CN112174914B - Method for gas phase epoxidation of olefins with hydroperoxides - Google Patents
Method for gas phase epoxidation of olefins with hydroperoxides Download PDFInfo
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- CN112174914B CN112174914B CN202011070640.1A CN202011070640A CN112174914B CN 112174914 B CN112174914 B CN 112174914B CN 202011070640 A CN202011070640 A CN 202011070640A CN 112174914 B CN112174914 B CN 112174914B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
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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
Abstract
The invention relates to a process for the vapor phase epoxidation of an olefin with a hydroperoxide, comprising the steps of: a. proportioning raw materials; b. preheating and gasifying olefins; c. spraying hydroperoxide feedstock to the vaporized gaseous olefin to form a gas-liquid mixture stream; d. heating the temperature of the gas-liquid mixture stream to completely gasify the gas-liquid mixture stream to form a gas-phase epoxidation reactant stream; e. an epoxidation reaction is carried out in the presence of an epoxidation catalyst to form an epoxide discharge; transferring heat released by the epoxidation reaction; f. the epoxide discharged material is used for heat exchange with the gas-liquid mixture flow in the step (d), and leaves the epoxidation reaction system for subsequent process to obtain propylene oxide. The invention forms a set of rapid and high-temperature reaction circulation process, reduces the decomposition amount of raw materials, improves the reaction rate and conversion rate, and improves the economy of the epoxidation reaction.
Description
Technical Field
The invention belongs to the technical field of chemical engineering reaction, and particularly relates to a gas phase reaction method for epoxidation of olefin and hydroperoxide, which is particularly suitable for epoxidation of propylene and hydroperoxide.
Background
Propylene oxide is one of the important intermediates in petrochemical industry. Propylene oxide is currently the third largest derivative next to polypropylene and acrylonitrile in propylene derived products. The epoxypropane is mainly used for preparing polyether polyol, propylene glycol, alcohol amine and various nonionic surfactants in industry, and the derivatives thereof are widely applied to industries of petrifaction, construction, household appliances, automobiles, medicines, pesticides, textile, daily chemicals and the like.
The traditional propylene oxide production method is a chlorohydrin method, and is characterized by shorter flow, mature process, higher operation load elasticity, good selectivity, high yield, safer production, low requirement on the purity of raw material propylene and less construction investment; however, a large amount of wastewater containing calcium chloride is generated in the process of producing propylene oxide by the chlorohydrin method, which causes serious pollution to the environment. Thus, clean and economical green oxypropane production technologies are actively developed in various countries.
The current production route of propylene oxide by a non-chlorohydrin method can be divided into three types, namely a co-oxidation method, a hydrogen peroxide method and a direct oxidation method. The co-oxidation method can be divided into ethylbenzene method, isobutane method, isopropylbenzene method and the like according to the difference of organic matter hydrogen peroxide, and the method is the most widely used green production technology of propylene oxide in the world at present; the hydrogen peroxide method is a technology for generating propylene oxide by oxidizing hydrogen peroxide and propylene, and has the advantages of simple technical process, small influence on environment and more research in China; while the direct oxidation of propylene is the most economically efficient production method, it remains in the experimental research stage and no suitable catalytic material has been found yet.
The olefin co-oxidation process was first published in 1967 by Halcon corporation (now Lyondell corporation) in US 3351635. The co-oxidation reaction of olefins with organic hydrogen peroxide is generally carried out at 50-120 ℃ and 1000psi for the purpose of reacting propylene in liquid phase.
The specific epoxypropane reaction process is as follows: r-ooh+ch3ch=ch2→r-oh+ch3choh2
Wherein R is an organic group, which can be ethyl phenyl, isopropyl phenyl, tertiary butyl, isopentyl, cyclopentyl, cyclohexyl and the like.
Currently, the industrialized co-oxidation epoxypropane process includes epoxypropane-styrene co-production process, epoxypropane-tertiary butyl alcohol (or methyl tertiary butyl ether) co-production process and isopropylbenzene epoxypropane process.
