CN114733449A - TS-1 integral catalyst-based reaction device and process for preparing propylene oxide by propylene epoxidation - Google Patents
TS-1 integral catalyst-based reaction device and process for preparing propylene oxide by propylene epoxidation Download PDFInfo
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- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 125
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 124
- 239000003054 catalyst Substances 0.000 title claims abstract description 93
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 84
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 238000006735 epoxidation reaction Methods 0.000 title claims abstract description 38
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 204
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- 239000001301 oxygen Substances 0.000 claims description 34
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- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 description 3
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- JDSQBDGCMUXRBM-UHFFFAOYSA-N 2-[2-(2-butoxypropoxy)propoxy]propan-1-ol Chemical compound CCCCOC(C)COC(C)COC(C)CO JDSQBDGCMUXRBM-UHFFFAOYSA-N 0.000 description 1
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- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
- B01J8/0446—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
- B01J8/0496—Heating or cooling the reactor
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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
- C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
- C07D301/08—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase
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- 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
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- 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
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Abstract
The invention relates to a reaction device and a process for preparing propylene oxide by propylene epoxidation based on a TS-1 integral catalyst, wherein the reaction device comprises a plurality of sections of beds which are sequentially communicated from top to bottom, uniformly distributed fillers are filled above the first section of bed from top to bottom, a hydrogen peroxide decomposition catalyst is filled above the last section of bed, and the TS-1 integral catalyst is filled in the rest middle section of bed; the specific process comprises the following steps: (1) filling the TS-1 integral catalyst into a reaction device for preparing propylene oxide by propylene epoxidation; (2) and (3) adding a solvent methanol from the top of the device after preheating, introducing propylene from the top of the device after the device is heated to the reaction temperature, continuously heating hydrogen peroxide to start catalytic reaction, and allowing the obtained reaction mixture to flow out from the bottom of the device for separation to finish the reaction. The invention can exert the TS-1 catalytic performance to the maximum extent, effectively eliminate internal diffusion, reduce the generation of byproducts, greatly improve the selectivity of the main product propylene oxide, greatly improve the production efficiency and reduce the production cost.
Description
Technical Field
The invention belongs to the technical field of fixed bed reactors, and relates to a reaction device and a process for preparing propylene oxide by propylene epoxidation based on a TS-1 integral catalyst.
Background
The propylene oxide is an important chemical raw material intermediate, is an important derivative of propylene, is a synthetic raw material of polyether polyol, propylene glycol ether, dimethyl carbonate, full biodegradable resin polypropylene carbonate, a nonionic surfactant and the like, and is a necessary raw material in the polyurethane industry. Plays an important role in the chemical industry.
The demand of the propylene oxide increases year by year, and particularly, with the rapid development of economic technologies in China, higher requirements are put forward on the safety, cleanliness and high efficiency of the propylene oxide production technology. The production method of the epoxypropane in China is mainly a chlorohydrin method with high pollution for many years, which brings great pressure to the environment, and the chlorohydrin method is strictly prohibited in developed countries and regions such as Europe, America and the like. In recent years, China forbids new production capacity of propylene oxide by a chlorohydrin method. Although the co-oxidation method has advanced technology, the co-oxidation method also has the defects of high proportion of co-produced products, large organic sewage treatment capacity, high energy consumption, high investment cost and the like. The method for preparing the propylene oxide by the one-step direct oxidation of the propylene is a clean and economic process technical route, and China also puts the propylene oxide into a new green technology which is mainly developed. The catalyst used by the one-step direct oxidation method is mainly a TS-1 molecular sieve, and long-term research of scientists shows that the preparation technology of the TS-1 catalyst and related scientific theories make important progress, and the activity and the selectivity reach better levels, but the TS-1 is extremely tiny particles with nanometer pores, and in the industrial process, the smaller the particle size is, the higher the activity and the selectivity are, but the bottleneck problem of separation of TS-1 powder and a liquid-phase product is brought. Although many documents report TS-1 forming synergistic methods, such as a spray drying granulation method, an extrusion forming granulation method, a carrier surface coating method, a hollow microsphere method and the like, the methods all have the problems of obvious reduction of activity and selectivity and increase of side reactions, particularly, after granulation, the particle size is increased, the problem of internal diffusion is obvious, the temperature rise inside the catalyst is aggravated due to strong heat release, deep oxidation side reactions are increased, and the industrialization process of the TS-1 catalytic reaction technology is slowed down. Although the catalyst formed and synergized is also provided with a matched reactor and an operation mode thereof to make up the defects of the catalyst, such as a semi-continuous stirred tank reactor, a fixed bed reactor and the like, the problems can not be fundamentally solved. Particularly, the granulated TS-1 particles with the particle size of about 2 mm-5 mm are stacked in a fixed bed reactor, and when the epoxidation operation of propylene is carried out, the catalyst has small particle size and high stacking density, so that the pressure drop of a bed layer is high, the heat transfer efficiency is low, deep oxidation byproducts appear, the selectivity is reduced, the subsequent separation efficiency is influenced by the byproducts in the products, and the separation cost is improved.
Disclosure of Invention
The invention aims to provide a reaction device and a process for preparing propylene oxide by propylene epoxidation based on a TS-1 monolithic catalyst, which aim to solve a plurality of problems of the existing TS-1 catalyst in the process of preparing propylene oxide by propylene epoxidation, so that the TS-1 catalytic performance is exerted to the maximum extent, internal diffusion is effectively eliminated, the generation of byproducts is reduced, the selectivity of the main product propylene oxide is greatly improved, the production efficiency is greatly improved, and the production cost is reduced.
The purpose of the invention can be realized by the following technical scheme:
one of the technical schemes of the invention provides a reaction device for preparing propylene oxide by propylene epoxidation based on a TS-1 integral catalyst, which comprises a plurality of sections of beds which are communicated in sequence from top to bottom, wherein uniformly distributed fillers are filled above the first section of bed from top to bottom, a hydrogen peroxide decomposition catalyst is filled above the last section of bed, and the TS-1 integral catalyst is filled in the rest middle section of bed.
Furthermore, the uniformly distributed fillers are glass beads with the diameter of 2-3 mm.
