WO2024060581A1 - Process for producing epoxypropane by using hppo method of liquid-solid circulating fluidized bed reaction-regeneration system - Google Patents

Process for producing epoxypropane by using hppo method of liquid-solid circulating fluidized bed reaction-regeneration system Download PDF

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WO2024060581A1
WO2024060581A1 PCT/CN2023/086467 CN2023086467W WO2024060581A1 WO 2024060581 A1 WO2024060581 A1 WO 2024060581A1 CN 2023086467 W CN2023086467 W CN 2023086467W WO 2024060581 A1 WO2024060581 A1 WO 2024060581A1
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liquid
catalyst
regeneration
reaction
hydrogen peroxide
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PCT/CN2023/086467
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French (fr)
Chinese (zh)
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黄家辉
刘应春
苏鑫
何古色
龙化云
何鹏
王昌云
李新菊
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中国科学院大连化学物理研究所
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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
    • C07D301/00—Preparation of oxiranes
    • C07D301/32—Separation; Purification
    • 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
    • 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
    • Y02P20/584—Recycling of catalysts

Definitions

  • the invention belongs to the technical field of propylene oxide production, and specifically relates to a process for directly oxidizing propylene with hydrogen peroxide to prepare propylene oxide by utilizing a liquid-solid circulating fluidized bed reaction-regeneration system.
  • Propylene oxide is the second largest derivative of propylene, second only to polypropylene. It can be used to produce polyether polyols, 1,2-propanediol, etc. It is also the fourth generation of nonionic surfactants for detergents, The main raw material for oilfield demulsifiers, pesticide emulsifiers, etc. Its terminals are widely used in industries such as construction, food, tobacco, medicine and cosmetics, and are important raw materials for fine chemicals. At present, the main production methods of propylene oxide include chlorohydrin method, co-oxidation method and direct oxidation method (HPPO).
  • the chlorohydrin method uses propylene, chlorine and lime milk as raw materials, and produces propylene oxide through chlorohydration and saponification of propylene.
  • This process has mature technology, great operating flexibility, and good raw material adaptability.
  • a large amount of waste water and waste residue are produced during the reaction process, causing serious environmental pollution.
  • the production of 1 ton of propylene oxide produces about 40 tons of chlorine-containing wastewater and 2 tons of calcium chloride waste residue.
  • the hypochlorous acid produced during the reaction seriously corrodes the equipment.
  • about 40% of the world's propylene oxide production is produced by the chlorohydrin process.
  • foreign countries had stopped building new projects for chlorohydrin process units, and gradually used other methods to eliminate existing production capacity.
  • the co-oxidation rule is to generate propylene oxide and organic alcohol through organic hydrogen peroxide and propylene. According to different raw materials and co-products, it is divided into isobutane co-oxidation method and ethylbenzene co-oxidation method.
  • the isobutane method uses the organic peroxide tert-butyl hydroperoxide (TBHP) of isobutane as an oxidant to oxidize propylene to produce propylene oxide. For every ton of propylene oxide produced, 2.3 tons of tert-butyl alcohol (TBA) are produced. ).
  • the ethylbenzene co-oxidation method uses ethylbenzene peroxide as an oxidant to oxidize propylene to produce propylene oxide. For every ton of propylene oxide produced, 2.2-2.6 tons of styrene are co-produced.
  • the source of raw materials and product sales have major mutual constraints. Only when the market demand for PO and co-products matches can the advantages of this process be revealed.
  • the HPPO process uses hydrogen peroxide and propylene as raw materials, in the role of titanium silicon molecular sieve catalyst
  • the epoxidation reaction is carried out to produce propylene oxide, and the only by-product is water.
  • the process conditions are mild and energy consumption is greatly reduced.
  • wastewater discharge can be reduced by 70-80% and energy consumption reduced by about 35%.
  • Propylene oxide production route At present, companies such as Dow/BASF, Degussa/Uhde, and Sinopec have realized the industrialization of the HPPO process.
  • the above-mentioned existing technologies all use fixed-bed processes. The raw materials stay in the reactor for a long time.
  • the purpose of the present invention is to provide a HPPO process for producing propylene oxide using a liquid-solid circulating fluidized bed reaction-regeneration system.
  • the conversion rate of hydrogen peroxide is as high as 99.51%, and the effective utilization rate of hydrogen peroxide is as high as 99.99%.
  • the selectivity of propylene oxide is as high as 99.03%.
  • the reaction time is significantly shortened and the reaction effect is significantly improved.
  • the present invention provides a HPPO method for producing propylene oxide using a liquid-solid circulating fluidized bed reaction-regeneration system.
  • the liquid-solid circulating fluidized bed reaction-regeneration system uses hydrogen peroxide to directly oxidize propylene to prepare propylene oxide.
  • the liquid-solid circulating fluidized bed reaction-regeneration system mainly includes a catalyst regenerator 16, a feed inclined pipe 7, a riser reactor 11, a liquid-solid separator 12 and a return inclined pipe 14, which are connected in series.
  • the outlet end is connected to the middle part of the side wall of the catalyst regenerator 16; the top of the catalyst regenerator 16 is connected to the solvent recovery and separation system 18 through a pipeline, and a regeneration liquid distributor 17 is provided at the bottom of the catalyst regenerator 16.
  • the catalyst regenerator 16 The regeneration liquid inlet 21 is provided at the axis of the bottom.
  • the regeneration liquid distributor 17 and the regeneration liquid inlet 21 are jointly used to evenly distribute the regeneration liquid to fully fluidize the catalyst flowing back to the catalyst regenerator 16.
  • the regeneration liquid The distributor 17 and the regeneration liquid inlet 21 are connected to the regeneration liquid storage tank 19 through pipelines; a filter 13 is provided on the top of the liquid-solid separator 12, and the filtration end of the filter 13 is connected to the solvent recovery and separation system 18 through pipelines.
  • the bottom of the material inclined tube 14 and the side wall of the inclined tube are provided with cleaning liquid inlets;
  • a feed control valve 8 is provided in the feed inclined pipe 7, and the connection between the riser reactor 11 and the feed inclined pipe 7 is provided with a main liquid flow inlet 5 located at the axis of the riser reactor 11 and an auxiliary liquid.
  • the inlet 6, the main liquid flow inlet 5 and the auxiliary liquid inlet 6 are respectively connected to the raw material mixer 4, and the raw material mixer 4 is connected to the raw material propylene storage tank 1 and the solvent storage tank 2 respectively through pipelines.
  • 1-10 hydrogen peroxide inlets 9 are arranged along the axial direction on the side wall of the riser reactor 11, and the inlets are higher than the main liquid flow inlet 5 and the auxiliary liquid inlet 6.
  • the hydrogen peroxide inlets 9 are connected to the hydrogen peroxide storage tank 3 through pipes.
  • a reaction heat exchange system 10 is provided on the lifting section of the riser reactor 11, and the cleaning liquid inlet provided on the return inclined pipe 14 is connected to the cleaning liquid storage tank 20 through a pipeline; between the return inclined pipe 14 and the catalyst regenerator 16
  • a return control valve 15 is provided in the inclined pipe between the two.
  • the riser reactor 11 is a liquid-solid two-phase system, and the solids are microspherical TS-1 catalyst particles.
  • the average particle diameter of the catalyst is 20-5000 ⁇ m, and the particle density is 600-3000kg/m 3 .
  • solvents described in S1 are methanol, ethanol, acetone, acetonitrile, chloroform, 1,4- One or a mixture of two or more of dioxane, isopropyl alcohol and tert-butyl alcohol.