The co-production process of propylene oxide and styrene mainly comprises three reactions of liquid phase oxidation of ethylbenzene to produce ethylbenzene hydroperoxide, liquid phase co-oxidation of ethylbenzene hydroperoxide and propylene to produce 1-phenethyl alcohol and propylene oxide, and dehydration of 1-phenethyl alcohol to produce styrene, and the specific description is shown in patent US5210354 of ARCO company. The co-production process of propylene oxide and tertiary butanol mainly comprises liquid phase oxidation of isobutane to form tertiary butyl hydroperoxide, liquid phase co-oxidation of tertiary butyl hydroperoxide with propylene to form tertiary butanol and propylene oxide, which tertiary butanol may also be further converted to Methyl Tertiary Butyl Ether (MTBE), for a specific description see patent US5424458 to ARCO company. The main difference between the propylene oxide process and the propylene oxide-styrene co-production process and the propylene oxide-tert-butyl alcohol (or methyl tert-butyl ether) co-production process is that the co-product dimethylbenzyl alcohol is hydrogenated to produce raw material cumene for recycling, while the liquid-phase oxidation of cumene, the liquid-phase co-oxidation process of cumene hydroperoxide and propylene are similar to the co-oxidation process of the ARCO company, and specific description is given in patent CN1856482 of Sumitomo chemistry.
In patent US3351635 by Halcon corporation, a process for the co-oxidation of olefins with organic peroxides is described: propylene and organic hydrogen peroxide are subjected to liquid phase epoxidation at preferably 50-120 c and 1000 psi. In the epoxidation process, a homogeneous catalyst of the molybdenum, tungsten, titanium, niobium, tantalum, rhenium, selenium, chromium, zirconium, tellurium, uranium series, which is soluble in the reaction mass, may be used.
In addition to the homogeneous catalysts described above, there are processes in which heterogeneous catalysts are used in the propylene co-oxidation reaction. The epoxidation of olefins is described in Shell's patent US8664412 and differs from the Halcon process in that a heterogeneous solid phase epoxidation catalyst is used. Shell describes in its patent US3829392 a solid phase catalyst of TiO2 supported on SiO2 for the epoxidation of olefins. In addition to the Shell TiO2-SiO2 catalyst, the Japanese Sumitomo chemical cumene process also uses a solid phase catalyst for the epoxidation reaction. Sumitomo chemistry in patent CN1953969 describes a process for preparing propylene oxide using a titanosilicate solid catalyst which is easier to produce and less costly.
Except for the co-oxidation method, the propylene oxide process of the hydrogen peroxide method directly adopts hydrogen peroxide to react with propylene to generate propylene oxide. Currently, the hydrogen peroxide process (HPPO process) propylene oxide has been industrially developed by BASF and Dow chemical (Dow) together, and by wining groups (Degussa) and woods (Uhde) together. The difference between the two technologies is mainly the reactor type of epoxidation, both of which are gradually maturing in the context of the development of catalytic technologies, in particular titanium silicalite molecular sieves TS-1. (Liu Bo, zhang Xiaoli, zhao Li, etc.. The state of the art for propylene oxide production [ J ]. Current chemical industry, 2016, 45 (2): 336-341).
Compared with the Halcon method epoxypropane process, the Shell method epoxypropane process, the Sumitomo method epoxypropane process and the current hydrogen peroxide method epoxypropane process all adopt solid phase epoxidation catalysts. Compared with the homogeneous phase epoxidation process, the solid phase co-oxidation catalyst is adopted, so that the separation step of the catalyst and materials is omitted, the reaction flow is simplified, and meanwhile, the reaction residence time is short, the reaction back mixing is less, the side reaction is less, the raw material consumption is low, and the product separation is relatively simple. Thus, to increase the selectivity of the co-oxidation reaction of propylene oxide, it is more advantageous to use a solid phase catalyst.
At present, the solid phase catalysts used for co-oxidation are basically SiO2 type catalysts which take TiO2 as an active component, and the type of catalysts are researched at China, such as Shanghai petrochemical institute (CN 1268400) and university of great company (CN 103464197A).
Either the Halcon process, the shell process, or the hydrogen peroxide process, propylene is reacted with organic hydrogen peroxide (or hydrogen peroxide) during the epoxidation reaction. The peroxide has poor thermal stability, decomposition occurs during the reaction, and the higher the temperature, the faster the decomposition rate. For example, japanese Sumitomo chemistry describes the decomposition of cumene hydroperoxide in its patent CN 01806929. Cumene hydroperoxide has a suitable use temperature and can be expressed by the following formula: t=150-0.8×w.
Wherein t is the allowable use temperature of the cumene hydroperoxide containing material and is at the temperature of DEG C; w is the mass content of cumene hydroperoxide in the material,%.