Further, a gas-liquid mixer is arranged at the top of the device and used for mixing the gas propylene with the liquid methanol and the hydrogen peroxide and then sending the mixture into a bed layer of the reaction device for reaction.
Furthermore, the bottom outlet of the reaction device is also connected with a liquid receiving tank, the top of the liquid receiving tank is provided with a gas phase outlet, and the gas phase outlet is also connected with a condenser and then returns to be connected with the liquid receiving tank so as to condense and reflux the gas phase product.
Furthermore, the outer side of the reaction device is also provided with a jacket, and a heat exchange medium is introduced into the jacket. The catalytic reaction process is exothermic, so the temperature and the flow rate of the jacket heat medium are required to be adjusted to remove the heat in the reactor, and the temperature of the reactor is controlled to be stabilized at the reaction temperature.
In the invention, because TS-1 is immobilized on the surface of the B-doped CNT with high specific surface area by ultrafine particles, and because BCNT is immobilized on the surface of a pore skeleton with three-dimensional intercommunicated 100 um-1 mm, reactant fluid can smoothly flow in a three-dimensional channel, the crystal grain of the immobilized TS-1 is less than 100nm, the thickness of the TS-1 is about 100um, and the heat generated by catalyzing propylene oxide generated by hydrogen peroxide to generate propylene oxide by the TS-1 can be quickly removed to enter the material flow in the pore channel and is removed out of a reactor along with the main body flow, so that the conversion rate of the hydrogen peroxide, the utilization rate of organic oxygen and the selectivity of the generated propylene oxide are higher. The TS-1 catalyst used in the present invention is a cylindrical monolithic TS-1/BCNT @ NF catalyst, the diameter of the body depends on the inner diameter of the reactor, which is determined by the propylene oxide production capacity.
The second technical scheme of the invention provides a reaction process for preparing propylene oxide by propylene epoxidation based on a TS-1 monolithic catalyst, which is based on the reaction device for preparing propylene oxide by propylene epoxidation, and comprises the following steps:
(1) filling the TS-1 integral catalyst into a reaction device for preparing propylene oxide by propylene epoxidation;
(2) and (3) adding a solvent methanol from the top of the device after preheating, introducing propylene from the top of the device after the device is heated to the reaction temperature, continuously heating hydrogen peroxide to start catalytic reaction, and allowing the obtained reaction mixture to flow out from the bottom of the device for separation to finish the reaction.
Further, in the step (2), the solvent methanol is preheated to the reaction temperature and then sent into the reaction device.
Further, in the step (3), the reaction temperature of the catalytic reaction is controlled to be 35-50 ℃.
Furthermore, in the reaction device, the flow rate of the methanol is 2mL/min to 50mL/min, the corresponding flow rate of the propylene is 50mL/min to 500mL/min, and the flow rate range of the hydrogen peroxide is 0.3mL/min to 25 mL/L.
And (4) before separation in the step (3), feeding the obtained reaction mixture into a liquid receiving tank, feeding the obtained gas phase into a condenser for condensation reflux at the temperature of-15 to-10 ℃, then, allowing the uncondensed propylene and oxygen to flow to a separation unit for recovering the propylene, and allowing the liquid phase in the liquid receiving tank to flow to a downstream separation unit for separation to obtain components including the product propylene oxide.
The key bottleneck problem in the propylene epoxidation industrial process is that the granularity of the stackable TS-1 is 2-3 mm, the pressure drop of a bed layer is large, the internal temperature of the catalyst is increased due to a strong exothermic reaction, and the side reactions are more. In order to solve the problem fundamentally, the invention essentially solves the problems of heat transfer and mass transfer in industrial TS-1 catalyst particles, so that the reaction heat is quickly removed from the inner pore channels of the catalystAnd leading the temperature of the inner pore passage of the catalyst to approach 0 by the main flow. Meanwhile, the TS-1 is further reduced to a nanometer scale, the nanometer TS-1 is fixedly carried on the surface of a chemical inert high-heat-conductivity carrier, the reaction heat in the nanometer TS-1 is quickly transferred to the high-heat-conductivity carrier and then transferred to the liquid-phase main body flow, and the side reaction in the TS-1 pore channel is expected to be fundamentally inhibited. The Carbon Nano Tube (CNT) has strong heat conductivity of 2000W/(m)2K) much higher than the TS-1 thermal conductivity of 0.21W/(m)2K) can be used for immobilizing the nano TS-1. The heat generated by oxidizing propylene to propylene oxide with hydrogen peroxide under the catalysis of TS-1 can be quickly removed to enter the material flow in the pore passage and is removed out of the reactor along with the main body flow.
Drawings
FIG. 1 is a process flow diagram of the present invention;
the reference numbers in the figures illustrate:
1-a methanol feed tank; 2-a hydrogen peroxide feed tank; 3-a stop valve; 4-a feed pump; 5-a pressure indicator; 6-a flow meter; 7-a heat exchanger; 8-sleeve type jet pipe gas-liquid mixer; 9-a temperature indicator; 10-nitrogen cylinder; 11-propylene cylinders; 12-a fixed bed reactor; 13-liquid receiving tank; 14-a vent valve; 15-a condenser; 16-refrigerating machine.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
In the following embodiments or examples, the TS-1 structured catalyst used was prepared according to the published techniques (Industrial & Engineering Chemistry Research 2020,59(7), 2761-.
Otherwise, unless otherwise specified, all the conventional commercial raw materials or conventional processing techniques are used in the art.
One of the technical solutions of the present invention provides a reaction apparatus for producing propylene oxide by epoxidation of propylene based on a TS-1 monolithic catalyst, i.e., a fixed bed reactor 12, referring to fig. 1, which includes several sections of beds sequentially connected from top to bottom, wherein a uniformly distributed filler is filled above a first section of bed from top to bottom, a hydrogen peroxide decomposition catalyst is filled above a last section of bed, and a TS-1 monolithic catalyst is filled in the remaining middle section of bed.
In some specific embodiments, the uniformly distributed filler is glass beads with the diameter of 2-3 mm, and is used for uniformly distributing a mixture of propylene, methanol and hydrogen peroxide from mixed gas and further performing intensive mixing. The catalyst is filled under the glass micro-beads.