  • the apparent liquid velocity of the mixture in the riser reactor 11 described in S1 is 3-5000m/h
  • the molar ratio of hydrogen peroxide to propylene is 1:1-1:5
  • the molar ratio of hydrogen peroxide to solvent is 1 :4-1:10
  • the concentration of hydrogen peroxide is 5-70%.
  • reaction temperature in S1 is controlled between 0-70°C, and the pressure in the reactor is controlled between 1-10MPa.
  • the effective height of the riser reactor 11 described in S1 is 5-60m, and the liquid phase residence time is 5-240min.
  • the cleaning liquid described in S3 is one or a mixture of two or more of methanol, ethanol, acetone, acetonitrile, chloroform, 1,4-dioxane, isopropanol, and tert-butanol.
  • the regeneration process described in S4 adopts physical regeneration or chemical regeneration, and the control range of the superficial liquid velocity of the regeneration liquid in the catalyst regenerator 16 is 0.01-5m/h.
  • the physical regeneration mainly uses a regeneration liquid to clean the catalyst to remove attachments on the catalyst surface and in the pores;
  • the regeneration liquid is methanol, ethanol, acetone, acetonitrile, chloroform, 1,4-dioxane , isopropyl alcohol, tert-butyl alcohol, or a mixture of two or more thereof;
  • the control temperature is normal temperature -200°C, and the residence time of the catalyst in the catalyst regenerator 16 is 2-72 hours.
  • the chemical regeneration is performed by adding hydrogen peroxide to the regeneration liquid, using the hydrogen peroxide to chemically react with oligomers on the catalyst surface or in the pores, and removing carbon deposits on the catalyst surface or in the pores; the hydrogen peroxide in the chemical regeneration liquid
  • concentration 0.2%-5%
  • control temperature during chemical regeneration is 50-100°C
  • residence time of the catalyst in the catalyst regenerator 16 is 2-72 hours.
  • the catalyst stored in the catalyst regenerator 16 has a stacking height of 0.5-50 m.
  • the present invention has a conversion rate of hydrogen peroxide as high as 99.51%, an effective utilization rate of hydrogen peroxide as high as 99.99%, and a selectivity of propylene oxide as high as 99.03%, which is different from the existing fixed Compared with the bed reactor process, the reaction time is significantly shortened and the reaction effect is significantly improved.
  • Figure 1 is a flow chart of the HPPO method for producing propylene oxide using a liquid-solid circulating fluidized bed reaction-regeneration system according to the present invention
  • Figure 2 is a schematic diagram of the structure of the liquid-solid circulating fluidized bed reaction-regeneration system of the present invention, in which 1-raw material propylene storage tank, 2-solvent storage tank, 3-hydrogen peroxide storage tank, 4-raw material mixer, 5-main liquid Inflow port, 6-auxiliary liquid inlet, 7-feed inclined tube, 8-feed control valve, 9-hydrogen peroxide inlet, 10-reaction heat exchange system, 11-riser reactor, 12-liquid-solid separator, 13 -Filter, 14-return inclined pipe, 15-return control valve, 16-catalyst regenerator, 17-regeneration liquid distributor, 18-solvent recovery and separation system, 19-regeneration liquid storage tank, 20-cleaning liquid Storage tank, 21-regeneration fluid inlet.
  • This embodiment provides a HPPO method for producing propylene oxide using a liquid-solid circulating fluidized bed reaction-regeneration system.
  • the process flow is shown in Figure 1.
  • the hydrogen peroxide is directly oxidized by using a liquid-solid circulating fluidized bed reaction-regeneration system.
  • Propylene prepares propylene oxide; the structural diagram of the liquid-solid circulating fluidized bed reaction-regeneration system used is shown in Figure 2.
  • the liquid-solid circulating fluidized bed reaction-regeneration The system mainly includes a catalyst regenerator 16, a feed inclined pipe 7, a riser reactor 11, a liquid-solid separator 12 and a return inclined pipe 14 in series. The outlet end of the return inclined pipe 14 is connected to the side of the catalyst regenerator 16.
  • the middle part of the wall is connected; the top of the catalyst regenerator 16 is connected to the solvent recovery and separation system 18 through a pipeline, the bottom of the catalyst regenerator 16 is provided with a regeneration liquid distributor 17, and the axis of the bottom of the catalyst regenerator 16 is provided with a regeneration liquid.
  • the inlet 21 and the regeneration liquid distributor 17 are annular coil type liquid distributors.
  • the regeneration liquid distributor 17 and the regeneration liquid inlet 21 are jointly used to evenly distribute the regeneration liquid to fully fluidize the catalyst flowing back to the catalyst regenerator 16 for regeneration.
  • the liquid distributor 17 and the regeneration liquid inlet 21 are connected to the regeneration liquid storage tank 19 through pipelines; a feed control valve 8 is provided in the feed inclined pipe 7, and a connection point between the riser reactor 11 and the feed inclined pipe 7 is provided.
  • the main liquid flow inlet 5 and the auxiliary liquid inlet 6 at the axis of the riser reactor 11 are respectively connected to the raw material mixer 4, and the raw material mixer 4 is respectively connected to the raw material propylene storage tank 1 through pipelines.
  • the solvent storage tank 2 Connected to the solvent storage tank 2; three hydrogen peroxide inlets 9 are arranged along the axial direction on the side wall of the riser reactor 11.
  • the hydrogen peroxide inlets 9 are connected to the hydrogen peroxide storage tank 3 through pipelines, and the inlets are higher than the main liquid flow inlet 5 and the auxiliary liquid.
  • Inlet 6 a reaction heat exchange system 10 is provided on the lifting section of the riser reactor 11, the liquid-solid separator 12 is a sedimentation separator, and a filter 13 is provided on the top of the liquid-solid separator 12.
  • the filtration of the filter 13 The end is connected to the solvent recovery and separation system 18 through a pipeline.
  • the bottom of the return inclined pipe 14 and the side wall of the inclined pipe are provided with a cleaning liquid inlet, which is connected to the cleaning liquid storage tank 20 through a pipeline; the return inclined pipe 14 is connected to the catalyst regeneration
  • a return control valve 15 is provided in the inclined pipe between the devices 16;
  • the process mainly includes the following steps:
  • the specific process of S1 is: propylene from the raw material propylene storage tank 1 and methanol from the solvent storage tank 2 are mixed in the raw material mixer 4, and enter the riser reactor through the main liquid flow inlet 5 and the auxiliary liquid inlet 6 respectively.
  • the bottom is evenly mixed with the TS-1 catalyst particles from the feed inclined tube 7 (the median particle diameter of the catalyst particles is 85 ⁇ m, and the particle density is 2000kg/m 3 ), and is moved along the riser reactor under the action of the liquid flow 11 moves axially upward; use the feed control valve 8 to control the catalyst entering the bottom of the reactor through the feed inclined pipe 7
  • the hydrogen peroxide is fully mixed with propylene, solvent methanol and catalyst to cause epoxidation reaction.
  • the residence time of the liquid is controlled to 12 minutes; the apparent liquid velocity of the liquid phase mixture in the riser reactor 11 is 40m/h, and the hydrogen peroxide and propylene
  • the molar ratio is 1:4, and the molar ratio of hydrogen peroxide to solvent methanol is 1:7.5; by adjusting the temperature and flow rate of the circulating water in the reaction heat exchange system 10, the reaction temperature of the riser reactor 11 is controlled to 35°C, and the reaction pressure is 3MPa .
  • the specific process of S2 is: as the reaction proceeds, the hydrogen peroxide is basically consumed by the reaction, and the reaction catalyst and liquid phase products (mainly including the solvent methanol, propylene, the generated propylene oxide and water) enter the liquid-solid separator 12, and pass through After liquid-solid separation, the liquid phase product passes through the filter 13 to remove fine catalyst particles, and then enters the solvent recovery and separation system 18; the catalyst particles settle to the bottom of the separator 12 and enter the return inclined pipe 14.
