CN112174914A - Method for gas-phase epoxidation reaction of olefin and hydroperoxide - Google Patents
Method for gas-phase epoxidation reaction of olefin and hydroperoxide Download PDFInfo
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- CN112174914A CN112174914A CN202011070640.1A CN202011070640A CN112174914A CN 112174914 A CN112174914 A CN 112174914A CN 202011070640 A CN202011070640 A CN 202011070640A CN 112174914 A CN112174914 A CN 112174914A
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- 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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- 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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Abstract
The invention relates to a process for the gas-phase epoxidation of an olefin with a hydroperoxide, comprising the steps of: a. proportioning raw materials; b. preheating and gasifying olefins; c. spraying a hydroperoxide raw material on the gasified gas-phase olefin to form a gas-liquid mixture flow; d. heating the gas-liquid mixture stream to a temperature such that the gas-liquid mixture stream is completely vaporized to form a vapor phase epoxidation reaction stream; e. carrying out epoxidation reaction under an epoxidation catalyst to form an epoxide discharge; and transferring heat released by the epoxidation reaction; f. and (d) the epoxide discharge is used for carrying out heat exchange with the gas-liquid mixture flow in the step (d), and then the epoxide discharge leaves an epoxidation reaction system for carrying out subsequent processes to obtain the 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 the conversion rate, and simultaneously improves the economy of the epoxidation reaction.
Description
Technical Field
The invention belongs to the technical field of chemical 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. Among propylene derived products, propylene oxide is currently second only to the third largest derivatives of polypropylene and acrylonitrile. The propylene oxide is mainly used for preparing polyether polyol, propylene glycol, alcohol amine and various nonionic surfactants in industry, and derivatives of the propylene oxide are widely applied to industries such as petrifaction, buildings, household appliances, automobiles, medicines, pesticides, textiles, daily chemicals and the like.
The traditional production method of the propylene oxide is a chlorohydrin method and is characterized by shorter flow, mature process, larger operation load elasticity, good selectivity, high yield, safer production, low requirement on the purity of the raw material propylene and less construction investment; but the chlorohydrin method can produce a large amount of waste water containing calcium chloride in the process of producing the propylene oxide, and causes serious pollution to the environment. Thus, clean and economical green propylene oxide production technologies are actively developed in various countries.
The current production routes 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 an ethylbenzene method, an isobutane method, an isopropylbenzene method and the like according to the difference of organic hydrogen peroxide, and the methods are the most extensive 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 the technology has the advantages of simple flow, small influence on the environment and more domestic researches; the direct oxidation method of propylene is the most economical production method, but still stays in the experimental research stage at present, and no suitable catalytic material is found.
Olefin co-oxidation processes were first published in US3351635 by Halcon corporation (now Lyondell corporation) in 1967. The co-oxidation reaction of olefin and organic hydrogen peroxide is generally carried out at 50 to 120 ℃ and 1000psi, in order to react propylene in a liquid phase.
The specific reaction process of the propylene oxide is as follows: R-OOH + CH3CH = CH2 → R-OH + CH3CHOCH2
Wherein R is an organic group which can be ethylphenyl, cumyl, tert-butyl, isoamyl, cyclopentyl, cyclohexyl and the like.
At present, the industrialized co-oxidation propylene oxide process comprises a propylene oxide-styrene co-production process, a propylene oxide-tert-butyl alcohol (or methyl tert-butyl ether) co-production process and a propylene oxide process by an isopropyl benzene method.
The process for co-producing propylene oxide and styrene mainly comprises three reactions of liquid-phase oxidation of ethylbenzene to generate ethylbenzene hydroperoxide, liquid-phase co-oxidation of the ethylbenzene hydroperoxide and propylene to generate 1-phenethyl alcohol and propylene oxide, and dehydration of the 1-phenethyl alcohol to generate styrene, and the specific description is disclosed in US5210354 of the ARCO company. The process for co-producing propylene oxide and tert-butyl alcohol mainly comprises the steps of carrying out liquid-phase oxidation on isobutane to generate tert-butyl hydroperoxide, carrying out liquid-phase co-oxidation on the tert-butyl hydroperoxide and propylene to generate tert-butyl alcohol and propylene oxide, and further converting the tert-butyl alcohol into methyl tert-butyl ether (MTBE), and the specific description is in a patent US5424458 of ARCO company. The main difference between the propylene oxide process by the cumene method, the propylene oxide-styrene co-production process and the propylene oxide-tert-butyl alcohol (or methyl tert-butyl ether) co-production process lies in that the dimethyl benzyl alcohol serving as a co-product is hydrogenated to generate raw material cumene for recycling, and the liquid phase oxidation of the cumene and the liquid phase co-oxidation process of cumene hydroperoxide and propylene are similar to the co-oxidation process of ARCO company, and the specific description refers to the Sumitomo chemical patent CN 1856482.
