CN115197171A - Method and system for producing propylene oxide - Google Patents
Method and system for producing propylene oxide Download PDFInfo
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- CN115197171A CN115197171A CN202110396001.2A CN202110396001A CN115197171A CN 115197171 A CN115197171 A CN 115197171A CN 202110396001 A CN202110396001 A CN 202110396001A CN 115197171 A CN115197171 A CN 115197171A
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- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 238000000034 method Methods 0.000 title claims description 47
- 239000007788 liquid Substances 0.000 claims abstract description 102
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 100
- 238000006243 chemical reaction Methods 0.000 claims abstract description 78
- 239000003054 catalyst Substances 0.000 claims abstract description 51
- 239000007787 solid Substances 0.000 claims abstract description 33
- 239000000463 material Substances 0.000 claims abstract description 32
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 32
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 27
- 230000003647 oxidation Effects 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- 239000012071 phase Substances 0.000 claims description 115
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 239000002245 particle Substances 0.000 claims description 18
- 239000012530 fluid Substances 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 239000012528 membrane Substances 0.000 claims description 10
- 239000002808 molecular sieve Substances 0.000 claims description 7
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 239000008346 aqueous phase Substances 0.000 claims description 4
- 239000000919 ceramic Substances 0.000 claims description 3
- 238000011010 flushing procedure Methods 0.000 claims description 2
- 208000012839 conversion disease Diseases 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 23
- 238000000926 separation method Methods 0.000 description 16
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- 230000001590 oxidative effect Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- 238000004581 coalescence Methods 0.000 description 2
- 239000002826 coolant Substances 0.000 description 2
- 239000006184 cosolvent Substances 0.000 description 2
- 238000006735 epoxidation reaction Methods 0.000 description 2
- 239000012527 feed solution Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
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- HWOWEGAQDKKHDR-UHFFFAOYSA-N 4-hydroxy-6-(pyridin-3-yl)-2H-pyran-2-one Chemical compound O1C(=O)C=C(O)C=C1C1=CC=CN=C1 HWOWEGAQDKKHDR-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000012822 chemical development Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
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- 239000000706 filtrate Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000007764 o/w emulsion Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
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- 238000000638 solvent extraction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
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- 230000003068 static effect Effects 0.000 description 1
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- 239000002341 toxic gas Substances 0.000 description 1
- 238000010977 unit operation Methods 0.000 description 1
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Images
Classifications
-
- 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
Abstract
Propylene and hydrogen peroxide are mixed and contacted in a reactor in the presence of an oxidation catalyst to carry out oxidation reaction, and the material flow after the reaction is separated to obtain the propylene oxide; the adopted device for producing the propylene oxide consists of a riser reactor (5), a liquid-solid separator (8), a liquid-liquid separator (13) and a tubular mixer (4), wherein the top of the reactor is communicated with the inlet of the solid-liquid separator through an external circulating pipe (7), the intercepted liquid outlet of the solid-liquid separator is communicated with the bottom of the reactor through the external circulating pipe and the tubular mixer, and the clear liquid outlet (10) of the solid-liquid separator is communicated with the inlet of the liquid-liquid separator; the hydrogen peroxide and the solvent in the reaction mass are used as a dispersed phase or a continuous phase. The method for producing the propylene oxide strengthens liquid-liquid mass transfer, can improve the reaction conversion rate and selectivity, and realizes long-period operation of the device.
Description
Technical Field
The invention relates to a method and a reaction system for producing propylene oxide, in particular to a method and a reaction system for preparing propylene oxide by catalyzing hydrogen peroxide and propylene oxide by adopting a liquid-solid multiphase reaction device.
Technical Field
Propylene Oxide (PO) is an important basic organic chemical raw material, is the third largest organic chemical product with the yield second to that of polypropylene and acrylonitrile in propylene derivatives, is widely applied to the industries of chemical industry, light industry, medicine, food, textile and the like, and has profound influence on the development of chemical industry and national economy. The demand in the PO market is growing with the expansion of PO use and the increase in downstream product usage. At present, the industrial production of propylene oxide mainly adopts a chlorohydrin method and an oxidation method. When propylene oxide is synthesized by a chlorohydrination method, equipment is seriously corroded, a large amount of toxic gas is consumed, a large amount of waste water is generated, the requirements of green chemistry and clean production are not met, and the propylene oxide is gradually eliminated; the co-oxidation process has long flow, high investment cost and limited by the market. The titanium silicalite molecular sieve is used as a catalyst, the propylene oxide is synthesized by directly epoxidizing the propylene by the hydrogen peroxide (HPPO process), the process condition is mild, the environment is friendly, no pollution is caused, the existing green chemical development concept is met, and the method is a green new process for producing the propylene oxide.