In some embodiments, the fixed bed reactor 12 has an internal diameter of 5mm to 500mm, which is 15mm for ease of description and illustration of the operation of the process of this patent. The fixed bed reactor 12 has a total height of 50mm to 2000mm, and for the convenience of description and illustration of the operation of the patented process, the reactor height may be set to 1500mm according to the present invention. The reactor is divided into 4 sections, the height of the upper three sections is 400mm, the height of the lowest section is 300mm, and the like. The hydrogen peroxide decomposition catalyst filled in the reactor is used for decomposing residual hydrogen peroxide which is not completely reacted, so that unsafe factors such as possible undefined side reactions and the like caused by the fact that the hydrogen peroxide which is not completely reacted enters a subsequent working section are avoided, and the fact that the method is limited to the size, the installation mode and the filling mode is also meant. Since this patent focuses on the fixed bed reactor 12, process and method of operation for loading the monolithic catalyst, the catalyst for decomposition of residual hydrogen peroxide, etc., is not required to be described in detail.
In some specific embodiments, a gas-liquid mixer is further installed on the top of the apparatus, and is used for mixing gaseous propylene with liquid methanol and hydrogen peroxide, and then feeding the mixture into a bed layer of the reaction apparatus for reaction. Preferably, the gas-liquid mixer is a sleeve type injection pipe gas-liquid mixer 8. Gaseous propylene flows out from the inner pipe of the mixer, the mixture of liquid methanol and hydrogen peroxide flows out from the ring pipe of the mixer, and the mixture is rapidly mixed at the outlets of the inner pipe and the ring pipe due to the difference of flow rates. The gas propylene can flow through a loop pipe, and the liquid methanol and the hydrogen peroxide can flow through an inner pipe.
In some specific embodiments, the bottom outlet of the reaction device is further connected with a liquid receiving tank 13, and the top of the liquid receiving tank 13 is provided with a gas phase outlet, and after the gas phase outlet is further connected with a condenser 15, the gas phase outlet is returned and connected with the liquid receiving tank 13 so as to condense and reflux the gas phase product. Specifically, the gas phase substance in the liquid receiving tank 13 contains oxygen, propylene oxide, methanol, water, propylene glycol monomethyl ether and the like, and the compositions thereof conform to the phase equilibrium composition at the temperature, and because the liquid phase product contains lower water and propylene glycol monomethyl ether and has a higher boiling point, the gas phase contains a small amount of water and propylene glycol monomethyl ether, and the main components are unreacted propylene, water produced by the decomposition of hydrogen peroxide, propylene oxide and methanol. Meanwhile, the condenser 15 is generally a secondary condenser 15, the condensation temperature is set to be-15 ℃ to-10 ℃, after secondary condensation, the epoxypropane and the methanol in the gas phase are condensed into liquid and flow back to the liquid receiving tank 13, the main components of the gas phase are propylene and oxygen, and because of the high activity and the high selectivity of the catalyst, the oxygen amount generated by secondary decomposition of the hydrogen peroxide is low, so that the composition of the gas phase propylene and the oxygen is out of the explosion limit range, and the safety is ensured. The mixture of the propylene and the oxygen is sent to a downstream separation unit, and the propylene obtained by separation is recycled. The separation of propylene and oxygen is not within the scope of the present invention as claimed and disclosed. Meanwhile, the liquid phase in the liquid receiving tank 13 is composed of a mixture of propylene oxide, methanol, water, propylene glycol monomethyl ether and propylene glycol from which propylene and oxygen are removed. The mixture is sent to a downstream separation unit to separate pure substances, and the separation of liquid phase materials is not within the protection and disclosure of the invention.
In some specific embodiments, the outside of the reaction device is further provided with a jacket, and the jacket is internally filled with a heat exchange medium. The catalytic reaction process is exothermic, so the temperature and the flow rate of the jacket heat medium are required to be adjusted to remove the heat in the reactor, and the temperature of the reactor is controlled to be stabilized at the reaction temperature.
In the invention, because TS-1 is immobilized on the surface of the B-doped CNT with high specific surface area by ultrafine particles, and because BCNT is immobilized on the surface of a pore skeleton with three-dimensional intercommunicated 100 um-1 mm, reactant fluid can smoothly flow in a three-dimensional channel, the crystal grain of the immobilized TS-1 is less than 100nm, the thickness of the TS-1 is about 100um, and the heat generated by catalyzing propylene oxide generated by hydrogen peroxide to generate propylene oxide by the TS-1 can be quickly removed to enter the material flow in the pore channel and is removed out of a reactor along with the main body flow, so that the conversion rate of the hydrogen peroxide, the utilization rate of organic oxygen and the selectivity of the generated propylene oxide are higher. The TS-1 catalyst used in the present invention is a cylindrical monolithic TS-1/BCNT @ NF catalyst, the diameter of the body depends on the inner diameter of the reactor, which is determined by the propylene oxide production capacity.
The second technical scheme of the invention provides a reaction process for preparing propylene oxide by propylene epoxidation based on a TS-1 monolithic catalyst, which is based on the reaction device for preparing propylene oxide by propylene epoxidation, and comprises the following steps:
(1) filling the TS-1 integral catalyst into a reaction device for preparing propylene oxide by propylene epoxidation;
(2) preheating the solvent methanol, adding the preheated solvent methanol from the top of the device, introducing propylene from the top of the device after the device is heated to the reaction temperature, continuously heating hydrogen peroxide to start catalytic reaction, and allowing the obtained reaction mixture to flow out from the bottom of the device and separating to finish the reaction.
In some embodiments, in step (2), the solvent methanol is preheated to the reaction temperature and then fed into the reaction apparatus.
In some embodiments, in step (3), the reaction temperature of the catalytic reaction is controlled to be 35 ℃ to 50 ℃.
In some specific embodiments, the flow rate of the propylene in the reaction apparatus is 50mL/min to 500mL/min based on the flow rate of the methanol being 2mL/min to 50mL/min,
in some specific embodiments, before separation in step (3), the obtained reaction mixture is sent to a liquid receiving tank 13, the obtained gas phase is sent to a condenser 15 to be condensed and refluxed at the temperature of-15 ℃ to-10 ℃, then, uncondensed propylene and oxygen flow to a separation unit to recover propylene, and the liquid phase in the liquid receiving tank 13 flows to a downstream separation unit to be separated to obtain components including the product propylene oxide.
