidation reaction product is transported to the inside of the gas-liquid separator for gas-liquid separation, the separated propylene gas is transported to the inside of the third micro-interface generator, and the third micro-interface generator will separate the separated propylene gas It is broken into micron-sized bubbles and released to the third reaction zone to undergo an epoxidation reaction with the hydrogen peroxide in the mixed solution, and the separated propylene oxide is collected through the lower outlet of the separator.
  • the micro-interface generator converts the pressure energy of the gas and/or the kinetic energy of the liquid into the surface energy of the gas and transmits it to the propylene gas, so that The propylene gas is broken into micron-sized bubbles with a micron-sized diameter.
  • the micron-level bubbles are micron-level bubbles with a diameter greater than or equal to 1 ⁇ m and less than 1 mm.
  • the reaction pressure of the epoxidation reaction is 0.12-0.2 MPa.
  • the reaction temperature of the epoxidation reaction is 50-58°C.
  • the beneficial effect of the present invention is that the non-etherification system and process for preparing propylene oxide from enhanced propylene epoxidation provided by the present invention select acetonitrile as the solvent, and because acetonitrile is used as the aprotic solvent, the epoxidation The reaction activity is lower than when alcohol solvents are used.
  • the inertness and weak alkali properties of acetonitrile can effectively inhibit the ring opening of propylene oxide, thereby avoiding the formation of etherification and hydrolysis by-products, and there is no large amount of salt-containing wastewater and Organic chloride, so as not to cause serious corrosion of the equipment, and the system is equipped with a micro-interface generator, so that before the epoxidation reaction of propylene, the micro-interface generator breaks the propylene gas into those with a diameter greater than or equal to 1 ⁇ m and less than 1mm Micron-sized bubbles, thereby increasing the contact area of propylene and hydrogen peroxide in the mixed solution, making the epoxidation reaction of propylene more complete, and achieving no equipment corrosion and no ether during the process of preparing propylene oxide
  • the range of preset operating conditions can be flexibly adjusted according to different working conditions, different product requirements or different catalysts to further ensure the full and effective progress of the reaction, thereby ensuring the reaction rate, and
  • the system is equipped with a first reaction zone, a second reaction zone, and a third reaction zone, which are respectively used to receive propylene into the inside of the reaction tank, and serve as the main reaction site for the propylene epoxidation reaction, and receive the mixed liquid.
  • a first reaction zone Enter the inside of the reaction tank and serve as the propylene that does not fully undergo epoxidation in the first reaction zone, where the epoxidation reaction is carried out and the epoxidation reaction product is transported to the inside of the gas-liquid separator, and separated as a gas-liquid separator
  • the propylene epoxidation reaction site that comes out enables the propylene to be fully utilized in the system, thereby reducing production costs.
  • a buffer grid is arranged above the second micro-interface generator of the second reaction zone in the system.
  • the buffer grid can effectively avoid the violent boiling inside the reaction tank. Damage to the reaction tank, thereby prolonging the service life of the reaction tank.
  • Fig. 1 is a schematic structural diagram of a non-etherification system and process for preparing propylene oxide by enhanced propylene epoxidation according to an embodiment of the present invention.
  • the terms “installed”, “connected”, and “connected” should be understood in a broad sense. For example, they can be fixed or fixed. It is a detachable connection or an integral connection; it can be a mechanical connection or an electrical connection; it can be directly connected or indirectly connected through an intermediate medium, and it can be the internal communication between two components.
  • installed e.g., they can be fixed or fixed. It is a detachable connection or an integral connection; it can be a mechanical connection or an electrical connection; it can be directly connected or indirectly connected through an intermediate medium, and it can be the internal communication between two components.
  • the specific meaning of the above-mentioned terms in the present invention can be understood according to specific circumstances.
  • the non-etherification system for preparing propylene oxide by enhanced propylene epoxidation includes a reaction tank 3 with a first reaction zone, a second reaction zone, and a third reaction zone inside.
  • the first reaction zone is connected with a propylene storage tank 1 for storing and transporting propylene
  • the second reaction zone is connected with a mixed solvent storage tank 2 for preparing and transporting a mixture of hydrogen peroxide, acetonitrile and catalyst
  • the third reaction zone is connected
  • a gas-liquid separator 4 for receiving the propylene epoxidation product and performing gas-liquid separation of the epoxidation product
  • a circulation pump 36 connecting the second reaction zone and the third reaction zone is provided outside the reaction tank 3.
  • a first reaction zone is arranged below the inside of the reaction tank 3, and a first micro-interface generator 31 is arranged in the first reaction zone.
  • the first micro-interface generator 31 is fixedly connected to the inside of the reaction tank 3, and its inlet end is connected to the propylene storage tank 1.
  • Start the system transport the propylene to the first micro-interface generator 31, and then release it to the first reaction zone.
  • the propylene gradually enters the third reaction zone and then enters the second reaction through the second micro-interface generator 32 on the separation layer 34 Zone until the inside of the reaction tank 3 is filled with propylene. Then the mixed solution is transported to the second reaction zone inside the reaction tank 3.
  • the reaction tank 3 Since the reaction tank 3 is filled with propylene, the mixed solution will not flow into the third reaction zone from the second micro-interface generator 32 under the action of air pressure. It can only enter the third micro-interface generator 33 through the circulation pump 36, and then be released to the third reaction zone and the first reaction zone.
  • the first micro-interface generator 31 breaks propylene into micro-sized bubbles with a diameter greater than or equal to 1 ⁇ m and less than 1 mm, and releases the micro-sized bubbles to the first reaction zone.
  • the mixed solution flows into the first reaction zone, the propylene micro-sized bubbles and The hydrogen peroxide in the mixed solution undergoes an epoxidation reaction.
  • a second reaction zone connected to the mixed solvent storage tank 2 is provided above the inside of the reaction tank 3, and a separation layer 34 is fixedly connected to the second reaction zone for connecting the second reaction zone and the first reaction zone.
  • the substances in the first reaction zone and the third reaction zone are separated.