Because the reaction raw materials of the process for synthesizing the propylene oxide by directly epoxidizing the propylene with the hydrogen peroxide have poor intermiscibility with the hydrogen peroxide, the current methods for mixing oil, water and liquid mainly comprise the following steps: first, the miscibility of the two phases is improved by the addition of a co-solvent. For example, CN 101293813A discloses a method for producing propylene oxide, in which an emulsifier is used to form an oil-in-water emulsion of carbon four and water, and then olefin hydration reaction is performed, so that the conversion rate of isobutene can be increased to about 70%. Methanol is also commonly used as a solvent in the process of synthesizing propylene oxide from hydrogen peroxide and propylene to improve the mutual contact of two phases (CN 102898405A, CN 102442979A, CN 106632148A), but the addition of such non-raw materials may cause a series of side reactions and have great influence on the subsequent separation and product purity. In addition, in the conventional means, for strengthening the liquid-liquid mixing process, methods generally adopted in industry include mechanical stirring, design of a tortuous flow passage, high-speed impact of liquid and the like, and the purpose of the method is to generate fluid turbulence so as to increase the mixing efficiency of the liquid. The most common reactor is a stirred tank, which utilizes the mechanical stirring action of a stirrer to realize the mixing and reaction of raw materials. However, due to the limitation of the stirred tank device, the mixing time scale is between several minutes and even several hours, and the mixing time scale is usually used for reaction systems with slower reaction rate. For example, CN 202527171a discloses a reaction apparatus for gas-liquid-solid multiphase reaction, in which a flow guide cylinder is installed inside a reactor, and a stirrer is installed inside the flow guide cylinder, so as to realize contact reaction of raw materials by means of stirring. The conventional pipeline static mixer adopts a zigzag flow channel to perform intensified mixing on fluid, but the mixing effect is relatively poor.
The reactors adopted by the existing process for synthesizing propylene oxide by hydrogen peroxide and propylene mainly have the following forms, such as a fixed bed reactor (EP 0659473, CN 1678A) or a tubular reactor, or a stirring method (CN 101279957A), or a slurry bed reactor (CN 101314596A), or the series/parallel use of a plurality of reactor forms, such as a process of combining a fixed bed pipeline reactor and a slurry bed reaction kettle is adopted in CN 104311513A, and a method of carrying out epoxidation reaction by combining a bubble column slurry bed reactor and a stirring tank slurry bed reactor is disclosed in CN 106632148A. The main purpose of the different processes described above is to improve the mass transfer between the phases and the heat of reaction. The method aims to solve the problems of heat release and process amplification in the chemical reaction process.
From the reports of the existing documents and patents, the process for synthesizing propylene oxide from hydrogen peroxide and propylene still has more problems in the practical application process, so that a new propylene epoxidation process needs to be developed, especially a new reactor form is required to be developed, and the problems of incomplete hydrogen peroxide conversion, low effective utilization rate of hydrogen peroxide, low selectivity of product propylene oxide, strong reaction and heat release possibly caused temperature runaway and the like in the process for synthesizing propylene oxide from hydrogen peroxide and propylene are simply and efficiently solved.
Disclosure of Invention
One of the technical problems to be solved by the invention is to provide a method for producing propylene oxide by oxidizing propylene with hydrogen peroxide in the presence of a solid molecular sieve catalyst.
The second technical problem to be solved by the invention is to provide a reaction system for producing propylene oxide.
Propylene and hydrogen peroxide are mixed and contacted in a reactor in the presence of an oxidation catalyst for oxidation reaction, and the reacted material flow is separated to obtain propylene oxide; the adopted device for producing the propylene oxide consists of a riser reactor 5, a liquid-solid separator 8, a liquid-liquid separator 13 and a tubular mixer 4, wherein the bottom of the riser reactor is provided with a dispersed phase inlet 1 and a catalyst discharge outlet 6, the top of the reactor is communicated with the inlet of the solid-liquid separator through an external circulating pipe 7, the intercepted liquid outlet of the solid-liquid separator is communicated with the bottom of the reactor through the external circulating pipe and the tubular mixer, the clear liquid outlet 10 of the solid-liquid separator is communicated with the inlet of the liquid-liquid separator, the liquid-liquid separator is provided with a water phase outlet and an oil phase outlet, and the water phase outlet or the oil phase outlet is communicated with the inlet of the tubular mixer 4.