The cumene hydroperoxide stream of the same concentration has a cumene hydroperoxide decomposition rate of 2-3% when operated for 30min at an operating temperature T < T, and as high as 20-25% when operated for 30min at an operating temperature T > T.
The thermal decomposition rate of cumene hydroperoxide increases with increasing temperature, and the significant decomposition temperature point of cumene hydroperoxide decreases with increasing concentration of cumene hydroperoxide in the material, which is not only the property of cumene hydroperoxide but also the presence of oxides such as ethylbenzene hydroperoxide, tert-butyl hydroperoxide, hydrogen peroxide, etc.
In the co-oxidation reaction, in order to increase the selectivity of propylene oxide, the decomposition of the organic hydrogen peroxide must be reduced. Among them, reduction of thermal decomposition is one of the factors that have a great influence, and in particular, organic hydrogen peroxide is also susceptible to acid decomposition and alkali decomposition (Cao Gang. Cumene process for producing phenol aceton [ M ]. Chemical industry Press, 1983.). When organic hydrogen peroxide (hydrogen peroxide) is decomposed to generate corresponding alcohol and ketone, atomic oxygen is lost at the same time: R-OOH→R-OH+ [ O ]
The presence of atomic oxygen causes excessive oxidation of the organic matter, which increases the acid content in the reaction system, which in turn promotes acid decomposition of the organic hydrogen peroxide, while the organic acid itself is an alkylation catalyst and causes polymerization of the olefin, which causes an increase in undesirable side reactions.
Thus, in order to increase the selectivity of propylene oxide, it is advantageous to operate the co-oxidation reaction at low temperatures. The co-oxidation of olefins with organic peroxides, such as the Halcon process, is preferably carried out at a temperature of 50-120 ℃ (US 335 1635).
Since the co-oxidation reaction is exothermic, heat of reaction is evolved as the co-oxidation reaction proceeds, resulting in a continual increase in the reaction temperature, which in turn leads to an increase in side reactions and even to uncontrolled thermal decomposition of the organic hydrogen peroxide. However, the reaction at low temperature obviously cannot utilize the reaction heat at low temperature, so that the production cost is high.
To solve this problem, the gas phase epoxidation of olefins has been studied to some extent. Klemm et al in IEC.Res. 2008,47,2086-2090 reported the study of propylene gas phase epoxidation by gasifying 50% (wt) hydrogen peroxide with a special glass vaporizer or a microchannel falling film evaporator and using a microchannel reactor with an internal TS-1 titanium silicalite catalyst coating to enhance heat transfer and avoid reaction hot spots. Experimental results were obtained at atmospheric pressure and 140℃with propylene oxide selectivity greater than 90% and propylene oxide yield of 1kg/kg catalyst/hr. The effective utilization rate of hydrogen peroxide is more than 25%. The method has a certain industrialized prospect. In 2013, ferrandez et al, gas phase epoxidation was also investigated using a fixed bed epoxidation reactor. IEC res.2013, 52, 10126-10132, but no data for hydrogen peroxide availability are seen. Because the micro reaction device in the laboratory has the defect that the gas-phase residence time is too long, hydrogen peroxide is easy to decompose at high temperature, so that the higher hydrogen peroxide utilization rate cannot be obtained, the result of the epoxidation reaction is not necessarily the result, and the reactant is more likely to be caused by the thermal decomposition because of the too long residence time of the reactant in the catalyst-free area.
The invention patent application CN201910515976.5 describes a gas-solid fluidization process for the gas-phase epoxidation of propylene and hydrogen peroxide. Attempts to change the reactor type based on the newly developed epoxidation catalyst to obtain better heat transfer effect and reaction effect, but the thermal decomposition loss of hydrogen peroxide is necessarily caused due to the inherent serious gas phase back mixing defect of the fluidized bed reactor.