  • a second micro-interface generator 32 is arranged above the separation layer 34, and the inlet end of the second non-micro-interface generator is connected to the first reaction zone and the third reaction zone.
  • the incompletely reacted propylene and the generated waste gas in the first reaction zone enter the second micro-interface generator 32 through the separation layer 34.
  • the second micro-interface generator 32 breaks the incompletely reacted propylene into a diameter greater than or equal to 1 ⁇ m and less than 1 mm.
  • the micron-sized bubbles are released to the second reaction zone and the hydrogen peroxide in the mixed solution undergoes an epoxidation reaction.
  • the epoxidation reaction product and the mixed solution are transported to the third reaction zone through a circulating pump 36, The exhaust gas is removed from the reaction tank 3.
  • a third reaction zone connected to the inlet end of the gas-liquid separator 4 is provided in the middle of the reaction tank 3, and a third micro-interface generator 33 is fixedly connected to the third reaction zone.
  • the third micro-interface generator 33 is connected to the gas-liquid separator respectively.
  • the outlet end is connected to the outlet end of the circulating pump 36, and a heat exchanger 37 is provided between the third micro-interface generator 33 and the circulating pump 36.
  • a buffer grid 35 is arranged above the third micro-interface generator 33 to prevent the solution inside the reaction tank 3 from boiling violently.
  • the epoxidation reaction products in the first reaction zone and the second reaction zone are transported to the inside of the gas-liquid separator 4 for gas-liquid separation, and the separated propylene gas is transported to the inside of the third interface generator, and the third micro-interface
  • the generator 33 breaks the separated propylene gas into micron-sized bubbles with a diameter greater than or equal to 1 ⁇ m and less than 1 mm, and releases the micron-sized bubbles to the third reaction zone to undergo epoxidation reaction with the hydrogen peroxide in the mixed solution.
  • the separated propylene oxide product is collected through the outlet under the separator, and the waste liquid generated in the reaction tank 3 is discharged through the waste liquid channel.
  • the micro-interface generator converts the pressure energy of the gas and/or the kinetic energy of the liquid into the surface energy of the liquid and transmits it to the liquid chlorine, so that the liquid chlorine is broken into micron-sized bubbles with a diameter of micrometers, according to the energy input mode or the gas
  • the liquid ratio is divided into a pneumatic micro-interface generator, a hydraulic micro-interface generator and a gas-liquid linkage micro-interface generator.
  • the pneumatic micro-interface generator is driven by gas, and the input gas volume is much larger than the liquid volume; the hydraulic micro-interface generator is driven by liquid.
  • the input gas volume is generally less than the liquid volume; the gas-liquid linkage micro-interface generator is driven by both gas and liquid, and the input gas volume is close to the liquid volume.
  • the first micro-interface generator 31 and the second micro-interface generator 32 are pneumatic micro-interface generators, and the third micro-interface generator 33 is a hydraulic micro-interface generator.
  • the non-etherification system for preparing propylene oxide by enhanced propylene epoxidation uses acetonitrile as the solvent. Since acetonitrile is used as the aprotic solvent, the epoxidation reaction activity is lower than that when alcohol solvents are used.
  • the inertness and weak alkali properties of propylene oxide effectively inhibit the ring opening of propylene oxide, thereby avoiding the formation of etherification and hydrolysis by-products, and there is no large amount of salt-containing wastewater and organic chlorides in the product, which will not cause serious corrosion of the equipment, and the cost
  • the system is equipped with a micro-interface generator, so that before the propylene epoxidation reaction occurs, the micro-interface generator breaks the propylene gas into micron-sized bubbles with a diameter greater than or equal to 1 ⁇ m and less than 1 mm, thereby increasing the propylene and the mixed solution
  • the contact area of medium hydrogen peroxide makes the epoxidation reaction of propylene more complete, and achieves the effect of not causing equipment corrosion and no ether products during the process of preparing propylene oxide.
  • a non-etherification process for preparing propylene oxide by enhanced propylene epoxidation including:
  • the propylene is transported to the first micro-interface generator, and then released to the first reaction zone.
  • the propylene gradually enters the third reaction zone and then enters the second reaction zone through the second micro-interface generator on the separation layer until the inside of the reaction tank It is filled with propylene, and then the mixed solution is transported to the second reaction zone inside the reaction tank. Since the inside of the reaction tank is filled with propylene, the mixed solution will not flow into the third reaction zone from the second micro-interface generator under the action of air pressure. , Can only enter the third micro-interface generator through the circulation pump, and then be released to the third reaction zone and the first reaction zone;
  • the first micro-interface generator breaks the propylene into micro-sized bubbles and releases the micro-sized bubbles to the first reaction zone.
  • the mixed solution flows into the first reaction zone, the propylene micro-sized bubbles and the mixed solution Of hydrogen peroxide undergoes epoxidation reaction;
  • the incompletely reacted propylene in the first reaction zone enters the second micro-interface generator through the separation layer, and the second micro-interface generator breaks the incompletely reacted propylene into micro-sized bubbles and releases the micro-sized bubbles to the second micro-interface generator.
  • the second reaction zone undergoes an epoxidation reaction with the hydrogen peroxide in the mixed solution, and the epoxidation reaction product and the mixed solution are transported to the inside of the third micro-interface generator through a circulating pump, and then released to the third reaction zone;
  • the epoxidation reaction product is transported to the inside of the gas-liquid separator for gas-liquid separation, the separated propylene gas is transported to the inside of the third micro-interface generator, and the third micro-interface generator will separate the separated propylene gas It is broken into micron-sized bubbles and released to the third reaction zone to undergo an epoxidation reaction with the hydrogen peroxide in the mixed solution, and the separated propylene oxide is collected through the lower outlet of the separator.
  • the reaction pressure of the epoxidation reaction is 0.1-0.2 MPa.
  • the reaction temperature of the epoxidation reaction is 50-58°C.
  • the type of catalyst is not specifically limited in this embodiment. It can be one or a combination of iron-based catalysts, molybdenum-based catalysts, nickel-based catalysts, cobalt-based catalysts, and tungsten-based catalysts, as long as the strengthening reaction can be ensured smoothly. Go ahead.