Preferably, the hydrogen peroxide in the reaction materials is used as a dispersed phase, and the propylene is used as a continuous phase.
A system for producing propylene oxide comprises a device for producing propylene oxide, a reaction system consisting of water-oil two-phase reaction raw materials and oxidation catalyst particles, wherein the water phase is hydrogen peroxide and a solvent or not, the oil phase is propylene, the particle size of the oxidation catalyst particles is 0.05-3.0 mm, the device for producing propylene oxide consists of a riser reactor 5, a liquid-solid separator 8, a liquid-liquid separator 13 and a tubular mixer 4, wherein the bottom of the riser reactor is provided with a dispersed phase inlet 1 and a catalyst discharge outlet 6, the top of the reactor is communicated with the inlet of the solid-liquid separator through an external circulating pipe 7, the retained liquid outlet of the solid-liquid separator is communicated with the bottom of the reactor through the external circulating pipe and the tubular mixer, the clear liquid outlet 10 of the solid-liquid separator is communicated with the liquid inlet, the liquid-liquid separator is provided with a water phase outlet and an oil phase outlet, and the water phase outlet or the oil phase outlet is communicated with the inlet of the tubular mixer 4.
The novel multiphase reaction system and the application thereof in the preparation process of the propylene oxide have the beneficial effects that:
compared with the prior art, the reaction method for producing the propylene oxide by directly oxidizing the hydrogen peroxide adopts the special reaction device, disperses one phase reactant into micro liquid by the dispersed phase feeder, adopts the molecular sieve oxidation catalyst with small particle size, and improves the interphase mass transfer by micro liquid drops and micro particles, thereby greatly improving the reaction efficiency, needing no or reducing the use of cosolvent as much as possible, reducing the occurrence of side reactions, and being beneficial to reducing the subsequent separation difficulty and energy consumption. The coupling of the reaction and the (liquid-liquid) separation process is realized, the internal circulation of a large amount of propylene is realized, and only chemical consumption needs to be supplemented when the propylene is newly added; in addition, the existence of high-concentration continuous phase propylene is beneficial to improving the reaction selectivity of hydrogen peroxide. The solid-phase catalyst in the reaction system is in a circulating flow state, so that the online updating of the catalyst is facilitated, and the shutdown and overhaul period of the device is prolonged.
Drawings
FIG. 1 is a schematic flow diagram of a first embodiment of a process for producing propylene oxide according to the present invention.
FIG. 2 is a schematic flow diagram of a second embodiment of a reaction apparatus for producing propylene oxide.
Description of reference numerals:
1-dispersed phase inlet 2-continuous phase inlet 3-dispersed phase feeder
4-tubular mixer 5-reactor 6-catalyst discharge outlet
7-external circulation pipe 8-liquid-solid separator 9-external circulation pipe lower section
10-clear liquid outlet 11-catalyst inlet 12-backwash liquid inlet
13-liquid separator 14-water phase outlet 15-oil phase outlet
16-product separation system I-tube pass II-shell pass
Detailed Description
The following describes the embodiments of the present invention in detail.
Propylene and hydrogen peroxide are mixed and contacted in a reactor in the presence of an oxidation catalyst to carry out oxidation reaction, and the material flow after the reaction is separated to obtain the propylene oxide; the adopted device for producing the propylene oxide consists of a riser reactor 5, a liquid-solid separator 8, a liquid-liquid separator 13 and a tubular mixer 4, wherein the bottom of the riser reactor is provided with a dispersed phase inlet 1 and a catalyst discharge outlet 6, the top of the reactor is communicated with the inlet of the solid-liquid separator through an external circulating pipe 7, the intercepted liquid outlet of the solid-liquid separator is communicated with the bottom of the reactor through the external circulating pipe and the tubular mixer, the clear liquid outlet 10 of the solid-liquid separator is communicated with the inlet of the liquid-liquid separator, the liquid-liquid separator is provided with a water phase outlet and an oil phase outlet, and the water phase outlet or the oil phase outlet is communicated with the inlet of the tubular mixer 4.
In the method for producing the propylene oxide, hydrogen peroxide and an added or not added solvent are water phases which can be used as a dispersed phase or a continuous phase; propylene is the oil phase as the other phase. Preferably, hydrogen peroxide and solvent are used as the dispersed phase and propylene is used as the continuous phase. The solvent is preferably methanol.