Disclosure of Invention
Aiming at the problems that the existing epoxidation reaction adopts a high-pressure low-temperature liquid phase method, the residence time of reactants is long, the heat of the epoxidation reaction cannot be utilized, and the hydroperoxide cannot be completely reacted, the invention provides a method for the gas-phase epoxidation of olefin and hydroperoxide, and the production cost of epoxide is greatly reduced.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
a process for the vapor phase epoxidation of an olefin with a hydroperoxide comprising the steps of:
a. proportioning olefin and hydroperoxide raw materials according to epoxidation reaction;
b. preheating and gasifying olefin at 0.5-1.5MPa to 60-150 deg.c;
c. spraying a hydroperoxide feedstock in the form of small droplets into the vaporized gaseous olefin and forming a stream of a gas-liquid mixture;
d. heating the gas-liquid mixture stream to 120-250 ℃ in a heat exchange manner, and completely gasifying the gas-liquid mixture stream to form a gas-phase epoxidation reactant stream;
e. under the action of an epoxidation catalyst, the gas-phase epoxidation reaction stream is subjected to an epoxidation reaction to form an epoxide discharge; the heat released by the epoxidation reaction is transferred by means of heat exchange;
f. the epoxide discharged material is used for heat exchange with the gas-liquid mixture flow in the step (d), and leaves the epoxidation reaction system for subsequent process to obtain propylene oxide.
As a further improvement of the invention: preheating the hydroperoxide feedstock sprayed in step (c) to a temperature of 5-20 ℃ below the self-accelerating decomposition temperature SADT of the peroxide. Thus, not only can the thermal decomposition of peroxide be controlled and the thermal decomposition amount be reduced, but also the gasification efficiency and the uniformity of material flow mixing can be improved. Different peroxides have slightly different temperatures.
As a further improvement of the invention: the olefin feed gasified in step (b) has a flow rate of from 10 to 50m/s.
As a preferred embodiment of the present invention: the olefin feed gasified in step (b) has a flow rate of from 20 to 30m/s.
In the present invention, controlling the flow rate can control the residence time and reaction time of the reactant stream in the reactor, and reducing the residence time and reaction time can reduce the decomposition rate of the stream.
As a preferred embodiment of the present invention: the temperature of the vapor phase epoxidation reactant stream in step (d) is controlled between 160 and 200 ℃.
According to the invention, on the basis of controlling the flow velocity of the material flow, the epoxidation reaction temperature is greatly improved, and the reaction rate can be greatly accelerated by improving the reaction temperature in the reaction system, so that the conversion rate of the reaction and the selectivity of the product are improved. Thus, a rapid reaction cycle is formed in the system of the present invention, and the hydroperoxide decomposition rate is greatly reduced because the residence time and reaction time are completed in a very short period of time.
As a preferred embodiment of the present invention: the molar ratio of olefin to hydroperoxide in the feed is 3-10:1.
as a preferred embodiment of the present invention: in order to adapt to the rapid reaction system, the invention designs an integrated reactor, wherein the integrated reactor is divided into two sections, the lower section is a shell-and-tube heat exchange section, the upper section is a shell-and-tube reaction section, and the step (d) and the step (e) are respectively carried out in the lower section and the upper section of the integrated reactor.
In the invention, the epoxidation reaction temperature is improved, the epoxidation reaction heat can be almost completely recovered in a heat exchange mode, and the recovered epoxidation reaction heat can be integrated into a pipe network for the procedures of separation and refining of propylene oxide and the like, thereby improving the energy utilization rate and greatly improving the economy of the epoxidation reaction.
The invention solves the problems that a large amount of low-temperature reaction heat of the existing olefin and hydroperoxide liquid phase low-temperature reaction cannot be utilized, the reaction residence time is too long, and the decomposition amount is large, and a set of rapid and relatively high-temperature reaction circulation process is innovatively designed, so that the decomposition amount of raw materials is reduced, the reaction rate and the conversion rate are improved, and meanwhile, the economy of the epoxidation reaction is improved.
Drawings
FIG. 1 is a process design of the present invention.
Description of the embodiments
In order to better understand the decomposition rate of the hydroperoxide in the high-speed and high-temperature system, so as to understand the advantages of the invention, the invention takes hydrogen peroxide as an example to carry out the following experiment:
experiment 1: under normal pressure, 30% (wt) hydrogen peroxide is atomized and gasified at 100 ℃ by taking nitrogen as carrier gas, then the gas phase residence time is 5 seconds, and then the mixture is cooled to room temperature, and the decomposition rate of the hydrogen peroxide is tested, as shown in table 1:
| sequence number | H 2 O 2 Concentration before gasification (%) | H 2 O 2 Post gasification concentration (%) | Concentration variation | H 2 O 2 Decomposition Rate (%) |
| 1 | 10.448 | 9.889 | 0.559 | 5.350 |
| 2 | 8.432 | 8.091 | 0.341 | 4.044 |
| 3 | 6.509 | 6.337 | 0.172 | 2.642 |
| 4 | 5.043 | 4.952 | 0.091 | 1.804 |
| 5 | 4.096 | 4.039 | 0.057 | 1.392 |
| 6 | 3.114 | 3.088 | 0.026 | 0.835 |
| 7 | 2.303 | 2.289 | 0.014 | 0.608 |
| 8 | 1.112 | 1.108 | 0.004 | 0.359 |
Table 1 shows the hydrogen peroxide vapor phase decomposition rate.