  • the propylene is transported to the first micro-interface generator, and then released to the first reaction zone.
  • the propylene gradually enters the third reaction zone and then enters the second reaction zone through the second micro-interface generator on the separation layer until the inside of the reaction tank Filled with propylene, then slowly transport 500g of mixed solution to the second reaction zone inside the reaction tank, enter the third micro-interface generator through the circulation pump, and then be released to the third reaction zone and the first reaction zone;
  • the first micro-interface generator breaks the propylene into micro-sized bubbles and releases the micro-sized bubbles to the first reaction zone.
  • the mixed solution flows into the first reaction zone, the propylene micro-sized bubbles and the mixed solution Of hydrogen peroxide undergoes epoxidation reaction;
  • the incompletely reacted propylene in the first reaction zone enters the second micro-interface generator through the separation layer, and the second micro-interface generator breaks the incompletely reacted propylene into micro-sized bubbles and releases the micro-sized bubbles to the second micro-interface generator.
  • the second reaction zone undergoes an epoxidation reaction with the hydrogen peroxide in the mixed solution, and the epoxidation reaction product and the mixed solution are transported to the inside of the third micro-interface generator through a circulating pump, and then released to the third reaction zone;
  • the epoxidation reaction product is transported to the inside of the gas-liquid separator for gas-liquid separation, the separated propylene gas is transported to the inside of the third interface generator, and the third micro-interface generator breaks the separated propylene gas Into micron-sized bubbles, and release the micron-sized bubbles to the third reaction zone to undergo an epoxidation reaction with the hydrogen peroxide in the mixed solution, and the separated propylene oxide is collected through the lower outlet of the separator;
  • the propylene is transported to the first micro-interface generator, and then released to the first reaction zone.
  • the propylene gradually enters the third reaction zone and then enters the second reaction zone through the second micro-interface generator on the separation layer until the inside of the reaction tank Filled with propylene, then slowly transport 1000g of mixed solution to the second reaction zone inside the reaction tank, enter the third micro-interface generator through the circulation pump, and then be released to the third reaction zone and the first reaction zone;
  • the first micro-interface generator breaks the propylene into micro-sized bubbles and releases the micro-sized bubbles to the first reaction zone.
  • the mixed solution flows into the first reaction zone, the propylene micro-sized bubbles and the mixed solution Of hydrogen peroxide undergoes epoxidation reaction;
  • the incompletely reacted propylene in the first reaction zone enters the second micro-interface generator through the separation layer, and the second micro-interface generator breaks the incompletely reacted propylene into micro-sized bubbles and releases the micro-sized bubbles to the second micro-interface generator.
  • the second reaction zone undergoes an epoxidation reaction with the hydrogen peroxide in the mixed solution, and the epoxidation reaction product and the mixed solution are transported to the inside of the third micro-interface generator through a circulating pump, and then released to the third reaction zone;
  • the epoxidation reaction product is transported to the inside of the gas-liquid separator for gas-liquid separation, the separated propylene gas is transported to the inside of the third interface generator, and the third micro-interface generator breaks the separated propylene gas Into micron-sized bubbles, and release the micron-sized bubbles to the third reaction zone to undergo an epoxidation reaction with the hydrogen peroxide in the mixed solution, and the separated propylene oxide is collected through the lower outlet of the separator;
  • the conversion rate of hydrogen peroxide was 95%
  • the selectivity of propylene oxide was 89%
  • the content of ether products was 0%
  • the content of organic chloride was 0%.
  • the propylene is transported to the first micro-interface generator, and then released to the first reaction zone.
  • the propylene gradually enters the third reaction zone and then enters the second reaction zone through the second micro-interface generator on the separation layer until the inside of the reaction tank Filled with propylene, then slowly transport 1000g of mixed solution to the second reaction zone inside the reaction tank, enter the third micro-interface generator through the circulation pump, and then be released to the third reaction zone and the first reaction zone;
  • the first micro-interface generator breaks the propylene into micro-sized bubbles and releases the micro-sized bubbles to the first reaction zone.
  • the mixed solution flows into the first reaction zone, the propylene micro-sized bubbles and the mixed solution Of hydrogen peroxide undergoes epoxidation reaction;
  • the incompletely reacted propylene in the first reaction zone enters the second micro-interface generator through the separation layer, and the second micro-interface generator breaks the incompletely reacted propylene into micro-sized bubbles and releases the micro-sized bubbles to the second micro-interface generator.
  • the second reaction zone undergoes an epoxidation reaction with the hydrogen peroxide in the mixed solution, and the epoxidation reaction product and the mixed solution are transported to the inside of the third micro-interface generator through a circulating pump, and then released to the third reaction zone;
  • the epoxidation reaction product is transported to the inside of the gas-liquid separator for gas-liquid separation, the separated propylene gas is transported to the inside of the third interface generator, and the third micro-interface generator breaks the separated propylene gas Into micron-sized bubbles, and release the micron-sized bubbles to the third reaction zone to undergo an epoxidation reaction with the hydrogen peroxide in the mixed solution, and the separated propylene oxide is collected through the lower outlet of the separator;
  • the present invention proposes a non-etherification process for preparing propylene oxide by enhanced epoxidation of propylene, which achieves the effect of not causing equipment corrosion and no ether products during the process of preparing propylene oxide.