  • the reaction catalyst and liquid phase products mainly including the solvent methanol, propylene, the generated propylene oxide and water
  • the specific process of S3 is: pass an appropriate amount of cleaning liquid through the side wall of the return inclined pipe 14 above the return control valve 15.
  • the cleaning liquid is methanol.
  • the reaction liquid phase products on the surface of the catalyst particles and in the pores are removed. It is cleaned and brought into the solid-liquid separator 12, and finally enters the solvent recovery and separation system 18 through the filter 13 and the reaction liquid phase product; the catalyst falls into the catalyst regenerator 16 after the reaction of liquid extraction in the return inclined pipe 14.
  • the specific process of S4 is: the physical regeneration method is used to regenerate the catalyst in the catalyst regenerator 16.
  • the regeneration liquid in the catalyst regenerator 16 is methanol.
  • a liquid-solid moving bed is formed in the dilute phase zone at the top of the catalyst regenerator 16 to further regenerate the catalyst surface. and clean the products attached in the pores to achieve catalyst regeneration and extend the service life of the catalyst.
  • the process of direct oxidation of propylene with hydrogen peroxide to produce propylene oxide is realized in the liquid-solid riser reactor 11, and the catalyst regenerator 16 is used to realize the regeneration of the catalyst.
  • the liquid-solid riser reactor 11 and the catalyst regenerator 16 are highly coupled and operate continuously to achieve The catalyst is continuously regenerated.
  • the conversion rate of hydrogen peroxide is as high as 99.51%, and the effective utilization rate of hydrogen peroxide is as high as 99.99% during the process of oxidizing propylene with hydrogen peroxide to produce propylene oxide using the liquid-solid circulating fluidized bed reaction-regeneration system.
  • the selection of propylene oxide The efficiency is as high as 99.03%.
  • the reaction time is significantly shortened and the reaction effect is significantly improved.
  • the specific results are shown in Table 1.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Epoxy Compounds (AREA)

Abstract

Disclosed is a process for producing epoxypropane by using an HPPO method of a liquid-solid circulating fluidized bed reaction-regeneration system, which belongs to the technical field of epoxypropane production. In the present invention, by means of the liquid-solid circulating fluidized bed reaction-regeneration system, hydrogen peroxide is used to directly oxidize propylene to prepare epoxypropane. The liquid-solid circulating fluidized bed reaction-regeneration system mainly comprises a catalyst regenerator, a feeding inclined pipe, a lifting pipe reactor, a liquid-solid separator, a return inclined pipe and other components. In the process, the liquid-solid circulating fluidized bed reaction-regeneration system is used for replacing a traditional tubular fixed bed reactor, the liquid-solid interphase heat transfer and mass transfer rate is enhanced in the reactor, the reaction rate is greatly increased, the reaction time is shortened, side reactions are inhibited, and the effective utilization rate of hydrogen peroxide and the selectivity of epoxypropane are increased. The present invention provides a brand-new process for the production of epoxypropane, which is beneficial to reducing the production cost of epoxypropane.

Description

一种利用液固循环流化床反应-再生系统的HPPO法生产环氧丙烷工艺A HPPO process for producing propylene oxide using a liquid-solid circulating fluidized bed reaction-regeneration system 技术领域Technical field
本发明属于环氧丙烷生产技术领域，具体涉及一种利用液固循环流化床反应-再生系统实现双氧水直接氧化丙烯制备环氧丙烷的工艺。The invention belongs to the technical field of propylene oxide production, and specifically relates to a process for directly oxidizing propylene with hydrogen peroxide to prepare propylene oxide by utilizing a liquid-solid circulating fluidized bed reaction-regeneration system.
背景技术Background technique
环氧丙烷(简称PO)是丙烯的第二大衍生物，仅次于聚丙烯，可以用来生产聚醚多元醇，1,2-丙二醇等，也是第四代洗涤剂非离子表面活性剂、油田破乳剂、农药乳化剂等的主要原料。其终端广泛用于建筑、食品、烟草、医药及化妆品等行业，是精细化工的重要原料。目前，环氧丙烷的生产方法主要有氯醇法、共氧化法和直接氧化法(HPPO)。Propylene oxide (PO for short) is the second largest derivative of propylene, second only to polypropylene. It can be used to produce polyether polyols, 1,2-propanediol, etc. It is also the fourth generation of nonionic surfactants for detergents, The main raw material for oilfield demulsifiers, pesticide emulsifiers, etc. Its terminals are widely used in industries such as construction, food, tobacco, medicine and cosmetics, and are important raw materials for fine chemicals. At present, the main production methods of propylene oxide include chlorohydrin method, co-oxidation method and direct oxidation method (HPPO).
氯醇法以丙烯、氯气和石灰乳为原料，经丙烯氯醇化和皂化生成环氧丙烷，该工艺技术成熟，操作弹性大，原料适应性好。但反应过程中产生大量的废水和废渣，环境污染严重。生产1吨的环氧丙烷就产生约40吨的含氯废水和2吨的氯化钙废渣。同时，反应过程中产生的次氯酸对设备腐蚀严重。目前世界环氧丙烷约40％左右的产能为氯醇法。本世纪初，国外就已经停止了氯醇法装置的新建项目，并逐渐用其他方法淘汰现有产能。The chlorohydrin method uses propylene, chlorine and lime milk as raw materials, and produces propylene oxide through chlorohydration and saponification of propylene. This process has mature technology, great operating flexibility, and good raw material adaptability. However, a large amount of waste water and waste residue are produced during the reaction process, causing serious environmental pollution. The production of 1 ton of propylene oxide produces about 40 tons of chlorine-containing wastewater and 2 tons of calcium chloride waste residue. At the same time, the hypochlorous acid produced during the reaction seriously corrodes the equipment. At present, about 40% of the world's propylene oxide production is produced by the chlorohydrin process. At the beginning of this century, foreign countries had stopped building new projects for chlorohydrin process units, and gradually used other methods to eliminate existing production capacity.
共氧化法则是通过有机过氧化氢与丙烯生成环氧丙烷和有机醇。根据原料和联产品不同，分为异丁烷共氧化法和乙苯共氧化法。异丁烷法是以异丁烷的有机过氧化物叔丁基过氧化氢(TBHP)作为氧化剂来氧化丙烯生产环氧丙烷，每生产1吨环氧丙烷联产2.3吨的叔丁醇(TBA)。乙苯共氧化法是以乙苯的过氧化物作为氧化剂来氧化丙烯生产环氧丙烷，每生产1吨环氧丙烷联产2.2-2.6吨苯乙烯。原料来源和产品销售相互制约因素较大，只有PO和联产品市场需求匹配时才能显现出该工艺的优势。The co-oxidation rule is to generate propylene oxide and organic alcohol through organic hydrogen peroxide and propylene. According to different raw materials and co-products, it is divided into isobutane co-oxidation method and ethylbenzene co-oxidation method. The isobutane method uses the organic peroxide tert-butyl hydroperoxide (TBHP) of isobutane as an oxidant to oxidize propylene to produce propylene oxide. For every ton of propylene oxide produced, 2.3 tons of tert-butyl alcohol (TBA) are produced. ). The ethylbenzene co-oxidation method uses ethylbenzene peroxide as an oxidant to oxidize propylene to produce propylene oxide. For every ton of propylene oxide produced, 2.2-2.6 tons of styrene are co-produced. The source of raw materials and product sales have major mutual constraints. Only when the market demand for PO and co-products matches can the advantages of this process be revealed.