In the above embodiments, any one may be implemented alone, or any two or more may be implemented in combination.
The above embodiments will be described in detail with reference to specific examples.
Example 1:
a cylindrical integral TS-1/BCNT @ NF catalyst is filled in a fixed bed reactor 12, the diameter of the catalyst is 15mm, the total height of a catalyst bed layer is 1000mm, the bed layer is divided into 4 sections, the height of each section is respectively 200mm, 300mm and 200mm, and the solid carrying capacity of TS-1 is 45%. The process flow is explained by combining fig. 1, wherein gas propylene, liquid methanol and hydrogen peroxide are respectively output from a propylene steel cylinder 11, a methanol raw material tank 1 and a hydrogen peroxide raw material tank 2, and can be introduced into a sleeve type injection pipe gas-liquid mixer 8 above a fixed bed through a feed pump 4 (the gas propylene does not need pumping) to be uniformly mixed and then enter a fixed bed reactor 12, a stop valve 3, a pressure indicator 5, a flowmeter 6 and the like can be arranged on a raw material conveying pipeline of the methanol and the hydrogen peroxide to control the conveying flow, and meanwhile, nitrogen flow from a nitrogen steel cylinder 10 can be conveyed into the fixed bed reactor 12 together with gas phase propylene. Wherein, gas propylene is introduced into an inner tube of the mixer at the flow rate of 275 mL/min; solvent methanol is premixed with the flow of 25mL/min and hydrogen peroxide is premixed with the flow of 12.5mL/min, then enters a heat exchanger 7, is preheated to 40 ℃, and is introduced into a loop of the mixer. The gas-liquid phase enters a glass bead bed layer in the fixed bed reactor 12 to be uniformly mixed again, the propylene epoxidation reaction is carried out at 40 ℃, the heat in the reactor is removed by adjusting the temperature and the flow of a heat medium in an outer jacket of the reactor, the temperature of the reactor is controlled to be stabilized within the reaction temperature range (plus or minus 2 ℃), and a plurality of temperature indicators 9 are arranged on the fixed bed reactor 12 to conveniently control the reaction temperature. The gas-liquid mixture flows out of the catalyst bed layer and then enters a hydrogen peroxide decomposition bed layer at the lower part of the reactor, the hydrogen peroxide which is not completely reacted in the catalytic decomposition flows into a liquid receiving tank 13, and the top of the liquid receiving tank 13 is also provided with a sampling emptying pipeline with an emptying valve 14. The gas phase in the liquid receiving tank 13 flows to a second-stage condenser 15 connected in series through a top pipeline for gas-liquid separation, the cold energy of the condenser 15 is provided by a refrigerator 16, wherein the propylene oxide, the methanol, the water, the propylene glycol monomethyl ether and the propylene glycol are condensed into liquid and then flow back to the liquid receiving tank 13, and the uncondensed propylene and the oxygen flow to a separation unit for recovering the propylene; the liquid phase in the liquid receiving tank 13 flows to a downstream separation unit, and propylene oxide, methanol, water, propylene glycol monomethyl ether and propylene glycol are separated. The conversion rate of hydrogen peroxide is 99.5%, the utilization rate of organic oxygen in hydrogen peroxide is 98.5%, the selectivity of propylene to propylene oxide is 97.0%, the selectivity of 1-hydroxy-2-methoxy propane is 1.8%, and the selectivity of 1-methoxy-2-hydroxy propane is 1.2%.
Example 2
A cylindrical integral TS-1/BCNT @ NF catalyst is filled in a fixed bed reactor 12, the diameter of the catalyst is 15mm, the total height of a catalyst bed layer is 1000mm, the bed layer is divided into 4 sections, the height of each section is respectively 200mm, 300mm and 200mm, and the solid carrying capacity of TS-1 is 5%. Referring to example 1, gaseous propylene, liquid methanol and hydrogen peroxide are introduced into a sleeve type injection pipe gas-liquid mixer 8 above a fixed bed, and are mixed uniformly, and then enter a fixed bed reactor 12. Wherein, the gas propylene is introduced into an inner tube of the mixer at the flow rate of 250 mL/min; solvent methanol is premixed with the flow of 25mL/min and hydrogen peroxide is premixed with the flow of 14mL/min, then enters a heat exchanger 7, is preheated to 42 ℃, and is introduced into a loop of the mixer. The gas-liquid phase enters a glass bead bed layer in the fixed bed reactor 12 to be mixed and uniformly distributed again, the propylene epoxidation reaction is carried out at 42 ℃, the heat in the reactor is removed by adjusting the temperature and the flow of a heat medium in an outer jacket of the reactor, and the temperature of the reactor is controlled to be stabilized within the reaction temperature range (+/-2 ℃). The gas-liquid mixture flows out of the catalyst bed layer and then enters a hydrogen peroxide decomposition bed layer at the lower part of the reactor, and the hydrogen peroxide which is not completely reacted is catalytically decomposed and flows into a liquid receiving tank 13. The gas phase in the liquid receiving tank 13 flows to a secondary condenser 15 connected in series through a top pipeline, wherein the epoxypropane, the methanol, the water, the propylene glycol monomethyl ether and the propylene glycol are condensed into liquid and then flow back to the liquid receiving tank 13, and the uncondensed propylene and oxygen flow to a separation unit to recover the propylene; the liquid phase in the liquid receiving tank 13 flows to a downstream separation unit, and propylene oxide, methanol, water, propylene glycol monomethyl ether and propylene glycol are separated. The conversion rate of hydrogen peroxide is 95.0%, the utilization rate of organic oxygen in hydrogen peroxide is 96.3%, the selectivity of propylene to propylene oxide is 96.1%, the selectivity of 1-hydroxy-2-methoxy propane is 2.3%, and the selectivity of 1-methoxy-2-hydroxy propane is 1.6%.