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  • Inorganic Chemistry (AREA)
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Abstract

本发明提供了一种强化丙烯环氧化制备环氧丙烷的无醚化系统及工艺，涉及丙烯环氧化制备环氧丙烷的技术领域，包括：内部设置有第一反应区、第二反应区和第三反应区的反应罐，第一反应区连接有用于制备和输送过氧化氢、乙腈和催化剂的混合液的混合溶剂存储罐，第二反应区连接有用于储存和输送丙烯的混合溶剂存储罐，第三反应区连接有用于接收丙烯环氧化产物，并对环氧化产物进行气液分离的气液分离器，且反应罐外部设置有连通第二反应区和第三反应区的循环泵，本发明提供的强化丙烯环氧化制备环氧丙烷的无醚化系统及工艺，达到了在制备环氧丙烷过程中，不会造成设备腐蚀且无醚类产物生成的效果的效果。

Description

一种强化丙烯环氧化制备环氧丙烷的无醚化系统及工艺 技术领域
本发明涉及丙烯环氧化制备环氧丙烷的技术领域，特别涉及一种强化丙烯环氧化制备环氧丙烷的无醚化系统及工艺。
背景技术
环氧丙烷(PO)是丙烯衍生物中产量仅次于聚丙烯和丙烯腈的第三大有机化工产品。环氧丙烷用途非常广泛，目前除了用于生产聚醚多元醇和丙三醇外，也可用于生产丙二醇、非离子表面活性剂、油田破乳剂、农药乳化剂和润湿剂等。环氧丙烷的衍生物还广泛用于汽车、建筑、食品、烟草、医药以及化妆品等行业。随着环氧丙烷用途的扩大和下游产物用量的不断增长，市场对环氧丙烷的需求量逐年增加。
目前，工业上生产环氧丙烷的主要方法是氯醇法和共氧化法(也称间接氧化法，或叫Halcon法)，这两种方法约占世界总生产能力的99％以上。氯醇法是将丙烯与氯气、水反应后生成氯丙醇，然后在碱液作用下经皂化反应得到环氧丙烷。该方法自20世纪30年代由美国联合碳化合物公司开发并进行工业生产以来，一直是生产PO的主要方法。共氧化法分异丁烷法和乙苯法。异丁烷(或乙苯)经过氧化反应生成异丁烷过氧化物(或乙苯过氧化物)，再与丙烯反应生成PO，同时联产叔丁醇(或α-甲基苯乙醇)。
但是，选用氯醇法生产环氧丙烷过程中，会产生大量的含盐废水和有机氯化物，使得设备腐蚀和排污严重，而选用共氧化法生产环氧丙烷，可以克服氯醇法的污染、腐蚀及需要氯气资源等缺点，但流程长、投资大且极易生成醚类产物，促使生产成本升高。
发明内容
鉴于此，本发明提供了一种强化丙烯环氧化制备环氧丙烷的无醚化系统及工艺，以达到在制备环氧丙烷过程中，不会造成设备腐蚀且无醚类产物生成的效果。
本发明的上述技术目的是通过以下技术方案得以实现。
一种强化丙烯环氧化制备环氧丙烷的无醚化系统，包括：
丙烯存储罐，用于储存和输送丙烯；
混合溶剂存储罐，用于制备和输送过氧化氢、乙腈和催化剂的混合液；
气液分离器，用于接收丙烯环氧化产物，并对环氧化产物进行气液分离，得到环氧丙烷和丙烯；
环氧化反应单元，包括第一反应区、第二反应区和第三反应区，所述第一反应区，设置于反应罐内部下方，用于接收所述丙烯进入反应罐内部，并作为丙烯环氧化反应的主要反应场所，第一反应区内部设置有与所述丙烯存储罐相连的第一微界面发生器；所述第二反应区，设置于反应罐内部上方且与所述混合溶剂存储罐相连，用于接收所述混合液进入反应罐内部，并作为所述第一反应区和所述第三反应区内未充分发生环氧化反应的丙烯进行环氧化反应的场所，第二反应区内部设置有分离层，用于将第二反应区和第三反应区进行完全分隔，分离层上方设置有第二微界面发生器，用于将第二反应区和第三反应区进行单向连通；所述第三反应区与所述第一反应区直接连通，第三反应区设置于反应罐中部且与气液分离器入口端连接，用于将环氧化反应产物输送至气液分离器内部，并作为气液分离器分离出来的丙烯的环氧化反应场所，内部设置有与气液分离器出口端相连的第三微界面发生器，反应罐外部设置有循环泵，循环泵进口端与第二反应区连接，出口端与第三微界面发生器连接，用于将第二反应区接收的混合液输送至第三反应区和第一反应区。
进一步地，上述强化丙烯环氧化制备环氧丙烷的无醚化系统中，所述第一微界面发生器采用气动式微界面发生器，用于在第一反应区的丙烯发生环氧化 反应之前，将丙烯气体破碎成微米级气泡，从而增大丙烯与所述混合溶液中过氧化氢的接触面积，使得丙烯的环氧化反应更加充分。
进一步地，上述强化丙烯环氧化制备环氧丙烷的无醚化系统中，所述第二微界面发生器采用气动式微界面发生器，用于作为第一反应区和第三反应内区未发生环氧化反应的丙烯进入第二反应区的通道，并将所述未发生环氧化反应的丙烯破碎成微米级气泡。
进一步地，上述强化丙烯环氧化制备环氧丙烷的无醚化系统中，所述第三微界面发生器采用液动式微界面发生器，用于将所述气液分离器分离出来的丙烯卷吸进入第三微界面发生器内部，并将卷吸进来的丙烯破碎成微米级气泡后释放到第三反应区。
进一步地，上述强化丙烯环氧化制备环氧丙烷的无醚化系统中，所述第三反应区的第三微界面发生器上方设置有缓冲栅板，用于防止反应罐内部溶液剧烈沸腾。
一种强化丙烯环氧化制备环氧丙烷的无醚化工艺，其特征在于，包括：
向丙烯储存罐内部添加足量的丙烯，同时将过氧化氢、乙腈和催化剂按相应比例添加至混合溶剂存储罐内部，制备成混合均匀的混合溶液，备用；