HPPO工艺则是以双氧水和丙烯为原料，在钛硅分子筛催化剂的作用 下进行环氧化反应生成环氧丙烷，其副产物仅有水。而且该工艺过程的条件温和，能耗大幅降低，与其他技术相比，废水排放量可以减少70-80％，能耗减少35％左右，属于环境友好型工艺路线，也被认为是最有前景的环氧丙烷生产路线。目前，陶氏(DOW)/巴斯夫(BASF)、赢创(Degussa)/伍德(Uhde)、中石化等企业实现了HPPO工艺的工业化。然而，现有的上述技术均采用固定床工艺，原料在反应器内停留时间较长，移热不及时容易产生床层“热点”引发副反应，并降低双氧水的有效利用率。同时，由于停留时间较长，生成的环氧丙烷容易在反应器内继续发生醇解或水解反应，影响产品收率。另外，由于钛硅分子筛催化剂的单程寿命较短，需要反复进行再生处理，再生操作时需要停工并更换催化剂，过程繁琐且影响装置运行周期，最终影响生产效益。The HPPO process uses hydrogen peroxide and propylene as raw materials, in the role of titanium silicon molecular sieve catalyst The epoxidation reaction is carried out to produce propylene oxide, and the only by-product is water. Moreover, the process conditions are mild and energy consumption is greatly reduced. Compared with other technologies, wastewater discharge can be reduced by 70-80% and energy consumption reduced by about 35%. It is an environmentally friendly process route and is also considered the most promising. Propylene oxide production route. At present, companies such as Dow/BASF, Degussa/Uhde, and Sinopec have realized the industrialization of the HPPO process. However, the above-mentioned existing technologies all use fixed-bed processes. The raw materials stay in the reactor for a long time. If the heat is not transferred in time, it is easy to produce "hot spots" in the bed, trigger side reactions, and reduce the effective utilization of hydrogen peroxide. At the same time, due to the long residence time, the generated propylene oxide is prone to continue alcoholysis or hydrolysis reactions in the reactor, affecting the product yield. In addition, due to the short single-pass life of the titanium-silicon molecular sieve catalyst, repeated regeneration processes are required. During the regeneration operation, the work needs to be stopped and the catalyst replaced. The process is cumbersome and affects the operation cycle of the device, ultimately affecting production efficiency.
发明内容Contents of the invention
鉴于此，本发明的目的是提供一种利用液固循环流化床反应-再生系统的HPPO法制环氧丙烷工艺，采用本申请的工艺，双氧水转化率高达99.51％，双氧水有效利用率高达99.99％，环氧丙烷的选择性高达99.03％，与现有固定床反应器工艺相对比，反应时间明显缩短，反应效果明显提升。In view of this, the purpose of the present invention is to provide a HPPO process for producing propylene oxide using a liquid-solid circulating fluidized bed reaction-regeneration system. Using the process of this application, the conversion rate of hydrogen peroxide is as high as 99.51%, and the effective utilization rate of hydrogen peroxide is as high as 99.99%. , the selectivity of propylene oxide is as high as 99.03%. Compared with the existing fixed bed reactor process, the reaction time is significantly shortened and the reaction effect is significantly improved.
本发明目的是通过以下方式实现：The object of the present invention is achieved in the following ways:
本发明提供一种利用液固循环流化床反应-再生系统的HPPO法生产环氧丙烷工艺，通过采用液固循环流化床反应-再生系统使用双氧水直接氧化丙烯制备环氧丙烷，所述的液固循环流化床反应-再生系统主要包括依次串联的催化剂再生器16、进料斜管7、提升管反应器11、液固分离器12和回料斜管14，回料斜管14的出口端与催化剂再生器16的侧壁的中部相连通；催化剂再生器16的顶部通过管道与溶剂回收及分离系统18相连，催化剂再生器16的底部设置有再生液分布器17，催化剂再生器16的底部的轴心设置有再生液入口21，再生液分布器17和再生液入口21共同用于均匀分布再生液以使流回到催化剂再生器16的催化剂充分流化，再生液 分布器17和再生液入口21通过管道与再生液储罐19相连；液固分离器12的顶部设置有过滤器13，过滤器13的滤过端通过管道与溶剂回收及分离系统18相连，回料斜管14的底部以及斜管的侧壁上设置有清洗液入口；The present invention provides a HPPO method for producing propylene oxide using a liquid-solid circulating fluidized bed reaction-regeneration system. The liquid-solid circulating fluidized bed reaction-regeneration system uses hydrogen peroxide to directly oxidize propylene to prepare propylene oxide. The liquid-solid circulating fluidized bed reaction-regeneration system mainly includes a catalyst regenerator 16, a feed inclined pipe 7, a riser reactor 11, a liquid-solid separator 12 and a return inclined pipe 14, which are connected in series. The outlet end is connected to the middle part of the side wall of the catalyst regenerator 16; the top of the catalyst regenerator 16 is connected to the solvent recovery and separation system 18 through a pipeline, and a regeneration liquid distributor 17 is provided at the bottom of the catalyst regenerator 16. The catalyst regenerator 16 The regeneration liquid inlet 21 is provided at the axis of the bottom. The regeneration liquid distributor 17 and the regeneration liquid inlet 21 are jointly used to evenly distribute the regeneration liquid to fully fluidize the catalyst flowing back to the catalyst regenerator 16. The regeneration liquid The distributor 17 and the regeneration liquid inlet 21 are connected to the regeneration liquid storage tank 19 through pipelines; a filter 13 is provided on the top of the liquid-solid separator 12, and the filtration end of the filter 13 is connected to the solvent recovery and separation system 18 through pipelines. The bottom of the material inclined tube 14 and the side wall of the inclined tube are provided with cleaning liquid inlets;
主要包括以下步骤：It mainly includes the following steps:
S1：反应物丙烯、双氧水和溶剂进入提升管反应器11内，与催化剂混合接触发生环氧化反应生成环氧丙烷；S1: The reactants propylene, hydrogen peroxide and solvent enter the riser reactor 11, and are mixed and contacted with the catalyst to undergo an epoxidation reaction to generate propylene oxide;
S2：反应后液固混合体系进入到液固分离器12，液相产物进入到溶剂回收及分离系统18，催化剂进入到回料斜管14；S2: After the reaction, the liquid-solid mixed system enters the liquid-solid separator 12, the liquid phase product enters the solvent recovery and separation system 18, and the catalyst enters the return inclined pipe 14;
S3：在回料斜管14内的催化剂经清洗液液提后，进入催化剂再生器16内；S3: The catalyst in the return inclined pipe 14 is extracted by the cleaning liquid and then enters the catalyst regenerator 16;
S4：对进入催化剂再生器16的催化剂进行再生处理，再生后的催化剂储存在催化剂再生器16的底部，通过进料斜管7再次进入提升管反应器11的底部，再次参与反应，循环进行催化反应-催化剂再生。S4: Regenerate the catalyst that enters the catalyst regenerator 16. The regenerated catalyst is stored at the bottom of the catalyst regenerator 16 and enters the bottom of the riser reactor 11 again through the feed inclined pipe 7 to participate in the reaction again and cycle for catalysis. Reaction - Catalyst regeneration.
进一步地，进料斜管7内设置有进料控制阀8，提升管反应器11与进料斜管7的连接处设置有位于提升管反应器11轴心的主液流入口5以及辅助液入口6，主液流入口5和辅助液入口6分别与原料混合器4相连，原料混合器4通过管道分别与原料丙烯储罐1和溶剂储罐2相连。Further, a feed control valve 8 is provided in the feed inclined pipe 7, and the connection between the riser reactor 11 and the feed inclined pipe 7 is provided with a main liquid flow inlet 5 located at the axis of the riser reactor 11 and an auxiliary liquid. The inlet 6, the main liquid flow inlet 5 and the auxiliary liquid inlet 6 are respectively connected to the raw material mixer 4, and the raw material mixer 4 is connected to the raw material propylene storage tank 1 and the solvent storage tank 2 respectively through pipelines.