Example 3
A cylindrical integral TS-1/BCNT @ NF catalyst is filled in a fixed bed reactor 12, the diameter of the catalyst is 15mm, the total height of a catalyst bed layer is 1000mm, the bed layer is divided into 4 sections, the height of each section is respectively 200mm, 300mm and 200mm, and the solid carrying capacity of TS-1 is 70%. Referring to example 1, gaseous propylene, liquid methanol and hydrogen peroxide are introduced into a sleeve type injection pipe gas-liquid mixer 8 above a fixed bed, and are mixed uniformly, and then enter a fixed bed reactor 12. Wherein, the gas propylene is introduced into an inner tube of the mixer at the flow rate of 250 mL/min; solvent methanol is premixed with the flow of 20mL/min and hydrogen peroxide is premixed with the flow of 12.5mL/min, then enters a heat exchanger 7, is preheated to 40 ℃, and is introduced into a loop of the mixer. The gas-liquid phase enters a glass bead bed layer in the fixed bed reactor 12 to be mixed and uniformly distributed again, the propylene epoxidation reaction is carried out at 40 ℃, the heat in the reactor is removed by adjusting the temperature and the flow of a heat medium in an outer jacket of the reactor, and the temperature of the reactor is controlled to be stabilized within the reaction temperature range (+/-2 ℃). The gas-liquid mixture flows out of the catalyst bed layer and then enters a hydrogen peroxide decomposition bed layer at the lower part of the reactor, and the hydrogen peroxide which is not completely reacted is catalytically decomposed and flows into a liquid receiving tank 13. The gas phase in the liquid receiving tank 13 flows to a secondary condenser 15 connected in series through a top pipeline, wherein propylene oxide, methanol, water, propylene glycol monomethyl ether and propylene glycol are condensed into liquid and then flow back to the liquid receiving tank 13, and uncondensed propylene and oxygen flow to a separation unit to recover propylene; the liquid phase in the liquid receiving tank 13 flows to a downstream separation unit, and propylene oxide, methanol, water, propylene glycol monomethyl ether and propylene glycol are separated. The conversion rate of hydrogen peroxide is 99.5%, the utilization rate of organic oxygen in hydrogen peroxide is 97.8%, the selectivity of propylene to propylene oxide is 96.6%, the selectivity of 1-hydroxy-2-methoxy propane is 2.0%, and the selectivity of 1-methoxy-2-hydroxy propane is 1.4%.
Example 4
A cylindrical integral TS-1/BCNT @ NF catalyst is filled in a fixed bed reactor 12, the diameter of the catalyst is 15mm, the total height of a catalyst bed layer is 1000mm, the bed layer is divided into 4 sections, the height of each section is respectively 200mm, 300mm and 200mm, and the solid carrying capacity of TS-1 is 45%. Referring to example 1, the gaseous propylene, liquid methanol and hydrogen peroxide are introduced into a sleeve type injection pipe gas-liquid mixer 8 above a fixed bed, mixed uniformly and then enter a fixed bed reactor 12. Wherein, the gas propylene is introduced into an inner tube of the mixer at the flow rate of 50 mL/min; solvent methanol is premixed with the flow of 25mL/min and hydrogen peroxide is premixed with the flow of 13mL/min, then enters a heat exchanger 7, is preheated to 40 ℃, and is introduced into a loop of the mixer. The gas-liquid phase enters a glass bead bed layer in the fixed bed reactor 12 to be mixed and uniformly distributed again, the propylene epoxidation reaction is carried out at 40 ℃, the heat in the reactor is removed by adjusting the temperature and the flow of a heat medium in an outer jacket of the reactor, and the temperature of the reactor is controlled to be stabilized within the reaction temperature range (+/-2 ℃). The gas-liquid mixture flows out of the catalyst bed layer and then enters a hydrogen peroxide decomposition bed layer at the lower part of the reactor, and the hydrogen peroxide which is not completely reacted is catalytically decomposed and flows into a liquid receiving tank 13. The gas phase in the liquid receiving tank 13 flows to a secondary condenser 15 connected in series through a top pipeline, wherein the epoxypropane, the methanol, the water, the propylene glycol monomethyl ether and the propylene glycol are condensed into liquid and then flow back to the liquid receiving tank 13, and the uncondensed propylene and oxygen flow to a separation unit to recover the propylene; the liquid phase in the liquid receiving tank 13 flows to a downstream separation unit, and propylene oxide, methanol, water, propylene glycol monomethyl ether and propylene glycol are separated. The conversion rate of hydrogen peroxide is 95.8%, the utilization rate of organic oxygen in hydrogen peroxide is 97.9%, the selectivity of propylene to propylene oxide is 96.7%, the selectivity of 1-hydroxy-2-methoxy propane is 1.9%, and the selectivity of 1-methoxy-2-hydroxy propane is 1.4%.
Example 5
A cylindrical integral TS-1/BCNT @ NF catalyst is filled in a fixed bed reactor 12, the diameter of the catalyst is 15mm, the total height of a catalyst bed layer is 1000mm, the bed layer is divided into 4 sections, the height of each section is respectively 200mm, 300mm and 200mm, and the solid carrying capacity of TS-1 is 45%. Referring to example 1, the gaseous propylene, liquid methanol and hydrogen peroxide are introduced into a sleeve type injection pipe gas-liquid mixer 8 above a fixed bed, mixed uniformly and then enter a fixed bed reactor 12. Wherein, the gas propylene is introduced into an inner tube of the mixer at the flow rate of 500 mL/min; solvent methanol is premixed with the flow of 30mL/min and hydrogen peroxide is premixed with the flow of 12.5mL/min, then enters a heat exchanger 7, is preheated to 42 ℃, and is introduced into a loop of the mixer. The gas-liquid phase enters a glass microsphere bed layer in the fixed bed reactor 12 to be mixed and uniformly distributed again, the propylene epoxidation reaction is carried out at 42 ℃, the heat in the reactor is removed by adjusting the temperature and the flow of a heat medium in an outer jacket of the reactor, and the temperature of the reactor is controlled to be stabilized within the reaction temperature range (+/-2 ℃). The gas-liquid mixture flows out of the catalyst bed layer and then enters a hydrogen peroxide decomposition bed layer at the lower part of the reactor, and the hydrogen peroxide which is not completely reacted is catalytically decomposed and flows into a liquid receiving tank 13. The gas phase in the liquid receiving tank 13 flows to a secondary condenser 15 connected in series through a top pipeline, wherein the epoxypropane, the methanol, the water, the propylene glycol monomethyl ether and the propylene glycol are condensed into liquid and then flow back to the liquid receiving tank 13, and the uncondensed propylene and oxygen flow to a separation unit to recover the propylene; the liquid phase in the liquid receiving tank 13 flows to a downstream separation unit, and propylene oxide, methanol, water, propylene glycol monomethyl ether and propylene glycol are separated. The conversion rate of hydrogen peroxide is 99.5%, the utilization rate of organic oxygen in hydrogen peroxide is 97.3%, the selectivity of propylene to propylene oxide is 96.1%, the selectivity of 1-hydroxy-2-methoxy propane is 2.4%, and the selectivity of 1-methoxy-2-hydroxy propane is 1.5%.