将所述丙烯输送至第一微界面发生器，再释放到第一反应区，丙烯逐渐进入第三反应区然后通过分离层上的第二微界面发生器进入第二反应区，直至反应罐内部被丙烯充满。然后将所述混合溶液输送至反应罐内部第二反应区，由于反应罐内部充满丙烯，顾混合溶液在气压的作用下，不会从第二微界面发生器流入第三反应区，仅能通过循环泵进入第三微界面发生器，再被释放到第三反应区和第一反应区；
第一微界面发生器将所述丙烯破碎成微米级气泡，并将微米级气泡释放至第一反应区，当所述混合溶液流入第一反应区时，丙烯微米级气泡与所述混合溶液中的过氧化氢发生环氧化反应；
所述第一反应区未发生充分反应的丙烯通过分离层进入第二微界面发生器 内部，第二微界面发生器将未充分反应的丙烯破碎成微米级气泡，并将微米级气泡释放至第二反应区与所述混合溶液中的过氧化氢发生环氧化反应，环氧化反应生成物与混合溶液通过循环泵输送至第三微界面发生器内部，再释放至第三反应区；
所述环氧化反应生成物被输送至气液分离器内部，进行气液分离，分离出来的丙烯气体被输送至第三微界面发生器内部，第三微界面发生器将分离出来的丙烯气体破碎成微米级气泡，并将微米级气泡释放至第三反应区与所述混合溶液中的过氧化氢发生环氧化反应，分离出来的环氧丙烷通过分离器下方出口进行收集。
进一步地，上述强化丙烯环氧化制备环氧丙烷的无醚化工艺中，所述微界面发生器通过将气体的压力能和/或液体的动能转变为气体表面能并传递给丙烯气体，使丙烯气体破碎成直径为微米级别的微米级气泡。
进一步地，上述强化丙烯环氧化制备环氧丙烷的无醚化工艺中，所述微米级别的微米级气泡为直径大于等于1μm、小于1mm的微米级气泡。
进一步地，上述强化丙烯环氧化制备环氧丙烷的无醚化工艺中，所述环氧化反应的反应压力为0.12-0.2MPa。
进一步地，上述强化丙烯环氧化制备环氧丙烷的无醚化工艺中，所述环氧化反应的反应温度为50-58℃。
综上所述，本发明的有益效果在于，本发明提供的强化丙烯环氧化制备环氧丙烷的无醚化系统及工艺，通过选用乙腈作为溶剂，由于乙腈作为非质子性溶剂，环氧化反应活性较采用醇类溶剂时偏低，乙腈所具有的惰性和弱碱性能有效抑制环氧丙烷的开环，从而避免生成醚化和水解副产物，并且生成物中没有大量的含盐废水和有机氯化物，从而不会造成设备严重腐蚀，且本系统中设置有微界面发生器，使得在丙烯发生环氧化反应之前，微界面发生器将丙烯气体破碎成直径大于等于1μm、小于1mm的微米级气泡，从而增大了丙烯与所述混合溶液中过氧化氢的接触面积，使得丙烯的环氧化反应更加充分，达到了 在制备环氧丙烷过程中，不会造成设备腐蚀且无醚类产物生成的效果。此外，可以根据不同工况、不同的产品要求或不同的催化剂，而对预设操作条件的范围进行灵活调整，进一步确保了反应的充分有效进行，进而保证了反应速率，达到了强化反应的目的。
尤其，本系统中设置了，第一反应区、第二反应区和第三反应区，分别用于接收丙烯进入反应罐内部，并作为丙烯环氧化反应的主要反应场所、接收所述混合液进入反应罐内部并作为第一反应区内未充分发生环氧化反应的丙烯，进行环氧化反应的场所和将环氧化反应产物输送至气液分离器内部，并作为气液分离器分离出来的丙烯的环氧化反应场所，使得丙烯在本系统中可以充分的利用，从而降低生产成本。
尤其，本系统中所述第二反应区的第二微界面发生器上方设置有缓冲栅板，当系统中温度过高或反应过于剧烈时，缓冲栅板有效的避免了由于反应罐内部剧烈沸腾对反应罐造成的损害，从而延长反应罐的使用寿命。
附图说明
通过阅读下文优选实施方式的详细描述，各种其他的优点和益处对于本领域普通技术人员将变得清楚明了。附图仅用于示出优选实施方式的目的，而并不认为是对本发明的限制。而且在整个附图中，用相同的参考符号表示相同的部件。在附图中：
图1为本发明实施例提供的一种强化丙烯环氧化制备环氧丙烷的无醚化系统及工艺的结构示意图。
具体实施方式
为了使本发明的目的和优点更加清楚明白，下面结合实施例对本发明作进一步描述；应当理解，此处所描述的具体实施例仅仅用于解释本发明，并不用于限定本发明。
需要说明的是，在本发明的描述中，术语“上”、“下”、“左”、“右”、“内”、“外”等指示的方向或位置关系的术语是基于附图所示的方向或位置关系，这仅仅是为了便于描述，而不是指示或暗示所述装置或元件必须具有特定的方位、以特定的方位构造和操作，因此不能理解为对本发明的限制。
此外，还需要说明的是，在本发明的描述中，除非另有明确的规定和限定，术语“安装”、“相连”、“连接”应做广义理解，例如，可以是固定连接，也可以是可拆卸连接，或一体地连接；可以是机械连接，也可以是电连接；可以是直接相连，也可以通过中间媒介间接相连，可以是两个元件内部的连通。对于本领域技术人员而言，可根据具体情况理解上述术语在本发明中的具体含义。
参阅图1所示，为本发明实施例提供的强化丙烯环氧化制备环氧丙烷的无醚化系统，包括内部设置有第一反应区、第二反应区和第三反应区的反应罐3，第一反应区连接有用于储存和输送丙烯的丙烯存储罐1，第二反应区连接有用于制备和输送过氧化氢、乙腈和催化剂的混合液的混合溶剂存储罐2，第三反应区连接有用于接收丙烯环氧化产物，并对环氧化产物进行气液分离的气液分离器4，且反应罐3外部设置有连通第二反应区和第三反应区的循环泵36。
系统启动前向丙烯储存罐内部添加足量的丙烯，同时将过氧化氢、乙腈和催化剂按相应比例添加至混合溶剂存储罐2内部，制备成混合均匀的混合溶液。