进一步地，提升管反应器11的侧壁上沿轴向设置1-10个双氧水入口9，且入口高于主液流入口5和辅助液入口6，双氧水入口9通过管道与双氧水储罐3相连，提升管反应器11的提升段上设置有反应换热系统10，回料斜管14上设置的清洗液入口通过管道与清洗液储罐20相连；回料斜管14与催化剂再生器16之间的斜管内设置有回料控制阀15。Further, 1-10 hydrogen peroxide inlets 9 are arranged along the axial direction on the side wall of the riser reactor 11, and the inlets are higher than the main liquid flow inlet 5 and the auxiliary liquid inlet 6. The hydrogen peroxide inlets 9 are connected to the hydrogen peroxide storage tank 3 through pipes. , a reaction heat exchange system 10 is provided on the lifting section of the riser reactor 11, and the cleaning liquid inlet provided on the return inclined pipe 14 is connected to the cleaning liquid storage tank 20 through a pipeline; between the return inclined pipe 14 and the catalyst regenerator 16 A return control valve 15 is provided in the inclined pipe between the two.
进一步地，所述提升管反应器11内为液固两相体系，固体为微球型TS-1催化剂颗粒，催化剂的颗粒平均直径为20-5000μm，颗粒密度为600-3000kg/m3。Further, the riser reactor 11 is a liquid-solid two-phase system, and the solids are microspherical TS-1 catalyst particles. The average particle diameter of the catalyst is 20-5000 μm, and the particle density is 600-3000kg/m 3 .
进一步地，S1中所述的溶剂为甲醇、乙醇、丙酮、乙腈、氯仿、1,4- 二氧六环、异丙醇、叔丁醇中的一种或两种以上的混合物。Further, the solvents described in S1 are methanol, ethanol, acetone, acetonitrile, chloroform, 1,4- One or a mixture of two or more of dioxane, isopropyl alcohol and tert-butyl alcohol.
进一步地，S1中所述提升管反应器11内的混合物的表观液速为3-5000m/h，双氧水与丙烯的摩尔比为1:1-1:5，双氧水与溶剂的摩尔比为1:4-1:10；所述双氧水的浓度为5-70％。Further, the apparent liquid velocity of the mixture in the riser reactor 11 described in S1 is 3-5000m/h, the molar ratio of hydrogen peroxide to propylene is 1:1-1:5, and the molar ratio of hydrogen peroxide to solvent is 1 :4-1:10; the concentration of hydrogen peroxide is 5-70%.
进一步地，S1中反应温度控制在0-70℃之间，反应器内压力控制在1-10MPa。Further, the reaction temperature in S1 is controlled between 0-70°C, and the pressure in the reactor is controlled between 1-10MPa.
进一步地，S1中所述提升管反应器11的有效高度为5-60m，液相停留时间为5-240min。Further, the effective height of the riser reactor 11 described in S1 is 5-60m, and the liquid phase residence time is 5-240min.
进一步地，S3中所述清洗液为甲醇、乙醇、丙酮、乙腈、氯仿、1,4-二氧六环、异丙醇、叔丁醇中的一种或两种以上的混合物。Further, the cleaning liquid described in S3 is one or a mixture of two or more of methanol, ethanol, acetone, acetonitrile, chloroform, 1,4-dioxane, isopropanol, and tert-butanol.
进一步地，S4中所述再生处理采用物理再生或化学再生，催化剂再生器16内再生液的表观液速的控制范围为0.01-5m/h。Further, the regeneration process described in S4 adopts physical regeneration or chemical regeneration, and the control range of the superficial liquid velocity of the regeneration liquid in the catalyst regenerator 16 is 0.01-5m/h.
进一步地，所述物理再生主要采用再生液对催化剂进行清洗以除掉催化剂表面和孔道内的附着物；所述再生液为甲醇、乙醇、丙酮、乙腈、氯仿、1,4-二氧六环、异丙醇、叔丁醇中的一种或或两种以上的混合物；物理再生时控制温度为常温-200℃，催化剂在催化剂再生器16内的停留时间为2-72小时。Further, the physical regeneration mainly uses a regeneration liquid to clean the catalyst to remove attachments on the catalyst surface and in the pores; the regeneration liquid is methanol, ethanol, acetone, acetonitrile, chloroform, 1,4-dioxane , isopropyl alcohol, tert-butyl alcohol, or a mixture of two or more thereof; during physical regeneration, the control temperature is normal temperature -200°C, and the residence time of the catalyst in the catalyst regenerator 16 is 2-72 hours.
进一步地，所述化学再生通过在再生液中加入双氧水，利用双氧水与催化剂表面或者孔道中的低聚物发生化学反应，除掉催化剂表面或孔道内的积碳物种；所述化学再生液中双氧水的浓度为0.2％-5％，化学再生时控制温度为50-100℃，催化剂在在催化剂再生器16内的停留时间为2-72小时。Further, the chemical regeneration is performed by adding hydrogen peroxide to the regeneration liquid, using the hydrogen peroxide to chemically react with oligomers on the catalyst surface or in the pores, and removing carbon deposits on the catalyst surface or in the pores; the hydrogen peroxide in the chemical regeneration liquid The concentration is 0.2%-5%, the control temperature during chemical regeneration is 50-100°C, and the residence time of the catalyst in the catalyst regenerator 16 is 2-72 hours.
进一步地，所述催化剂再生器16内储存的催化剂堆积高度为0.5-50m。Furthermore, the catalyst stored in the catalyst regenerator 16 has a stacking height of 0.5-50 m.
本发明相对于现有技术具有的有益效果如下： The beneficial effects of the present invention compared with the prior art are as follows:
本发明利用液固循环流化床反应-再生系统氧化丙烯制环氧丙烷过程中双氧水转化率高达99.51％，双氧水有效利用率高达99.99％，环氧丙烷的选择性高达99.03％，与现有固定床反应器工艺相对比，反应时间明显缩短，反应效果明显提升。In the process of oxidizing propylene to produce propylene oxide using a liquid-solid circulating fluidized bed reaction-regeneration system, the present invention has a conversion rate of hydrogen peroxide as high as 99.51%, an effective utilization rate of hydrogen peroxide as high as 99.99%, and a selectivity of propylene oxide as high as 99.03%, which is different from the existing fixed Compared with the bed reactor process, the reaction time is significantly shortened and the reaction effect is significantly improved.
附图说明Description of drawings
为了更清楚地说明本发明实施例，下面将对实施例涉及的附图进行简单地介绍。In order to explain the embodiments of the present invention more clearly, the drawings involved in the embodiments will be briefly introduced below.
图1为本发明应用液固循环流化床反应-再生系统的HPPO法生产环氧丙烷工艺流程图；Figure 1 is a flow chart of the HPPO method for producing propylene oxide using a liquid-solid circulating fluidized bed reaction-regeneration system according to the present invention;
图2为本发明液固循环流化床反应-再生系统结构的示意图，其中，1-原料丙烯储罐、2-溶剂储罐、3-双氧水储罐、4-原料混合器、5-主液流入口、6-辅助液入口、7-进料斜管、8-进料控制阀、9-双氧水入口、10-反应换热系统、11-提升管反应器、12-液固分离器、13-过滤器、14-回料斜管、15-回料控制阀、16-催化剂再生器、17-再生液分布器、18-溶剂回收及分离系统、19-再生液储罐、20-清洗液储罐，21-再生液入口。Figure 2 is a schematic diagram of the structure of the liquid-solid circulating fluidized bed reaction-regeneration system of the present invention, in which 1-raw material propylene storage tank, 2-solvent storage tank, 3-hydrogen peroxide storage tank, 4-raw material mixer, 5-main liquid Inflow port, 6-auxiliary liquid inlet, 7-feed inclined tube, 8-feed control valve, 9-hydrogen peroxide inlet, 10-reaction heat exchange system, 11-riser reactor, 12-liquid-solid separator, 13 -Filter, 14-return inclined pipe, 15-return control valve, 16-catalyst regenerator, 17-regeneration liquid distributor, 18-solvent recovery and separation system, 19-regeneration liquid storage tank, 20-cleaning liquid Storage tank, 21-regeneration fluid inlet.