In the method for producing the propylene oxide, hydrogen peroxide and propylene are subjected to oxidation reaction in the presence of an oxidation catalyst to obtain the propylene oxide; the oxidation reaction conditions are as follows: the pressure is 0.1-3.0 MPa, the temperature is 30-80 ℃, the reaction retention time is 0.3-3 h, and the molar ratio of the fresh feed propylene to the hydrogen peroxide is (1.0-3.0): 1, the molar ratio of the solvent to the hydrogen peroxide is (0-10): 1. preferably, a solvent is added into the reaction materials, and the molar ratio of the solvent to the hydrogen peroxide is (0.5-10): 1.
in the method for producing the propylene oxide, the oxidation catalyst is a titanium silicalite molecular sieve with an MFI structure, and the particle diameter of the oxidation catalyst is 0.05-3.0 mm.
In the device for producing propylene oxide, the riser reactor is preferably internally divided into a tube side and a shell side, the tube body and the shell are separated by a tube wall and are not communicated, material flows in the tube body and the shell can exchange heat, the tube side provides a reaction space for reaction materials, a heat exchange medium is introduced into the shell side to remove heat released by reaction, and the upper end and the lower end of the shell side are respectively provided with a heat exchange medium inlet and a heat exchange medium outlet.
In the apparatus for producing propylene oxide, preferably, the dispersed phase inlet 1 is provided with a dispersed phase feeder 3, and the dispersed phase feeder is a porous pipe, a sintered metal pipe, an inorganic membrane pipe or an atomizing nozzle.
Preferably, the pressure drop before and after the dispersed phase feeder 2 is 0.05-3.0 MPa, and the initial liquid flow rate at the outlet of the dispersed phase feeder is 5-40 m/s.
Preferably, the riser reactor is a shell-and-tube reactor, wherein a reaction space is provided for reaction materials in the tube pass I, and a cooling medium is introduced into the shell pass II to exchange heat with the reaction materials in the tube pass, so that reaction heat is taken out. The tube side number is preferably a plurality of round tubes uniformly distributed in the reactor shell, and the tube side and shell side materials are separated by arranging top and bottom baffles. And a disperse phase feeder 2 is arranged at the disperse phase inlet, and when a plurality of circular pipes are arranged in the straight pipe section, the bottom of each circular pipe is provided with one disperse phase feeder. In the production of propylene oxide, the dispersed phase may be either an oil phase or an aqueous phase. The dispersed phase feeder has obvious throttling effect, and the optimal range of the pressure difference between the front and the back of the feeder is required to be ensured to be 0.05-3.0 MPa, and the liquid flow rate of a feeding port is 5-40 m/s.
In the apparatus for producing propylene oxide, preferably, the liquid-solid separator is a filter module, the filter module comprises a housing and a filter pipe, and the filter pipe is selected from one or a combination of several of an inorganic ceramic membrane, a metal pipe membrane, a metal screen and a metal sintered pipe.
In the apparatus for producing propylene oxide, preferably, the housing of the liquid-solid separator is further provided with a catalyst inlet.
In the apparatus for producing propylene oxide, preferably, a back-flushing pipeline is arranged on the filtering component in the liquid-solid separator.
In the device for producing propylene oxide, preferably, the number of the external circulation pipes is one or more, wherein the upper section of the external circulation pipe is communicated between the outlet of the reactor and the liquid-solid separator, and the lower section of the external circulation pipe is communicated between the outlet of the liquid-solid separator and the tubular mixer;
preferably, the upper section of the external circulation pipe and the lower section of the external circulation pipe have the same inner diameter.
Preferably, the ratio of the diameter of the external circulation pipe to the reactor is (0.3 to 3): 1, preferably (0.5 to 2): 1.
in the apparatus for producing propylene oxide, preferably, the tubular mixer is a jet mixer, wherein the lower section of the circulating pipe is communicated with a main fluid inlet of the jet mixer, and a water phase outlet of the liquid-liquid mixer is communicated with a high-speed jet fluid inlet of the jet mixer.
The jet mixer is provided with a main fluid inlet, a high-speed jet fluid inlet and a jet port, and the flow speed of the high-speed jet fluid at the jet port of the jet mixer is 3-30 m/s in the reaction process.
Preferably, the high-speed jet fluid inlet of the jet mixer is also communicated with the continuous phase inlet so as to supplement reaction raw materials in the reaction process.
Preferably, the liquid-liquid separator is selected from one or a combination of a conventional gravity settling tank, an oil-water coalescence separator and a fiber membrane surface separator.