Implementation 2:0.5MPa, nitrogen is taken as carrier gas, 30% (wt) hydrogen peroxide is atomized and gasified at 140 ℃, then gas phase residence time is 1 second, then the mixture is cooled to room temperature, and the decomposition rate of the hydrogen peroxide is tested, as shown in table 2:
| sequence number | H 2 O 2 Concentration before gasification (%) | H 2 O 2 Post gasification concentration (%) | Concentration variation | Decomposition Rate (%) |
| 1 | 10.448 | 10.082 | 0.335 | 3.508 |
| 2 | 8.432 | 8.291 | 0.198 | 1.667 |
| 3 | 6.509 | 6.468 | 0.096 | 0.624 |
| 4 | 5.043 | 5.030 | 0.049 | 0.247 |
| 5 | 4.096 | 4.091 | 0.029 | 0.119 |
| 6 | 3.114 | 3.112 | 0.013 | 0.041 |
| 7 | 2.303 | 2.302 | 0.007 | 0.016 |
| 8 | 1.112 | 1.110 | 0.002 | 0.002 |
Table 2 shows the hydrogen peroxide vapor phase decomposition rate.
Therefore, the decomposition rate of hydrogen peroxide generated at high temperature is small under the condition of controlling the residence time.
For a clearer understanding of the present invention, the following examples are provided to illustrate further the process, features and advantages of the present invention.
In the embodiment 1, as shown in fig. 1, the equipment involved in the system is mainly an integrated reactor, and in the embodiment, the integrated reactor is divided into two sections, wherein the lower section is a shell-and-tube heat exchange section, and the upper section is a shell-and-tube reaction section.
As shown in fig. 1, the embodiment relates to a method for gas-phase epoxidation reaction of propylene and hydrogen peroxide, which specifically comprises the following steps: according to the mole ratio of propylene to hydrogen peroxide of 6:1, the concentration of hydrogen peroxide is 30% (wt); gasifying propylene under 1.0MPa, preheating to 120 ℃, adding hydrogen peroxide into the gas-phase propylene stream, and preheating the hydrogen peroxide to 10 ℃ below the self-accelerating decomposition temperature SADT so as to reduce the thermal decomposition amount of the hydrogen peroxide. Different peroxides have slightly different temperatures; the hydrogen peroxide material flow is sprayed into the propylene gas-phase material flow by the atomizing nozzle in the form of tiny liquid drops, so that most of the hydrogen peroxide material flow is gasified into the gas phase instantaneously, the gasification rate is 80%, the flow rate of the gas phase is controlled to be 25m/s, then a small amount of liquid drops are entrained in the propylene mixture material flow obtained by most of the hydrogen peroxide gasification, the mixture material flow enters a shell-and-tube heat exchange section E-104 of the integrated reactor, the mixture material flow is heated to 170 ℃ by epoxide material discharged from the shell side, the liquid drops are completely gasified, and uniform propylene and hydrogen peroxide gas-phase material flows are formed, and the reaction temperature is determined according to different reaction systems and catalysts. And then, enabling uniform propylene and hydrogen peroxide gas-phase material flows to enter a reaction tube of a tubular reaction section R-100, further carrying out epoxidation under the action of an epoxidation catalyst to generate a reaction product flow rich in propylene oxide, and leaving a reaction system for subsequent separation and refining to obtain propylene oxide. The shell side of the tubular reaction section removes the heat of reaction from a heat medium, which may be water and steam or organic hydrocarbons, esters and other compounds with moderate phase transition points, or heat transfer oil or molten salt, etc., preferably water and steam. The catalyst is TS-1 catalyst or the catalyst disclosed in patent application No. 201910515501.6.
In the embodiment, the gas phase reaction residence time is 0.6 seconds, and through detection analysis, the proportion of propylene oxide in the product is 12.5% (wt), the propylene oxide is more than 97% of selectivity, the selectivity of impurities such as acrolein, acrylic acid and the like is less than 2.5%, and hydrogen peroxide is effectively transferred into oxygen-containing compounds, especially propylene oxide.