具体实施方式Detailed ways
下面结合实施例对本发明进行详细的说明，但本发明的实施方式不限于此，显而易见地，下面描述中的实施例仅是本发明的部分实施例，对于本领域技术人员来讲，在不付出创造性劳动性的前提下，获得其他的类似的实施例均落入本发明的保护范围。The present invention will be described in detail below with reference to the examples, but the implementation of the present invention is not limited thereto. Obviously, the embodiments described below are only some of the embodiments of the present invention. For those skilled in the art, without paying any attention to Under the premise of creative labor, other similar embodiments can be obtained and all fall within the protection scope of the present invention.
实施例1Example 1
本实施例提供一种利用液固循环流化床反应-再生系统的HPPO法生产环氧丙烷工艺，工艺流程如图1所示，通过采用液固循环流化床反应-再生系统使双氧水直接氧化丙烯制备环氧丙烷；采用的液固循环流化床反应-再生系统的结构示意图如图2所示，所述的液固循环流化床反应-再生 系统主要包括依次串联的催化剂再生器16、进料斜管7、提升管反应器11、液固分离器12和回料斜管14，回料斜管14的出口端与催化剂再生器16的侧壁的中部相连通；催化剂再生器16的顶部通过管道与溶剂回收及分离系统18相连，催化剂再生器16的底部设置有再生液分布器17，催化剂再生器16的底部的轴心设置有再生液入口21，再生液分布器17为环形盘管型液体分布器，再生液分布器17和再生液入口21共同用于均匀分布再生液以使流回到催化剂再生器16的催化剂充分流化，再生液分布器17和再生液入口21通过管道与再生液储罐19相连；进料斜管7内设置有进料控制阀8，提升管反应器11与进料斜管7的连接处设置有位于提升管反应器11轴心的主液流入口5以及辅助液入口6，主液流入口5和辅助液入口6分别与原料混合器4相连，原料混合器4通过管道分别与原料丙烯储罐1和溶剂储罐2相连；提升管反应器11的侧壁上沿轴向设置3个双氧水入口9，双氧水入口9通过管道与双氧水储罐3相连，且入口高于主液流入口5和辅助液入口6，提升管反应器11的提升段上设置有反应换热系统10，液固分离器12为沉降式分离器，液固分离器12的顶部设置有过滤器13，过滤器13的滤过端通过管道与溶剂回收及分离系统18相连，回料斜管14的底部以及斜管的侧壁上设置有清洗液入口，通过管道与清洗液储罐20相连；回料斜管14与催化剂再生器16之间的斜管内设置有回料控制阀15；This embodiment provides a HPPO method for producing propylene oxide using a liquid-solid circulating fluidized bed reaction-regeneration system. The process flow is shown in Figure 1. The hydrogen peroxide is directly oxidized by using a liquid-solid circulating fluidized bed reaction-regeneration system. Propylene prepares propylene oxide; the structural diagram of the liquid-solid circulating fluidized bed reaction-regeneration system used is shown in Figure 2. The liquid-solid circulating fluidized bed reaction-regeneration The system mainly includes a catalyst regenerator 16, a feed inclined pipe 7, a riser reactor 11, a liquid-solid separator 12 and a return inclined pipe 14 in series. The outlet end of the return inclined pipe 14 is connected to the side of the catalyst regenerator 16. The middle part of the wall is connected; the top of the catalyst regenerator 16 is connected to the solvent recovery and separation system 18 through a pipeline, the bottom of the catalyst regenerator 16 is provided with a regeneration liquid distributor 17, and the axis of the bottom of the catalyst regenerator 16 is provided with a regeneration liquid. The inlet 21 and the regeneration liquid distributor 17 are annular coil type liquid distributors. The regeneration liquid distributor 17 and the regeneration liquid inlet 21 are jointly used to evenly distribute the regeneration liquid to fully fluidize the catalyst flowing back to the catalyst regenerator 16 for regeneration. The liquid distributor 17 and the regeneration liquid inlet 21 are connected to the regeneration liquid storage tank 19 through pipelines; a feed control valve 8 is provided in the feed inclined pipe 7, and a connection point between the riser reactor 11 and the feed inclined pipe 7 is provided. The main liquid flow inlet 5 and the auxiliary liquid inlet 6 at the axis of the riser reactor 11 are respectively connected to the raw material mixer 4, and the raw material mixer 4 is respectively connected to the raw material propylene storage tank 1 through pipelines. Connected to the solvent storage tank 2; three hydrogen peroxide inlets 9 are arranged along the axial direction on the side wall of the riser reactor 11. The hydrogen peroxide inlets 9 are connected to the hydrogen peroxide storage tank 3 through pipelines, and the inlets are higher than the main liquid flow inlet 5 and the auxiliary liquid. Inlet 6, a reaction heat exchange system 10 is provided on the lifting section of the riser reactor 11, the liquid-solid separator 12 is a sedimentation separator, and a filter 13 is provided on the top of the liquid-solid separator 12. The filtration of the filter 13 The end is connected to the solvent recovery and separation system 18 through a pipeline. The bottom of the return inclined pipe 14 and the side wall of the inclined pipe are provided with a cleaning liquid inlet, which is connected to the cleaning liquid storage tank 20 through a pipeline; the return inclined pipe 14 is connected to the catalyst regeneration A return control valve 15 is provided in the inclined pipe between the devices 16;
该工艺主要包括以下步骤：The process mainly includes the following steps:
S1：反应物丙烯、双氧水和溶剂(优选甲醇)进入提升管反应器11内，与催化剂混合接触发生环氧化反应生成环氧丙烷；S1: The reactants propylene, hydrogen peroxide and solvent (preferably methanol) enter the riser reactor 11 and are mixed and contacted with the catalyst to undergo an epoxidation reaction to generate propylene oxide;
S2：反应后液固混合体系进入到液固分离器12，液相产物进入到溶剂回收及分离系统18，催化剂则进入到回料斜管14；S2: After the reaction, the liquid-solid mixed system enters the liquid-solid separator 12, the liquid phase product enters the solvent recovery and separation system 18, and the catalyst enters the return inclined pipe 14;
S3：在回料斜管14内的催化剂经清洗液液提后，进入催化剂再生器16内； S3: The catalyst in the return inclined pipe 14 is extracted by the cleaning liquid and then enters the catalyst regenerator 16;
S4：对进入催化剂再生器16的催化剂进行再生处理，再生后的催化剂储存在催化剂再生器16的底部，通过进料斜管7再次进入提升管反应器11的底部，再次参与反应，循环进行催化反应-催化剂再生。S4: Regenerate the catalyst that enters the catalyst regenerator 16. The regenerated catalyst is stored at the bottom of the catalyst regenerator 16 and enters the bottom of the riser reactor 11 again through the feed inclined pipe 7 to participate in the reaction again and cycle for catalysis. Reaction - Catalyst regeneration.