One or more external circulation pipes, one end of which is connected with the top end of the reactor and the other end is connected with the bottom of the reactor to form a circulation loop. Preferably, the upper section of the external circulation pipe and the lower section of the external circulation pipe have the same inner diameter, and the diameter ratio of the external circulation pipe to the straight pipe section of the reactor is (0.3-3): 1, preferably (0.5 to 2): 1.
preferably, the liquid-solid separator is a filtering component and is used for carrying out liquid-solid separation on the material from the top of the reactor. The filtering component comprises a shell and a filtering pipe, wherein the filtering pipe is selected from one or a combination of several of an inorganic ceramic membrane, a metal pipe membrane, a metal screen mesh, a metal sintering pipe and the like. The filter components can be one or more groups. The filtering component is provided with a clear liquid outlet and a trapped liquid outlet, the clear liquid outlet is communicated with the liquid-liquid separator, the trapped liquid outlet is communicated with the bottom of the reactor through the lower segment of the downcomer, and the trapped liquid is returned to the bottom of the reactor through the jet mixer as a circulating material in the using process.
The filter assembly is provided with a filter backwash inlet, and a preferable backwash inlet pipeline and a clear liquid outlet pipeline obtained by liquid-solid separation share one interface on the shell of the filter assembly. The backwash liquid is selected from the group consisting of a filtered supernatant or a fresh feed solution.
The lower section of the external circulation pipe is communicated with the jet mixer. The circulating material from the trapped liquid outlet of the liquid-solid separator is used as the suction fluid of the jet mixer, the raw material from the continuous phase inlet and the circulating liquid phase from the water phase outlet of the liquid-liquid separator are used as high-speed jet fluid, and the jet flow speed is preferably 3-30 m/s. The two materials are mixed by a jet mixer and then enter the bottom of the reactor.
The granular oxidation catalyst is added into a reaction device through a catalyst adding port arranged on a liquid-solid separator. As the abrasion and the inactivation of a part of catalyst are inevitably caused in the reaction process, in order to ensure the overall activity of the catalyst, the activity and the abrasion condition of the catalyst need to be regularly inspected, and a part of catalyst is discharged from a catalyst discharge outlet at the bottom of the riser reactor, so that the online updating of the catalyst is realized, and the influence on the operation period of the device caused by the shutdown of the device is avoided.
A system for producing propylene oxide comprises a device for producing propylene oxide, a reaction system consisting of water-oil two-phase reaction raw materials and oxidation catalyst particles, wherein the water phase is hydrogen peroxide and a solvent, the oil phase is propylene, the particle size of the oxidation catalyst particles is 0.05-3.0 mm, the device for producing propylene oxide consists of a riser reactor, a liquid-solid separator, a liquid-liquid separator and a tubular mixer, wherein the bottom of the riser reactor is provided with a dispersed phase inlet and a catalyst discharge outlet, the top of the reactor is communicated with the inlet of the solid-liquid separator through an external circulating pipe, the retained liquid outlet of the solid-liquid separator is communicated with the bottom of the reactor through the external circulating pipe and the tubular mixer, the clear liquid outlet of the solid-liquid separator is communicated with the inlet of the liquid-liquid separator, the liquid-liquid separator is provided with a water phase outlet and an oil phase outlet, and the water phase outlet or the oil phase outlet is communicated with the inlet of the tubular mixer; wherein the aqueous phase is used as a dispersed phase or a continuous phase. Hydrogen peroxide and solvents are preferred as the dispersed phase.
The process and system for producing propylene oxide of the present invention will be further described with reference to the accompanying drawings. But not to limit the invention accordingly.
FIG. 1 is a schematic flow diagram of a process for producing propylene oxide. As shown in the attached figure 1, the adopted reaction device for producing the propylene oxide consists of a reactor 5, a liquid-solid separator 8, a liquid-liquid separator 13 and a tubular mixer 4, wherein the bottom of the riser reactor is provided with a dispersed phase inlet 1 and a catalyst discharge outlet 6, the top of the reactor is communicated with the inlet of the solid-liquid separator 8 through an external circulating pipe 7, the intercepted liquid outlet of the solid-liquid separator 8 is communicated with the bottom of the reactor through the tubular mixer 4, the clear liquid outlet 10 of the solid-liquid separator is communicated with the inlet of the liquid-liquid separator 13, the liquid-liquid separator 13 is provided with a water phase outlet 14 and an oil phase outlet 15, and the water phase outlet 14 is communicated with the inlet of the tubular mixer 4.