继续参阅图1所示，反应罐3内部下方设置有第一反应区，第一反应区内设置有第一微界面发生器31。第一微界面发生器31与反应罐3内部固定连接，其入口端与所述丙烯存储罐1相连。启动系统，将所述丙烯输送至第一微界面发生器31，再释放到第一反应区，丙烯逐渐进入第三反应区然后通过分离层34上的第二微界面发生器32进入第二反应区，直至反应罐3内部被丙烯充满。然后将所述混合溶液输送至反应罐3内部第二反应区，由于反应罐3内部充满丙烯，顾混合溶液在气压的作用下，不会从第二微界面发生器32流入第三反应区，仅能通过循环泵36进入第三微界面发生器33，再被释放到第三反应区 和第一反应区。第一微界面发生器31将丙烯破碎成直径大于等于1μm、小于1mm的微米级气泡，并将微米级气泡释放至第一反应区，当混合溶液流入第一反应区时，丙烯微米级气泡与所述混合溶液中的过氧化氢发生环氧化反应。
继续参阅图1所示，反应罐3内部上方设置有与所述混合溶剂存储罐2相连的第二反应区，第二反应区内固定连接有分离层34，用于将第二反应区与第一反应区、第三反应区内的物质进行分离，分离层34上方设置有第二微界面发生器32，第二未微界面发生器入口端与第一反应区和第三反应区连通。第一反应区未发生充分反应的丙烯以及生成的废气通过分离层34进入第二微界面发生器32内部，第二微界面发生器32将未充分反应的丙烯破碎成直径大于等于1μm、小于1mm的微米级气泡，并将微米级气泡释放至第二反应区与混合溶液中的过氧化氢发生环氧化反应，环氧化反应生成物与混合溶液通过循环泵36输送至第三反应区，废气排除反应罐3。
反应罐3中部设置有与气液分离器4入口端连接的第三反应区，第三反应区内固定连接有第三微界面发生器33，第三微界面发生器33分别与气液分离器4出口端和循环泵36出口端相连，且在第三微界面发生器33和循环泵36之间设置有换热器37。第三微界面发生器33上方设置有缓冲栅板35，用于防止反应罐3内部溶液剧烈沸腾。第一反应区和第二反应区的环氧化反应生成物被输送至气液分离器4内部，进行气液分离，分离出来的丙烯气体被输送至第三界面发生器内部，第三微界面发生器33将分离出来的丙烯气体破碎成直径大于等于1μm、小于1mm的微米级气泡，并将微米级气泡释放至第三反应区与所述混合溶液中的过氧化氢发生环氧化反应，分离出来的环氧丙烷成品通过分离器下方出口进行收集，反应罐3反应罐3内部生成的废液通过废液通道排出。
优选的，微界面发生器通过将气体的压力能和/或液体的动能转变为液体表面能并传递给液氯，使液氯破碎成直径为微米级别的微米级气泡，根据能量输入方式或气液比分为气动式微界面发生器、液动式微界面发生器和气液联动式微界面发生器，其中气动式微界面发生器采用气体驱动，输入气量远大于液 体量；液动式微界面发生器采用液体驱动，输入气量一般小于液体量；气液联动式微界面发生器采用气液同时驱动，输入气量接近于液体量。所述第一微界面发生器31和所述第二微界面发生器32为气动式微界面发生器，所述第三微界面发生器33为液动式微界面发生器。
本发明提供的强化丙烯环氧化制备环氧丙烷的无醚化系统，通过选用乙腈作为溶剂，由于乙腈作为非质子性溶剂，环氧化反应活性较采用醇类溶剂时偏低，乙腈所具有的惰性和弱碱性能有效抑制环氧丙烷的开环，从而避免生成醚化和水解副产物，并且生成物中没有大量的含盐废水和有机氯化物，从而不会造成设备严重腐蚀，且本系统中设置有微界面发生器，使得在丙烯发生环氧化反应之前，微界面发生器将丙烯气体破碎成直径大于等于1μm、小于1mm的微米级气泡，从而增大了丙烯与所述混合溶液中过氧化氢的接触面积，使得丙烯的环氧化反应更加充分，达到了在制备环氧丙烷过程中不会造成设备腐蚀且无醚类产物生成的效果。
下面结合图1进一步说明本发明所述系统的具体方法与效果。
一种强化丙烯环氧化制备环氧丙烷的无醚化工艺，包括：
向丙烯储存罐内部添加足量的丙烯，同时将过氧化氢、乙腈和催化剂按相应比例添加至混合溶剂存储罐内部，制备成混合均匀的混合溶液，备用；
将所述丙烯输送至第一微界面发生器，再释放到第一反应区，丙烯逐渐进入第三反应区然后通过分离层上的第二微界面发生器进入第二反应区，直至反应罐内部被丙烯充满，然后将所述混合溶液输送至反应罐内部第二反应区，由于反应罐内部充满丙烯，顾混合溶液在气压的作用下，不会从第二微界面发生器流入第三反应区，仅能通过循环泵进入第三微界面发生器，再被释放到第三反应区和第一反应区；
第一微界面发生器将所述丙烯破碎成微米级气泡，并将微米级气泡释放至第一反应区，当所述混合溶液流入第一反应区时，丙烯微米级气泡与所述混合溶液中的过氧化氢发生环氧化反应；
所述第一反应区未发生充分反应的丙烯通过分离层进入第二微界面发生器内部，第二微界面发生器将未充分反应的丙烯破碎成微米级气泡，并将微米级气泡释放至第二反应区与所述混合溶液中的过氧化氢发生环氧化反应，环氧化反应生成物与混合溶液通过循环泵输送至第三微界面发生器内部，再释放至第三反应区；
所述环氧化反应生成物被输送至气液分离器内部，进行气液分离，分离出来的丙烯气体被输送至第三微界面发生器内部，第三微界面发生器将分离出来的丙烯气体破碎成微米级气泡，并将微米级气泡释放至第三反应区与所述混合溶液中的过氧化氢发生环氧化反应，分离出来的环氧丙烷通过分离器下方出口进行收集。