Example 6
A cylindrical integral TS-1/BCNT @ NF catalyst is filled in a fixed bed reactor 12, the diameter of the catalyst is 15mm, the total height of a catalyst bed layer is 1000mm, the bed layer is divided into 4 sections, the height of each section is respectively 200mm, 300mm and 200mm, and the solid carrying capacity of TS-1 is 45%. Referring to example 1, gaseous propylene, liquid methanol and hydrogen peroxide are introduced into a sleeve type injection pipe gas-liquid mixer 8 above a fixed bed, and are mixed uniformly, and then enter a fixed bed reactor 12. Wherein, gas propylene is introduced into an inner tube of the mixer at the flow rate of 275 mL/min; solvent methanol is premixed with the flow of 2mL/min and hydrogen peroxide is premixed with the flow of 14mL/min, then enters a heat exchanger 7, is preheated to 40 ℃, and is introduced into a loop of the mixer. The gas-liquid phase enters a glass bead bed layer in the fixed bed reactor 12 to be mixed and uniformly distributed again, the propylene epoxidation reaction is carried out at 40 ℃, the heat in the reactor is removed by adjusting the temperature and the flow of a heat medium in an outer jacket of the reactor, and the temperature of the reactor is controlled to be stabilized within the reaction temperature range (+/-2 ℃). The gas-liquid mixture flows out of the catalyst bed layer and then enters a hydrogen peroxide decomposition bed layer at the lower part of the reactor, and the hydrogen peroxide which is not completely reacted is catalytically decomposed and flows into a liquid receiving tank 13. The gas phase in the liquid receiving tank 13 flows to a secondary condenser 15 connected in series through a top pipeline, wherein propylene oxide, methanol, water, propylene glycol monomethyl ether and propylene glycol are condensed into liquid and then flow back to the liquid receiving tank 13, and uncondensed propylene and oxygen flow to a separation unit to recover propylene; the liquid phase in the liquid receiving tank 13 flows to a downstream separation unit, and propylene oxide, methanol, water, propylene glycol monomethyl ether and propylene glycol are separated. The conversion rate of hydrogen peroxide is 97.5%, the utilization rate of organic oxygen in hydrogen peroxide is 98.3%, the selectivity of propylene to propylene oxide is 96.2%, the selectivity of 1-hydroxy-2-methoxy propane is 2.2%, and the selectivity of 1-methoxy-2-hydroxy propane is 1.6%.
Example 7
A cylindrical integral TS-1/BCNT @ NF catalyst is filled in a fixed bed reactor 12, the diameter of the catalyst is 15mm, the total height of a catalyst bed layer is 1000mm, the bed layer is divided into 4 sections, the height of each section is respectively 200mm, 300mm and 200mm, and the solid carrying capacity of TS-1 is 45%. Referring to example 1, the gaseous propylene, liquid methanol and hydrogen peroxide are introduced into a sleeve type injection pipe gas-liquid mixer 8 above a fixed bed, mixed uniformly and then enter a fixed bed reactor 12. Wherein, the gas propylene is introduced into an inner tube of the mixer at the flow rate of 250 mL/min; solvent methanol is premixed with the flow of 50mL/min and hydrogen peroxide is premixed with the flow of 12mL/min, then enters a heat exchanger 7, is preheated to 38 ℃, and is introduced into a loop of the mixer. The gas-liquid phase enters a glass bead bed layer in the fixed bed reactor 12 to be mixed and uniformly distributed again, the propylene epoxidation reaction is carried out at 38 ℃, the heat in the reactor is removed by adjusting the temperature and the flow of a heat medium in an outer jacket of the reactor, and the temperature of the reactor is controlled to be stabilized within the reaction temperature range (+/-2 ℃). The gas-liquid mixture flows out of the catalyst bed layer and then enters a hydrogen peroxide decomposition bed layer at the lower part of the reactor, and the hydrogen peroxide which is not completely reacted is catalytically decomposed and flows into a liquid receiving tank 13. The gas phase in the liquid receiving tank 13 flows to a secondary condenser 15 connected in series through a top pipeline, wherein propylene oxide, methanol, water, propylene glycol monomethyl ether and propylene glycol are condensed into liquid and then flow back to the liquid receiving tank 13, and uncondensed propylene and oxygen flow to a separation unit to recover propylene; the liquid phase in the liquid receiving tank 13 flows to a downstream separation unit, and propylene oxide, methanol, water, propylene glycol monomethyl ether and propylene glycol are separated. The conversion rate of hydrogen peroxide is 99.1%, the utilization rate of organic oxygen in hydrogen peroxide is 98.0%, the selectivity of propylene to propylene oxide is 97.0%, the selectivity of 1-hydroxy-2-methoxy propane is 1.8%, and the selectivity of 1-methoxy-2-hydroxy propane is 1.2%.