FIG. 2 is a schematic flow diagram of a second embodiment of a process for producing propylene oxide. Unlike the attached FIG. 1, the reactor is divided into a tube side I and a shell side II, and the tube side and the shell side are not communicated. The upper end and the lower end of the shell pass are respectively provided with a heat exchange medium inlet 20 and a heat exchange medium outlet 21, wherein a reaction space is provided for reaction materials in the tube pass, and the heat exchange medium is introduced into the shell pass to exchange heat with the reaction materials in the tube pass so as to remove reaction heat and control the reaction temperature. The oil phase separated by the liquid-liquid separator 13 returns to the bottom of the reactor 5 through an oil phase outlet 15 for circular reaction, and the separated water phase enters a product separation system 16 through a water phase outlet 14 for further separation. In addition, the bottom of the reactor 5 is provided with a continuous phase inlet 2.
As shown in the attached figure 2, taking hydrogen peroxide as an example of a dispersed phase to illustrate the method for producing propylene oxide provided by the invention, a certain amount of oxidation catalyst is transferred into a riser reactor 5 in advance, the catalyst is preferably a titanium silicalite molecular sieve with an MFI structure, and the particle diameter is 0.05-3.0 mm. Fresh raw material propylene as a continuous phase enters from a continuous phase inlet 2 and fills the whole reactor, a certain amount of aqueous phase raw material mixed by hydrogen peroxide (usually containing water) and a solvent, preferably methanol, according to a certain proportion enters the bottom of a reactor pipe body 5 through a dispersed phase inlet 1 and a dispersed phase feeder 3, in order to achieve a better dispersion effect and ensure good circulation flow in the reactor, the pressure drop of the front and back of the dispersed phase feeder 3 is required to be 0.05-3.0 MPa, the initial liquid flow rate of an outlet of the dispersed phase feeder reaches 5-40 m/s, and the diameter of an obtained dispersed phase liquid drop is less than 1mm. And (3) catalyzing hydrogen peroxide and propylene oxide to generate propylene oxide by using a titanium silicalite molecular sieve in the reaction tube body I. Controlling the apparent liquid velocity in the reaction tube body to exceed 20-120% of the critical settling velocity (the two are larger) of the catalyst particles or the liquid drop particles. And introducing a heat exchange medium into the reactor shell II to take out reaction heat and control the temperature required by the reaction, wherein the preferred flow direction of the cooling medium is opposite to the flow direction of the reaction materials or the main body cross flow.
The reacted materials are extracted from the top of the reactor 5 and enter an external circulation pipe 7, and then enter a liquid-solid separator 8 for liquid-solid separation. The liquid-solid separator 8 is a filtering component, and the filtering component comprises a shell and a filtering pipe. The mixed material is subjected to cross-flow filtration on a filtration component. When too many particles are accumulated on the wall of the filter pipe, optionally when the pressure difference between two sides of the filter pipe is greater than 0.2MPa, switching to a back washing stage, and introducing back washing material flow through the back washing medium inlet 12 to back wash the particles accumulated on the filter pipe, thereby recovering the permeability of the filter pipe. The backwash inlet 12 preferably shares a common port with the filtered supernatant outlet 10. The backwash liquid is selected from the group consisting of a filtered supernatant or a fresh feed solution. The trapped liquid of the liquid-solid separator 8 is used as a circulating material and enters the jet flow jet mixer through the lower section of the external circulating pipe, and then enters the bottom of the riser reactor 5 after being mixed with the continuous phase feed. Wherein the circulating material is used as the suction fluid and the continuous liquid phase feed is used as the high velocity jet fluid. To ensure good mixing, the jet flow velocity is preferably from 3 to 30m/s.
The clear liquid filtered by the liquid-solid separator enters the liquid-liquid separator 13 through the clear liquid outlet 10. The liquid-liquid separator 13 is mainly used for separating oil phase and water phase, and can be a conventional gravity settling tank, a surface coalescence separator, a fiber membrane surface separator, a centrifugal separator, a cyclone separator or a combination of a plurality of types. Wherein the separated oil phase mainly containing propylene returns to the reactor through an oil phase outlet 15 to participate in the reaction again, the separated water phase rich in propylene oxide is extracted through a water phase outlet 14 and enters a subsequent product separation system 16 to separate a target product, and the product separation system 16 can adopt various unit operation modes or combination use, such as conventional distillation separation, liquid-liquid extraction, adsorption separation and the like.