优选的，环氧化反应的反应压力为0.1-0.2MPa。
优选的，环氧化反应的反应温度为50-58℃。
为了进一步验证本发明所提供的加工方法，结合实施例进一步说明本发明的有益效果。同时，本实施例中不具体限定催化剂的种类，其可以为铁系催化剂、钼系催化剂、镍系催化剂、钴系催化剂以及钨系催化剂中的一种或几种组合，只要能够确保强化反应顺利进行即可。
实施例1：
向丙烯储存罐内部添加足量的丙烯，同时将过氧化氢和乙腈添加至混合溶剂存储罐内部，制备成混合均匀的混合溶液，其混合溶液中过氧化氢的质量分数为40％，再向混合溶剂存储罐内部加入适量的TS-1催化剂，再将反应罐内温度控制在50℃，压力控制在0.1MPa；
将所述丙烯输送至第一微界面发生器，再释放到第一反应区，丙烯逐渐进入第三反应区然后通过分离层上的第二微界面发生器进入第二反应区，直至反应罐内部被丙烯充满，然后将500g混合溶液缓慢输送至反应罐内部第二反应区，通过循环泵进入第三微界面发生器，再被释放到第三反应区和第一反应区；
第一微界面发生器将所述丙烯破碎成微米级气泡，并将微米级气泡释放至 第一反应区，当所述混合溶液流入第一反应区时，丙烯微米级气泡与所述混合溶液中的过氧化氢发生环氧化反应；
所述第一反应区未发生充分反应的丙烯通过分离层进入第二微界面发生器内部，第二微界面发生器将未充分反应的丙烯破碎成微米级气泡，并将微米级气泡释放至第二反应区与所述混合溶液中的过氧化氢发生环氧化反应，环氧化反应生成物与混合溶液通过循环泵输送至第三微界面发生器内部，再释放至第三反应区；
所述环氧化反应生成物被输送至气液分离器内部，进行气液分离，分离出来的丙烯气体被输送至第三界面发生器内部，第三微界面发生器将分离出来的丙烯气体破碎成微米级气泡，并将微米级气泡释放至第三反应区与所述混合溶液中的过氧化氢发生环氧化反应，分离出来的环氧丙烷通过分离器下方出口进行收集；
反应结束后，测得过氧化氢的转化率为93％，环氧丙烷的选择性为85％，醚类产物含量0％，有机氯化物含量0％。
实施例2：
向丙烯储存罐内部添加足量的丙烯，同时将过氧化氢和乙腈添加至混合溶剂存储罐内部，制备成混合均匀的混合溶液，其混合溶液中过氧化氢的质量分数为40％，再向混合溶剂存储罐内部加入适量的TS-1催化剂，再将反应罐内温度控制在54℃，压力控制在0.15MPa；
将所述丙烯输送至第一微界面发生器，再释放到第一反应区，丙烯逐渐进入第三反应区然后通过分离层上的第二微界面发生器进入第二反应区，直至反应罐内部被丙烯充满，然后将1000g混合溶液缓慢输送至反应罐内部第二反应区，通过循环泵进入第三微界面发生器，再被释放到第三反应区和第一反应区；
第一微界面发生器将所述丙烯破碎成微米级气泡，并将微米级气泡释放至第一反应区，当所述混合溶液流入第一反应区时，丙烯微米级气泡与所述混合溶液中的过氧化氢发生环氧化反应；
所述第一反应区未发生充分反应的丙烯通过分离层进入第二微界面发生器内部，第二微界面发生器将未充分反应的丙烯破碎成微米级气泡，并将微米级气泡释放至第二反应区与所述混合溶液中的过氧化氢发生环氧化反应，环氧化反应生成物与混合溶液通过循环泵输送至第三微界面发生器内部，再释放至第三反应区；
所述环氧化反应生成物被输送至气液分离器内部，进行气液分离，分离出来的丙烯气体被输送至第三界面发生器内部，第三微界面发生器将分离出来的丙烯气体破碎成微米级气泡，并将微米级气泡释放至第三反应区与所述混合溶液中的过氧化氢发生环氧化反应，分离出来的环氧丙烷通过分离器下方出口进行收集；
反应结束后，测得过氧化氢的转化率为95％，环氧丙烷的选择性为89％，醚类产物含量0％，有机氯化物含量0％。
实施例3：
向丙烯储存罐内部添加足量的丙烯，同时将过氧化氢和乙腈添加至混合溶剂存储罐内部，制备成混合均匀的混合溶液，其混合溶液中过氧化氢的质量分数为40％，再向混合溶剂存储罐内部加入适量的TS-1催化剂，再将反应罐内温度控制在58℃，压力控制在0.2MPa；
将所述丙烯输送至第一微界面发生器，再释放到第一反应区，丙烯逐渐进入第三反应区然后通过分离层上的第二微界面发生器进入第二反应区，直至反应罐内部被丙烯充满，然后将1000g混合溶液缓慢输送至反应罐内部第二反应区，通过循环泵进入第三微界面发生器，再被释放到第三反应区和第一反应区；
第一微界面发生器将所述丙烯破碎成微米级气泡，并将微米级气泡释放至第一反应区，当所述混合溶液流入第一反应区时，丙烯微米级气泡与所述混合溶液中的过氧化氢发生环氧化反应；
所述第一反应区未发生充分反应的丙烯通过分离层进入第二微界面发生器内部，第二微界面发生器将未充分反应的丙烯破碎成微米级气泡，并将微米 级气泡释放至第二反应区与所述混合溶液中的过氧化氢发生环氧化反应，环氧化反应生成物与混合溶液通过循环泵输送至第三微界面发生器内部，再释放至第三反应区；
所述环氧化反应生成物被输送至气液分离器内部，进行气液分离，分离出来的丙烯气体被输送至第三界面发生器内部，第三微界面发生器将分离出来的丙烯气体破碎成微米级气泡，并将微米级气泡释放至第三反应区与所述混合溶液中的过氧化氢发生环氧化反应，分离出来的环氧丙烷通过分离器下方出口进行收集；
反应结束后，测得过氧化氢的转化率为97％，环氧丙烷的选择性为92％，醚类产物含量0％，有机氯化物含量0％。
鉴于此，本发明提出了一种强化丙烯环氧化制备环氧丙烷的无醚化工艺，达到了在制备环氧丙烷过程中，不会造成设备腐蚀且无醚类产物生成的效果。