Example 8
A cylindrical integral TS-1/BCNT @ NF catalyst is filled in a fixed bed reactor 12, the diameter of the catalyst is 15mm, the total height of a catalyst bed layer is 1000mm, the bed layer is divided into 4 sections, the height of each section is respectively 200mm, 300mm and 200mm, and the solid carrying capacity of TS-1 is 45%. Referring to example 1, the gaseous propylene, liquid methanol and hydrogen peroxide are introduced into a sleeve type injection pipe gas-liquid mixer 8 above a fixed bed, mixed uniformly and then enter a fixed bed reactor 12. Wherein, gas propylene is introduced into an inner tube of the mixer at the flow rate of 275 mL/min; solvent methanol is premixed with the flow of 30mL/min and hydrogen peroxide is premixed with the flow of 0.3mL/min, then enters a heat exchanger 7, is preheated to 40 ℃, and is introduced into a loop of the mixer. The gas-liquid phase enters a glass bead bed layer in the fixed bed reactor 12 to be mixed and uniformly distributed again, the propylene epoxidation reaction is carried out at 40 ℃, the heat in the reactor is removed by adjusting the temperature and the flow of a heat medium in an outer jacket of the reactor, and the temperature of the reactor is controlled to be stabilized within the reaction temperature range (+/-2 ℃). The gas-liquid mixture flows out of the catalyst bed layer and then enters a hydrogen peroxide decomposition bed layer at the lower part of the reactor, and the hydrogen peroxide which is not completely reacted is catalytically decomposed and flows into a liquid receiving tank 13. The gas phase in the liquid receiving tank 13 flows to a secondary condenser 15 connected in series through a top pipeline, wherein propylene oxide, methanol, water, propylene glycol monomethyl ether and propylene glycol are condensed into liquid and then flow back to the liquid receiving tank 13, and uncondensed propylene and oxygen flow to a separation unit to recover propylene; the liquid phase in the liquid receiving tank 13 flows to a downstream separation unit, and propylene oxide, methanol, water, propylene glycol monomethyl ether and propylene glycol are separated. The conversion rate of hydrogen peroxide is 99.4%, the utilization rate of organic oxygen in hydrogen peroxide is 98.3%, the selectivity of propylene to propylene oxide is 95.7%, the selectivity of 1-hydroxy-2-methoxy propane is 2.5%, and the selectivity of 1-methoxy-2-hydroxy propane is 1.8%.
Example 9
A cylindrical integral TS-1/BCNT @ NF catalyst is filled in a fixed bed reactor 12, the diameter of the catalyst is 15mm, the total height of a catalyst bed layer is 1000mm, the bed layer is divided into 4 sections, the height of each section is respectively 200, 300 and 200mm, and the solid carrying capacity of TS-1 is 45%. Referring to example 1, gaseous propylene, liquid methanol and hydrogen peroxide are introduced into a sleeve type injection pipe gas-liquid mixer 8 above a fixed bed, and are mixed uniformly, and then enter a fixed bed reactor 12. Wherein, the gas propylene is introduced into an inner tube of the mixer at the flow rate of 300 mL/min; solvent methanol is premixed with 25mL/min flow and hydrogen peroxide is premixed with 25mL/min flow, then enters a heat exchanger 7, is preheated to 40 ℃, and is introduced into a loop of the mixer. The gas-liquid phase enters a glass bead bed layer in the fixed bed reactor 12 to be mixed and uniformly distributed again, the propylene epoxidation reaction is carried out at 40 ℃, the heat in the reactor is removed by adjusting the temperature and the flow of a heat medium in an outer jacket of the reactor, and the temperature of the reactor is controlled to be stabilized within the reaction temperature range (+/-2 ℃). The gas-liquid mixture flows out of the catalyst bed layer and then enters a hydrogen peroxide decomposition bed layer at the lower part of the reactor, and the hydrogen peroxide which is not completely reacted is catalytically decomposed and flows into a liquid receiving tank 13. The gas phase in the liquid receiving tank 13 flows to a secondary condenser 15 connected in series through a top pipeline, wherein propylene oxide, methanol, water, propylene glycol monomethyl ether and propylene glycol are condensed into liquid and then flow back to the liquid receiving tank 13, and uncondensed propylene and oxygen flow to a separation unit to recover propylene; the liquid phase in the liquid receiving tank 13 flows to a downstream separation unit, and propylene oxide, methanol, water, propylene glycol monomethyl ether and propylene glycol are separated. The conversion rate of hydrogen peroxide is 95.6%, the utilization rate of organic oxygen in hydrogen peroxide is 97.1%, the selectivity of propylene to propylene oxide is 97%, the selectivity of 1-hydroxy-2-methoxy propane is 1.7%, and the selectivity of 1-methoxy-2-hydroxy propane is 1.3%.
Example 10
A cylindrical integral TS-1/BCNT @ NF catalyst is filled in a fixed bed reactor 12, the diameter of the catalyst is 15mm, the total height of a catalyst bed layer is 1000mm, the bed layer is divided into 4 sections, the height of each section is respectively 200mm, 300mm and 200mm, and the solid carrying capacity of TS-1 is 45%. Referring to example 1, the gaseous propylene, liquid methanol and hydrogen peroxide are introduced into a sleeve type injection pipe gas-liquid mixer 8 above a fixed bed, mixed uniformly and then enter a fixed bed reactor 12. Wherein, the gas propylene is introduced into an inner tube of the mixer at the flow rate of 250 mL/min; solvent methanol is premixed with the flow of 30mL/min and hydrogen peroxide is premixed with the flow of 12.5mL/min, then enters a heat exchanger 7, is preheated to 37.5 ℃, and is introduced into a loop of the mixer. The gas-liquid phase enters a glass bead bed layer in the fixed bed reactor 12 to be mixed and uniformly distributed again, the propylene epoxidation reaction is carried out at 37.5 ℃, the heat in the reactor is removed by adjusting the temperature and the flow of a heat medium in an outer jacket of the reactor, and the temperature of the reactor is controlled to be stabilized within the reaction temperature range (+/-2 ℃). The gas-liquid mixture flows out of the catalyst bed layer and then enters a hydrogen peroxide decomposition bed layer at the lower part of the reactor, and the hydrogen peroxide which is not completely reacted is catalytically decomposed and flows into a liquid receiving tank 13. The gas phase in the liquid receiving tank 13 flows to a secondary condenser 15 connected in series through a top pipeline, wherein propylene oxide, methanol, water, propylene glycol monomethyl ether and propylene glycol are condensed into liquid and then flow back to the liquid receiving tank 13, and uncondensed propylene and oxygen flow to a separation unit to recover propylene; the liquid phase in the liquid receiving tank 13 flows to a downstream separation unit, and propylene oxide, methanol, water, propylene glycol monomethyl ether and propylene glycol are separated. The conversion rate of hydrogen peroxide is 97.1%, the utilization rate of organic oxygen in hydrogen peroxide is 97.7%, the selectivity of propylene to propylene oxide is 97.2%, the selectivity of 1-hydroxy-2-methoxy propane is 1.7%, and the selectivity of 1-methoxy-2-hydroxy propane is 1.1%.