The catalyst feeding port 11 is preferably arranged on the liquid-solid separator 8, and the catalyst discharging port 6 is preferably arranged at the bottom of the reactor. As abrasion and inactivation of a part of catalyst are inevitably caused in the reaction process, in order to ensure the overall activity of the catalyst, the activity and abrasion condition of the catalyst need to be regularly checked, a part of catalyst is discharged from a discharge outlet according to the condition, and a part of fresh catalyst is supplemented, so that the online updating of the catalyst is realized, and the influence on the operation period of the device caused by the shutdown of the device is avoided.
The following specific examples further illustrate the application effects of the method and system for producing propylene oxide provided by the present invention, but do not limit the present invention.
In the examples and comparative examples, in which the propylene purity of the starting material was more than 99.6%, a titanium silicalite catalyst was used under the designation HTS (the company Jian, hunan). The hydrogen peroxide is commercially available, the concentration of the hydrogen peroxide is 30wt%, and the concentration of the residual hydrogen peroxide adopts KMnO 4 The titration method was used to determine the product composition, which was analyzed by gas chromatography.
Comparative example 1
Comparative example 1 adopts a traditional fixed bed reactor to prepare propylene oxide by oxidizing propylene with hydrogen peroxide, and the reactor Gao Jingbi is 20. The material flow is fed in and discharged out from the top, a side gap type inlet distributor is arranged at the inlet of the reactor, and the material flow in the reactor is naturally distributed.
The reaction inlet material is a mixture of propylene, hydrogen peroxide and a solvent methanol, wherein the molar ratio of the methanol to the hydrogen peroxide is 40. The reactor outlet temperature was 78 ℃.
The conversion rate of hydrogen peroxide obtained by sampling, analyzing and calculating the reaction result is less than 90 percent, and the selectivity of propylene oxide is 82 percent.
Wherein the conversion rate of the hydrogen peroxide is the ratio of the hydrogen peroxide consumed by the reaction to the hydrogen peroxide added. The propylene oxide selectivity is the ratio of the amount of the material generating propylene oxide to the amount of the material consuming hydrogen peroxide.
Example 1
Example 1 illustrates the effect of the process for producing propylene oxide provided by the present invention.
The reaction device and the process for producing the propylene oxide as shown in the attached figure 2 are adopted, the mixed solution composed of hydrogen peroxide and methanol is used as a dispersed phase, wherein the molar ratio of the methanol to the hydrogen peroxide is 2.0, the molar ratio of the fresh propylene feed to the hydrogen peroxide is 1.5, and the diameter of catalyst particles is 10-200 mu m. The reactor contains 3 uniformly distributed tubes, the bottom of each tube corresponds to a dispersed phase feeder, the top end of each dispersed phase feeder is a 6mm sintered metal tube, the average pore diameter of the sintered metal tube is 7 mu m, the three dispersed phase feeders are connected with the dispersed phase feeding tube through an annular tube, and the total pressure drop of the feeders is 0.25MPa. The external circulation pipeline is provided with a metal sintering pipe filtering component, and the average filtering aperture is 6 mu m. The liquid-solid mixture at the interception side of the filtering component circularly returns to the reactor, the filtrate extracted by the filtering component enters a gravity settling tank for liquid-liquid separation, the upper oil phase obtained by separation returns to the reactor, and the lower water phase is extracted for product separation and analysis.
The temperature of a reaction inlet is 45 ℃, the temperature of an outlet of the reactor is controlled to be 68 ℃ by introducing cooling water into a shell of the reactor, the pressure of a reaction part is 1.2MPa, and the residence time of reaction materials in the reactor is 1.0h.
The conversion rate of hydrogen peroxide obtained by sampling, analyzing and calculating the reaction result is more than 96 percent, and the selectivity of propylene oxide is 95 percent.
Claims (13)
1. Propylene and hydrogen peroxide are mixed and contacted in a reactor in the presence of an oxidation catalyst for oxidation reaction, and the reacted material flow is separated to obtain propylene oxide; the device for producing the propylene oxide is characterized by comprising a riser reactor (5), a liquid-solid separator (8), a liquid-liquid separator (13) and a tubular mixer (4), wherein the bottom of the riser reactor is provided with a dispersed phase inlet (1) and a catalyst discharge outlet (6), the top of the reactor is communicated with the inlet of the solid-liquid separator through an external circulating pipe (7), a trapped liquid outlet of the solid-liquid separator is communicated with the bottom of the reactor through the external circulating pipe and the tubular mixer, a clear liquid outlet (10) of the solid-liquid separator is communicated with the inlet of the liquid-liquid separator, the liquid-liquid separator is provided with a water phase outlet and an oil phase outlet, and the water phase outlet or the oil phase outlet is communicated with the inlet of the tubular mixer (4);
preferably, the hydrogen peroxide in the reaction materials is used as a dispersed phase, and the propylene is used as a continuous phase.