上述具体实施例仅仅是对本发明的解释，其并不是对本发明的限制，本领域技术人员在阅读完本说明书后可以根据需要对本实施例做出没有创造性贡献的修改，但只要在本发明的权利要求范围内都受到专利法的保护。

Claims (10)

  1. 一种强化丙烯环氧化制备环氧丙烷的无醚化系统，其特征在于，包括：
    丙烯存储罐，用于储存和输送丙烯；
    混合溶剂存储罐，用于制备和输送过氧化氢、乙腈和催化剂的混合液；
    气液分离器，用于接收丙烯环氧化产物，并对环氧化产物进行气液分离，得到环氧丙烷和丙烯；
    环氧化反应单元，包括第一反应区、第二反应区和第三反应区，所述第一反应区，设置于反应罐内部下方，用于接收所述丙烯进入反应罐内部，并作为丙烯环氧化反应的主要反应场所，第一反应区内部设置有与所述丙烯存储罐相连的第一微界面发生器；所述第二反应区，设置于反应罐内部上方且与所述混合溶剂存储罐相连，用于接收所述混合液进入反应罐内部，并作为所述第一反应区和所述第三反应区内未充分发生环氧化反应的丙烯进行环氧化反应的场所，第二反应区内部设置有分离层，用于将第二反应区和第三反应区进行完全分隔，分离层上方设置有第二微界面发生器，用于将第二反应区和第三反应区进行单向连通；所述第三反应区与所述第一反应区直接连通，第三反应区设置于反应罐中部且与气液分离器入口端连接，用于将环氧化反应产物输送至气液分离器内部，并作为气液分离器分离出来的丙烯的环氧化反应场所，内部设置有与气液分离器出口端相连的第三微界面发生器，反应罐外部设置有循环泵，循环泵进口端与第二反应区连接，出口端与第三微界面发生器连接，用于将第二反应区接收的混合液输送至第三反应区和第一反应区。
  2. 根据权利要求1所述的强化丙烯环氧化制备环氧丙烷的无醚化系统，其特征在于,所述第一微界面发生器采用气动式微界面发生器，用于在第一反应区的丙烯发生环氧化反应之前，将丙烯气体破碎成微米级气泡，从而增大丙烯与所述混合溶液中过氧化氢的接触面积，使得丙烯的环氧化反应更加充分。
  3. 根据权利要求1所述的强化丙烯环氧化制备环氧丙烷的无醚化系统，其特征在于,所述第二微界面发生器采用气动式微界面发生器，用于作为第一反 应区和第三反应内区未发生环氧化反应的丙烯进入第二反应区的通道，并将所述未发生环氧化反应的丙烯破碎成微米级气泡。
  4. 根据权利要求1所述的强化丙烯环氧化制备环氧丙烷的无醚化系统，其特征在于,所述第三微界面发生器采用液动式微界面发生器，用于将所述气液分离器分离出来的丙烯卷吸进入第三微界面发生器内部，并将卷吸进来的丙烯破碎成微米级气泡后释放到第三反应区。
  5. 根据权利要求1所述的强化丙烯环氧化制备环氧丙烷的无醚化系统，其特征在于,所述第三反应区的第三微界面发生器上方设置有缓冲栅板，用于防止反应罐内部溶液剧烈沸腾。
  6. 一种强化丙烯环氧化制备环氧丙烷的无醚化工艺，其特征在于，包括：
    向丙烯储存罐内部添加足量的丙烯，同时将过氧化氢、乙腈和催化剂按相应比例添加至混合溶剂存储罐内部，制备成混合均匀的混合溶液，备用；
    将所述丙烯输送至第一微界面发生器，再释放到第一反应区，丙烯逐渐进入第三反应区然后通过分离层上的第二微界面发生器进入第二反应区，直至反应罐内部被丙烯充满，然后将所述混合溶液输送至反应罐内部第二反应区，由于反应罐内部充满丙烯，顾混合溶液在气压的作用下，不会从第二微界面发生器流入第三反应区，仅能通过循环泵进入第三微界面发生器，再被释放到第三反应区和第一反应区；
    第一微界面发生器将所述丙烯破碎成微米级气泡，并将微米级气泡释放至第一反应区，当所述混合溶液流入第一反应区时，丙烯微米级气泡与所述混合溶液中的过氧化氢发生环氧化反应；
    所述第一反应区未发生充分反应的丙烯通过分离层进入第二微界面发生器内部，第二微界面发生器将未充分反应的丙烯破碎成微米级气泡，并将微米级气泡释放至第二反应区与所述混合溶液中的过氧化氢发生环氧化反应，环氧化反应生成物与混合溶液通过循环泵输送至第三微界面发生器内部，再释放至第三反应区；
    所述环氧化反应生成物被输送至气液分离器内部，进行气液分离，分离出来的丙烯气体被输送至第三微界面发生器内部，第三微界面发生器将分离出来的丙烯气体破碎成微米级气泡，并将微米级气泡释放至第三反应区与所述混合溶液中的过氧化氢发生环氧化反应，分离出来的环氧丙烷通过分离器下方出口进行收集。
  7. 根据权利要求6所述的强化丙烯环氧化制备环氧丙烷的无醚化工艺，其特征在于,所述微界面发生器通过将气体的压力能和/或液体的动能转变为气体表面能并传递给丙烯气体，使丙烯气体破碎成直径为微米级别的微米级气泡。
  8. 根据权利要求1-7所述的强化丙烯环氧化制备环氧丙烷的无醚化工艺，其特征在于,所述微米级别的微米级气泡为直径大于等于1μm、小于1mm的微米级气泡。
  9. 根据权利要求6所述的强化丙烯环氧化制备环氧丙烷的无醚化工艺，其特征在于,所述环氧化反应的反应压力为0.1-0.2MPa。
  10. 根据权利要求6所述的强化丙烯环氧化制备环氧丙烷的无醚化工艺，其特征在于,所述环氧化反应的反应温度为50-58℃。
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