Example 11
A cylindrical integral TS-1/BCNT @ NF catalyst is filled in a fixed bed reactor 12, the diameter of the catalyst is 15mm, the total height of a catalyst bed layer is 1000mm, the bed layer is divided into 4 sections, the height of each section is respectively 200mm, 300mm and 200mm, and the solid carrying capacity of TS-1 is 45%. Referring to example 1, the gaseous propylene, liquid methanol and hydrogen peroxide are introduced into a sleeve type injection pipe gas-liquid mixer 8 above a fixed bed, mixed uniformly and then enter a fixed bed reactor 12. Wherein, the gas propylene is introduced into an inner tube of the mixer at the flow rate of 250 mL/min; solvent methanol is premixed with the flow rate of 25mL/min and hydrogen peroxide is premixed with the flow rate of 14mL/min, then enters a heat exchanger 7, is preheated to 47.5 ℃, and is introduced into a loop of the mixer. The gas-liquid phase enters a glass bead bed layer in the fixed bed reactor 12 to be mixed and uniformly distributed again, propylene epoxidation reaction is carried out at 47.5 ℃, heat in the reactor is removed by adjusting the temperature and the flow of a heat medium in an outer jacket of the reactor, and the temperature of the reactor is controlled to be stabilized within a reaction temperature range (+/-2 ℃). The gas-liquid mixture flows out of the catalyst bed layer and then enters a hydrogen peroxide decomposition bed layer at the lower part of the reactor, and the hydrogen peroxide which is not completely reacted is catalytically decomposed and flows into a liquid receiving tank 13. The gas phase in the liquid receiving tank 13 flows to a secondary condenser 15 connected in series through a top pipeline, wherein propylene oxide, methanol, water, propylene glycol monomethyl ether and propylene glycol are condensed into liquid and then flow back to the liquid receiving tank 13, and uncondensed propylene and oxygen flow to a separation unit to recover propylene; the liquid phase in the liquid receiving tank 13 flows to a downstream separation unit, and propylene oxide, methanol, water, propylene glycol monomethyl ether and propylene glycol are separated. The conversion rate of hydrogen peroxide is 99.4%, the utilization rate of organic oxygen in hydrogen peroxide is 94.3%, the selectivity of propylene to propylene oxide is 95.2%, the selectivity of 1-hydroxy-2-methoxy propane is 2.8%, and the selectivity of 1-methoxy-2-hydroxy propane is 2.0%.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. A reaction device for preparing propylene oxide by propylene epoxidation based on a TS-1 monolithic catalyst is characterized by comprising a plurality of sections of beds which are sequentially communicated from top to bottom, wherein uniformly distributed fillers are filled above the first section of bed from top to bottom, a hydrogen peroxide decomposition catalyst is filled above the last section of bed, and the TS-1 monolithic catalyst is filled in the rest middle section of bed.
2. The TS-1 monolithic catalyst-based reaction device for preparing propylene oxide through epoxidation of propylene according to claim 1, wherein the uniformly distributed fillers are glass beads with diameters of 2-3 mm.
3. The reaction device for preparing propylene oxide by epoxidation of propylene based on the TS-1 monolithic catalyst as claimed in claim 1, wherein a gas-liquid mixer is further installed at the top of the device, and is used for mixing gaseous propylene with liquid methanol and hydrogen peroxide, and then feeding the mixture into a bed layer of the reaction device for reaction.
4. The reaction device for preparing propylene oxide through epoxidation of propylene based on TS-1 monolithic catalyst as claimed in claim 1, wherein the bottom outlet of the reaction device is further connected with a liquid receiving tank, and the top of the liquid receiving tank is provided with a gas phase outlet, and the gas phase outlet is further connected with a condenser and then is connected with the liquid receiving tank again, so as to condense and reflux the gas phase product.
5. The reactor for preparing propylene oxide by epoxidation of propylene based on TS-1 monolithic catalyst as claimed in claim 1, wherein the reactor is further provided with a jacket at the outside, and a heat exchange medium is introduced into the jacket.
6. A reaction process for preparing propylene oxide by propylene epoxidation based on a TS-1 monolithic catalyst, which is based on the reaction device for preparing propylene oxide by propylene epoxidation according to any one of claims 1 to 5, and is characterized by comprising the following steps:
(1) filling the TS-1 integral catalyst into a reaction device for preparing propylene oxide by propylene epoxidation;
(2) and (3) adding a solvent methanol from the top of the device after preheating, introducing propylene from the top of the device after the device is heated to the reaction temperature, continuously heating hydrogen peroxide to start catalytic reaction, and allowing the obtained reaction mixture to flow out from the bottom of the device for separation to finish the reaction.
7. The process of claim 6, wherein in step (2), the solvent methanol is preheated to the reaction temperature and then fed into the reaction device.
8. The process for preparing propylene oxide by epoxidation of propylene based on TS-1 monolithic catalyst according to claim 6, wherein the reaction temperature of the catalytic reaction in step (3) is controlled to be 35-50 ℃.
9. The reaction process for preparing propylene oxide by epoxidation of propylene based on the TS-1 monolithic catalyst, according to claim 6, wherein in the reaction device, the flow rate of methanol is 2mL/min to 50mL/min, the corresponding flow rate of propylene is 50mL/min to 500mL/min, and the flow rate of hydrogen peroxide is 0.3mL/min to 25 mL/L.
10. The process of claim 6, wherein before separation in step (3), the reaction mixture is fed into a liquid receiver, the gas phase is fed into a condenser to be condensed and refluxed at a temperature of-15 ℃ to-10 ℃, the uncondensed propylene and oxygen flow to a separation unit to recover propylene, and the liquid phase in the liquid receiver flows to a downstream separation unit to be separated to obtain components including product propylene oxide.
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