The embodiments of the present invention are merely preferred embodiments of the present invention, the protection scope of the present invention is not limited thereto, and any person skilled in the art should cover the protection scope of the present invention by substituting or changing the technical scheme of the present invention and the inventive concept thereof.
Claims (6)
1. A process for the vapor phase epoxidation of an olefin with a hydroperoxide, comprising the steps of:
a. proportioning olefin and hydroperoxide raw materials according to epoxidation reaction;
b. preheating and gasifying olefin at 0.5-1.5MPa to 60-150 deg.c;
c. preheating the hydroperoxide raw material to a temperature which is 5-20 ℃ below the self-accelerating decomposition temperature SADT of the peroxide; spraying the preheated hydroperoxide feedstock in the form of droplets into the vaporized gaseous olefin and forming a gas-liquid mixture stream;
d. heating the gas-liquid mixture stream to a temperature of 120-250 ℃ in a heat exchange manner and allowing the gas-liquid mixture stream to fully gasify to form a gas-phase epoxidation reactant stream;
e. under the action of an epoxidation catalyst, the gas-phase epoxidation reaction stream is subjected to an epoxidation reaction to form an epoxide discharge; the heat released by the epoxidation reaction is transferred by means of heat exchange;
f. the epoxide discharged material is used for heat exchange with the gas-liquid mixture flow in the step (d), and leaves the epoxidation reaction system for subsequent process to obtain propylene oxide.
2. The method for vapor phase epoxidation according to claim 1, characterized in that: the olefin feed gasified in step (b) has a flow rate of from 10 to 50m/s.
3. The method for vapor phase epoxidation according to claim 2, characterized in that: the olefin feed gasified in step (b) has a flow rate of from 20 to 30m/s.
4. The method for vapor phase epoxidation according to claim 1 or 2, characterized in that: the temperature of the vapor phase epoxidation reactant stream in step (d) is controlled between 160 ℃ and 200 ℃.
5. The method for vapor phase epoxidation according to claim 1, characterized in that: the molar ratio of olefin to hydroperoxide in the feed is 3-10:1.
6. the method for vapor phase epoxidation according to claim 1, characterized in that: the reactor is provided with an integrated reactor, the integrated reactor is divided into two sections, the lower section is a shell-and-tube heat exchange section, the upper section is a shell-and-tube reaction section, and the step (d) and the step (e) are respectively carried out in the lower section and the upper section of the integrated reactor.
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| CN102532063A (en) * | 2011-11-17 | 2012-07-04 | 大连理工大学 | Device and method for performing olefin gaseous phase epoxidation by using industrial hydrogen peroxide |
| CN103880783A (en) * | 2012-12-20 | 2014-06-25 | 中国科学院大连化学物理研究所 | Method for preparing epoxypropane by catalyzing propylene epoxidation with phase-transfer catalyst under reaction control |
| CN110180586A (en) * | 2019-06-14 | 2019-08-30 | 大连理工大学 | The alkali metal ion modifying titanium-silicon molecular sieve TS-1 and preparation method thereof reacted for propylene and hydrogen peroxide gas-phase epoxidation |
| CN110256376A (en) * | 2019-06-14 | 2019-09-20 | 大连理工大学 | A kind of fluidization reaction method of propylene and hydrogen peroxide gas-phase epoxidation synthesizing epoxypropane |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102532063A (en) * | 2011-11-17 | 2012-07-04 | 大连理工大学 | Device and method for performing olefin gaseous phase epoxidation by using industrial hydrogen peroxide |
| CN103880783A (en) * | 2012-12-20 | 2014-06-25 | 中国科学院大连化学物理研究所 | Method for preparing epoxypropane by catalyzing propylene epoxidation with phase-transfer catalyst under reaction control |
| CN110180586A (en) * | 2019-06-14 | 2019-08-30 | 大连理工大学 | The alkali metal ion modifying titanium-silicon molecular sieve TS-1 and preparation method thereof reacted for propylene and hydrogen peroxide gas-phase epoxidation |
| CN110256376A (en) * | 2019-06-14 | 2019-09-20 | 大连理工大学 | A kind of fluidization reaction method of propylene and hydrogen peroxide gas-phase epoxidation synthesizing epoxypropane |
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