2. The process for producing propylene oxide according to claim 1, wherein the oxidation catalyst is a titanium silicalite molecular sieve having an MFI structure, and the oxidation catalyst has a particle diameter of 0.05 to 3.0mm.
3. The process for producing propylene oxide according to claim 1 or 2, wherein the oxidation reaction conditions are: the pressure is 0.1-3.0 MPa, the temperature is 30-80 ℃, the reaction residence time is 0.3-3 h, and the molar ratio of the fresh feed propylene to the hydrogen peroxide is (1.0-3.0): 1, wherein a solvent is added or not added into the reaction materials, and the molar ratio of the solvent to the hydrogen peroxide is (0-10): 1;
the preferred solvent is methanol.
4. A process for producing propylene oxide according to any one of claims 1 to 3, wherein the riser reactor is divided into a tube side and a shell side, the upper and lower ends of the shell side are provided with a heat exchange medium inlet and a heat exchange medium outlet, respectively, wherein the tube side provides a reaction space for the reaction material, and the shell side is fed with a heat exchange medium to control the temperature.
5. A process for producing propylene oxide according to any one of claims 1 to 3, wherein the dispersed phase inlet (1) is provided with a dispersed phase feeder (3) which is a perforated pipe, a sintered metal pipe, an inorganic membrane pipe or an atomizing nozzle.
6. A process for producing propylene oxide according to claim 5, wherein the dispersed phase feeder 2 has a pressure drop before and after 0.05 to 3.0MPa and an initial liquid flow rate at the outlet of the dispersed phase feeder is 5 to 40m/s.
7. The method for producing propylene oxide according to any one of claims 1 to 3, wherein the liquid-solid separator is a filter module, the filter module comprises a shell and a filter tube, and the filter tube is one or a combination of inorganic ceramic membrane, metal tube membrane, metal screen and metal sintered tube.
8. A process for producing propylene oxide according to any one of claims 1 to 3, wherein said liquid-solid separator casing is further provided with a catalyst-feeding port.
9. The process for producing propylene oxide according to claim 8, wherein the liquid-solid separator is provided with a back-flushing line on the filter unit.
10. The process for producing propylene oxide according to claim 1, wherein the number of the external circulation pipes is one or more, wherein the upper section of the external circulation pipe is communicated between the outlet of the reactor and the liquid-solid separator, and the lower section of the external circulation pipe is communicated between the outlet of the liquid-solid separator and the tubular mixer;
preferably, the upper section of the external circulation pipe and the lower section of the external circulation pipe have the same inner diameter.
11. The process for producing propylene oxide according to claim 10, wherein the ratio of the diameter of the external circulation pipe to that of the reactor is (0.3 to 3): 1, preferably (0.5 to 2): 1.
12. a process for producing propylene oxide according to claim 1, wherein said tubular mixer is a jet mixer, wherein said lower section of said circulation pipe is in communication with a main fluid inlet of said jet mixer, and wherein an aqueous phase outlet of said liquid-liquid mixer is in communication with a high velocity jet fluid inlet of said jet mixer.
13. A system for producing propylene oxide is characterized by comprising a device for producing propylene oxide and a reaction system consisting of water phase and oil phase and oxidation catalyst particles, wherein the water phase is hydrogen peroxide and a solvent, the oil phase is propylene, the particle size of the oxidation catalyst particles is 0.05-3.0 mm, the device for producing propylene oxide consists of a riser reactor, a liquid-solid separator, a liquid-liquid separator and a tubular mixer, wherein the bottom of the riser reactor is provided with a dispersed phase inlet and a catalyst discharge outlet, the top of the reactor is communicated with the inlet of the solid-liquid separator through an external circulating pipe, the intercepted liquid outlet of the solid-liquid separator is communicated with the bottom of the reactor through an external circulating pipe and the tubular mixer, the clear liquid outlet of the solid-liquid separator is communicated with the inlet of the liquid-liquid separator, the liquid is provided with a water phase outlet and an oil phase outlet, and the water phase outlet or the oil phase outlet is communicated with the inlet of the tubular mixer.
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