S1的具体过程为：来源于原料丙烯储罐1中的丙烯与溶剂储罐2中的甲醇在原料混合器4中混合，分别经由主液流入口5和辅助液入口6进入到提升管反应器11底部与来自于进料斜管7的TS-1催化剂颗粒(催化剂颗粒的中位粒径为85μm，颗粒密度2000kg/m3)均匀混合，并在液流的作用下沿着提升管反应器11轴向向上运动；利用进料控制阀8控制经由进料斜管7进入反应器底部的催The specific process of S1 is: propylene from the raw material propylene storage tank 1 and methanol from the solvent storage tank 2 are mixed in the raw material mixer 4, and enter the riser reactor through the main liquid flow inlet 5 and the auxiliary liquid inlet 6 respectively. 11 The bottom is evenly mixed with the TS-1 catalyst particles from the feed inclined tube 7 (the median particle diameter of the catalyst particles is 85 μm, and the particle density is 2000kg/m 3 ), and is moved along the riser reactor under the action of the liquid flow 11 moves axially upward; use the feed control valve 8 to control the catalyst entering the bottom of the reactor through the feed inclined pipe 7
化剂的量，控制提升管反应器11内催化剂的质量分数为1％；提升管反应器11的有效高度为8m，在提升管反应器11底部以上0.3m的高度处双氧水入口9加入50％的双氧水，并与丙烯、溶剂甲醇和催化剂充分混合发生环氧化反应，液体的停留时间控制为12min；提升管反应器11内液相混合物的表观液速为40m/h，双氧水与丙烯的摩尔比为1:4，双氧水与溶剂甲醇的摩尔比为1:7.5；通过调整反应换热系统10中循环水的温度和流量控制提升管反应器11的反应温度为35℃，反应压力为3MPa。The amount of chemical agent, control the mass fraction of the catalyst in the riser reactor 11 to 1%; the effective height of the riser reactor 11 is 8m, add 50% hydrogen peroxide inlet 9 at a height of 0.3m above the bottom of the riser reactor 11 The hydrogen peroxide is fully mixed with propylene, solvent methanol and catalyst to cause epoxidation reaction. The residence time of the liquid is controlled to 12 minutes; the apparent liquid velocity of the liquid phase mixture in the riser reactor 11 is 40m/h, and the hydrogen peroxide and propylene The molar ratio is 1:4, and the molar ratio of hydrogen peroxide to solvent methanol is 1:7.5; by adjusting the temperature and flow rate of the circulating water in the reaction heat exchange system 10, the reaction temperature of the riser reactor 11 is controlled to 35°C, and the reaction pressure is 3MPa .
S2的具体过程为：随着反应的进行双氧水基本被反应消耗，反应后的催化剂与液相产物(主要包括溶剂甲醇、丙烯，生成的环氧丙烷和水)进入到液固分离器12，经过液固分离之后，液相产物再经过滤器13去除细小的催化剂颗粒后，进入溶剂回收及分离系统18；催化剂颗粒则沉降到分离器12底部并进入回料斜管14内。The specific process of S2 is: as the reaction proceeds, the hydrogen peroxide is basically consumed by the reaction, and the reaction catalyst and liquid phase products (mainly including the solvent methanol, propylene, the generated propylene oxide and water) enter the liquid-solid separator 12, and pass through After liquid-solid separation, the liquid phase product passes through the filter 13 to remove fine catalyst particles, and then enters the solvent recovery and separation system 18; the catalyst particles settle to the bottom of the separator 12 and enter the return inclined pipe 14.
S3的具体过程为：通过回料控制阀15的上方的回料斜管14侧壁通入适量的清洗液，清洗液为甲醇，经过液提过程将催化剂颗粒表面和孔道内的反应液相产物清洗并带入固液分离器12内，最终经过滤器13与反应液相产物进入溶剂回收及分离系统18；经在回料斜管14内液提的反应后催化剂落入催化剂再生器16内。 The specific process of S3 is: pass an appropriate amount of cleaning liquid through the side wall of the return inclined pipe 14 above the return control valve 15. The cleaning liquid is methanol. Through the liquid extraction process, the reaction liquid phase products on the surface of the catalyst particles and in the pores are removed. It is cleaned and brought into the solid-liquid separator 12, and finally enters the solvent recovery and separation system 18 through the filter 13 and the reaction liquid phase product; the catalyst falls into the catalyst regenerator 16 after the reaction of liquid extraction in the return inclined pipe 14.
S4的具体过程为：在催化剂再生器16内采用物理再生方法再生催化剂，催化剂再生器16内的再生液为甲醇，在催化剂再生器16内顶部稀相区形成液固移动床，进一步对催化剂表面和孔道内附着的产物清洗，实现催化剂再生并延长催化剂使用寿命。The specific process of S4 is: the physical regeneration method is used to regenerate the catalyst in the catalyst regenerator 16. The regeneration liquid in the catalyst regenerator 16 is methanol. A liquid-solid moving bed is formed in the dilute phase zone at the top of the catalyst regenerator 16 to further regenerate the catalyst surface. and clean the products attached in the pores to achieve catalyst regeneration and extend the service life of the catalyst.
在液固提升管反应器11内实现双氧水直接氧化丙烯生产环氧丙烷的过程，并利用催化剂再生器16实现催化剂的再生，液固提升管反应器11和催化剂再生器16高度耦合连续运行，实现催化剂连续再生。The process of direct oxidation of propylene with hydrogen peroxide to produce propylene oxide is realized in the liquid-solid riser reactor 11, and the catalyst regenerator 16 is used to realize the regeneration of the catalyst. The liquid-solid riser reactor 11 and the catalyst regenerator 16 are highly coupled and operate continuously to achieve The catalyst is continuously regenerated.
按照上述实施例的操作过程，利用液固循环流化床反应-再生系统双氧水氧化丙烯制环氧丙烷的工艺过程中双氧水转化率高达99.51％，双氧水有效利用率高达99.99％，环氧丙烷的选择性高达99.03％，与现有固定床反应器工艺相对比，反应时间明显缩短，反应效果明显提升，其具体结果如表1所示。According to the operation process of the above embodiment, the conversion rate of hydrogen peroxide is as high as 99.51%, and the effective utilization rate of hydrogen peroxide is as high as 99.99% during the process of oxidizing propylene with hydrogen peroxide to produce propylene oxide using the liquid-solid circulating fluidized bed reaction-regeneration system. The selection of propylene oxide The efficiency is as high as 99.03%. Compared with the existing fixed-bed reactor process, the reaction time is significantly shortened and the reaction effect is significantly improved. The specific results are shown in Table 1.
表1.应用不同反应器进行双氧水氧化丙烯反应的效果对比
Table 1. Comparison of the effects of hydrogen peroxide oxidation of propylene using different reactors
最后应说明的是：以上各实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述各实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。 Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention, but not to limit it. Although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that: The technical solutions described in the foregoing embodiments can still be modified, or some or all of the technical features can be equivalently replaced; and these modifications or substitutions do not deviate from the essence of the corresponding technical solutions from the technical solutions of the embodiments of the present invention. scope.

Claims (10)

  1. 一种利用液固循环流化床反应-再生系统的HPPO法生产环氧丙烷工艺，其特征在于，通过采用液固循环流化床反应-再生系统使用双氧水直接氧化丙烯制备环氧丙烷，所述的液固循环流化床反应-再生系统主要包括依次串联的催化剂再生器、进料斜管、提升管反应器、液固分离器和回料斜管，回料斜管的出口端与催化剂再生器的侧壁的中部相连通；催化剂再生器的顶部通过管道与溶剂回收及分离系统相连，催化剂再生器的底部设置有再生液分布器，催化剂再生器的底部的轴心设置有再生液入口，再生液分布器和再生液入口通过管道与再生液储罐相连；液固分离器的顶部设置有过滤器，过滤器的滤过端通过管道与溶剂回收及分离系统相连，液固分离器的底部以及回料斜管的侧壁上设置有清洗液入口；A HPPO method for producing propylene oxide using a liquid-solid circulating fluidized bed reaction-regeneration system, which is characterized in that propylene oxide is prepared by directly oxidizing propylene with hydrogen peroxide using a liquid-solid circulating fluidized bed reaction-regeneration system, as described The liquid-solid circulating fluidized bed reaction-regeneration system mainly includes a catalyst regenerator, a feed inclined tube, a riser reactor, a liquid-solid separator and a return inclined tube connected in series. The outlet end of the return inclined tube is connected with the catalyst regeneration The middle part of the side wall of the catalyst regenerator is connected; the top of the catalyst regenerator is connected to the solvent recovery and separation system through a pipeline, the bottom of the catalyst regenerator is provided with a regeneration liquid distributor, and the axis of the bottom of the catalyst regenerator is provided with a regeneration liquid inlet. The regeneration liquid distributor and the regeneration liquid inlet are connected to the regeneration liquid storage tank through pipelines; a filter is provided on the top of the liquid-solid separator, and the filter end of the filter is connected to the solvent recovery and separation system through pipelines. The bottom of the liquid-solid separator And the side wall of the return inclined pipe is provided with a cleaning liquid inlet;
    主要包括以下步骤：It mainly includes the following steps:
    S1：反应物丙烯、双氧水和溶剂进入提升管反应器内，与催化剂混合接触发生环氧化反应生成环氧丙烷；S1: The reactants propylene, hydrogen peroxide and solvent enter the riser reactor, and are mixed and contacted with the catalyst to undergo an epoxidation reaction to generate propylene oxide;
    S2：反应后液固混合体系进入到液固分离器，液相产物进入到溶剂回收及分离系统，催化剂进入到回料斜管；S2: After the reaction, the liquid-solid mixed system enters the liquid-solid separator, the liquid phase product enters the solvent recovery and separation system, and the catalyst enters the return inclined tube;
    S3：在回料斜管内的催化剂经清洗液液提后，进入催化剂再生器内；S3: The catalyst in the return inclined pipe is extracted by the cleaning liquid and then enters the catalyst regenerator;
    S4：对进入催化剂再生器的催化剂进行再生处理，再生后的催化剂储存在催化剂再生器的底部，通过进料斜管再次进入提升管反应器的底部，再次参与反应，循环进行催化反应-催化剂再生。S4: Regenerate the catalyst entering the catalyst regenerator. The regenerated catalyst is stored at the bottom of the catalyst regenerator, enters the bottom of the riser reactor again through the feed inclined tube, participates in the reaction again, and performs catalytic reaction-catalyst regeneration in a cycle. .
  2. 根据权利要求1所述的工艺，其特征在于，进料斜管内设置有进料控制阀，提升管反应器与进料斜管的连接处设置有位于提升管反应器轴心的主液流入口以及辅助液入口，主液流入口和辅助液入口分别与原料混合器相连，原料混合器通过管道分别与原料丙烯储罐和溶剂储罐相连。The process according to claim 1, characterized in that a feed control valve is provided in the feed inclined tube, and a main liquid flow inlet located at the axis of the riser reactor is provided at the connection between the riser reactor and the feed inclined tube. As well as the auxiliary liquid inlet, the main liquid flow inlet and the auxiliary liquid inlet are respectively connected to the raw material mixer, and the raw material mixer is connected to the raw material propylene storage tank and the solvent storage tank through pipelines.
  3. 根据权利要求1所述的工艺，其特征在于，提升管反应器的侧壁上沿轴向设置1-10个双氧水入口，且入口高于主液流入口和辅助液入口，双 氧水入口通过管道与双氧水储罐相连；提升管反应器的提升段上设置有反应换热系统；回料斜管上设置的清洗液入口通过管道与清洗液储罐相连，回料斜管与催化剂再生器之间的斜管内设置有回料控制阀。The process according to claim 1, characterized in that 1-10 hydrogen peroxide inlets are arranged along the axial direction on the side wall of the riser reactor, and the inlets are higher than the main liquid flow inlet and the auxiliary liquid inlet. The oxygenated water inlet is connected to the hydrogen peroxide storage tank through a pipeline; a reaction heat exchange system is provided on the lifting section of the riser reactor; the cleaning liquid inlet provided on the return inclined pipe is connected to the cleaning liquid storage tank through a pipeline, and the return inclined pipe is connected to the cleaning liquid storage tank. A return control valve is provided in the inclined tube between the catalyst regenerators.
  4. 根据权利要求1所述的工艺，其特征在于，所述提升管反应器内为液固两相体系，固体为微球型TS-1催化剂颗粒，催化剂的颗粒平均直径为20-5000μm，颗粒密度为600-3000kg/m3。The process according to claim 1, characterized in that the riser reactor is a liquid-solid two-phase system, the solids are microspherical TS-1 catalyst particles, the average diameter of the catalyst particles is 20-5000 μm, and the particle density is 600-3000kg/m 3 .
  5. 根据权利要求1所述的工艺，其特征在于，S1中所述的溶剂为甲醇、乙醇、丙酮、乙腈、氯仿、1,4-二氧六环、异丙醇、叔丁醇中的一种或两种以上的混合物。The process according to claim 1, wherein the solvent in S1 is one of methanol, ethanol, acetone, acetonitrile, chloroform, 1,4-dioxane, isopropanol and tert-butanol. or a mixture of two or more.
  6. 根据权利要求1所述的工艺，其特征在于，S1中所述提升管反应器内的混合物的表观液速为3-5000m/h，双氧水与丙烯的摩尔比为1:1-1:5，双氧水与溶剂的摩尔比为1:4-1:10；所述双氧水的浓度为5-70％。The process according to claim 1, characterized in that the apparent liquid velocity of the mixture in the riser reactor in S1 is 3-5000m/h, and the molar ratio of hydrogen peroxide to propylene is 1:1-1:5 , the molar ratio of hydrogen peroxide to solvent is 1:4-1:10; the concentration of hydrogen peroxide is 5-70%.
  7. 根据权利要求1所述的工艺，其特征在于，S1中反应温度控制在0-70℃之间，反应器内压力控制在1-10MPa。The process according to claim 1, characterized in that the reaction temperature in S1 is controlled between 0-70°C, and the pressure in the reactor is controlled between 1-10MPa.
  8. 根据权利要求1所述的工艺，其特征在于，S1中所述提升管反应器的有效高度为5-60m，液相停留时间为5-240min。The process according to claim 1, characterized in that the effective height of the riser reactor in S1 is 5-60m, and the liquid phase residence time is 5-240min.
  9. 根据权利要求1所述的工艺，其特征在于，S3中所述清洗液为甲醇、乙醇、丙酮、乙腈、氯仿、1,4-二氧六环、异丙醇、叔丁醇中的一种或两种以上的混合物。The process according to claim 1, characterized in that the cleaning liquid in S3 is one of methanol, ethanol, acetone, acetonitrile, chloroform, 1,4-dioxane, isopropyl alcohol and tert-butanol. or a mixture of two or more.
  10. 根据权利要求1所述的工艺，其特征在于，S4中所述再生处理采用物理再生或化学再生，催化剂再生器内再生液的表观液速的控制范围为0.01-5m/h。 The process according to claim 1, characterized in that the regeneration process in S4 adopts physical regeneration or chemical regeneration, and the control range of the superficial liquid velocity of the regeneration liquid in the catalyst regenerator is 0.01-5m/h.
PCT/CN2023/086467 2022-09-19 2023-04-06 Process for producing epoxypropane by using hppo method of liquid-solid circulating fluidized bed reaction-regeneration system WO2024060581A1 (en)

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