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 ℃ at 1000 psi. In the epoxidation process, homogeneous catalysts of the molybdenum, tungsten, titanium, niobium, tantalum, rhenium, selenium, chromium, zirconium, tellurium and uranium series which are soluble in the reaction mass can be used.
In addition to the homogeneous catalysts described above, there are also processes in which heterogeneous catalysts are used for the co-oxidation of propylene. The patent US8664412 from Shell company describes the epoxidation of olefins, differing from the Halcon process by the use of a heterogeneous solid phase epoxidation catalyst. The Shell company in its patent US3829392 describes a solid-phase catalyst for the epoxidation of olefins, in which TiO2 is supported on SiO 2. In addition to the TiO2-SiO2 type catalyst from Shell, the cumene process of Sumitomo chemical in Japan also employs a solid phase catalyst for the epoxidation reaction. Sumitomo chemistry in patent CN1953969 describes a process for the preparation of propylene oxide using a titanosilicate solid-phase catalyst which is easier and less costly to produce.
In addition to the co-oxidation method, the propylene oxide process by the hydrogen peroxide method directly adopts hydrogen peroxide to react with propylene to generate propylene oxide. Currently, propylene oxide produced by the hydrogen peroxide process (HPPO process) has been commercialized by technologies developed by BASF and Dow chemical (Dow) and by the winning group (Degussa) and wood (Uhde). The difference between the two technologies is mainly the reactor type of the epoxidation reaction, and both technologies gradually mature under the development background of the catalytic technology, in particular the titanium silicalite TS-1. (Liubo, Zhang Xiaoli, Zhao Li, et al. State of the Art of propylene oxide production [ J ] contemporary chemical industry 2016, 45(2): 336-.
Compared with the Halcon method propylene oxide process, the Shell method propylene oxide process, the Sumitomo method propylene oxide process and the existing hydrogen peroxide method propylene oxide process all adopt solid phase epoxidation catalysts. Compared with homogeneous epoxidation process, the solid phase co-oxidation catalyst is adopted, so that the separation step of the catalyst and the materials is omitted, the reaction flow is simplified, and meanwhile, the reaction retention time is short, the reaction back mixing is less, so that the side reaction is less, the raw material consumption is less, and the product separation is relatively simple. Thus, in order to increase the selectivity of the co-oxidation reaction to propylene oxide, it is more advantageous to use a solid phase catalyst.
At present, the solid phase catalysts for co-oxidation are basically SiO2 type catalysts with TiO2 as an active component, and the national institute of petrochemical industry (CN1268400) and university of China (CN103464197A) are all researching the type of catalysts.
Either the Halcon process, the shell process or the hydrogen peroxide process, propylene reacts with organic hydrogen peroxide (or hydrogen peroxide) during the epoxidation reaction. Peroxide has poor thermal stability, and is decomposed during the reaction, and the higher the temperature is, the faster the decomposition speed is. For example, sumitomo chemical in japan 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 material containing the cumene hydroperoxide and the DEG C; w is the mass content of cumene hydroperoxide in the material, percent.
The cumene hydroperoxide decomposition rate of the same concentration is 2-3% when the stream is operated for 30min at an operating temperature T < T, and the cumene hydroperoxide decomposition rate is up to 20-25% when the stream is operated for 30min at an operating temperature T > T.
The thermal decomposition rate of cumene hydroperoxide increases with the temperature increase, and the significant decomposition temperature point of cumene hydroperoxide decreases with the increase in the concentration of cumene hydroperoxide in the feed, which is not only a property of cumene hydroperoxide but also a phenomenon in which an oxide is present such as ethylbenzene hydroperoxide, tert-butyl hydroperoxide, hydrogen peroxide, etc.
In the co-oxidation reaction, in order to improve the selectivity of propylene oxide, it is necessary to reduce the decomposition of organic hydrogen peroxide. Among them, reduction of thermal decomposition is a factor which has a large influence, and particularly, organic hydrogen peroxide is also easily subjected to acid decomposition and alkali decomposition (Cao. isopropyl benzene method for producing phenol acetone [ M ], chemical industry Press, 1983.). When organic hydrogen peroxide (hydrogen peroxide) is decomposed to generate corresponding alcohol and ketone, atomic oxygen is lost: R-OOH → R-OH + [ O ]
The presence of atomic oxygen causes excessive oxidation of organic substances, which increases the acid content in the reaction system, which in turn promotes acid decomposition of organic hydrogen peroxide, and the organic acid itself is an alkylation catalyst and causes polymerization of olefins, 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 preferred temperature for co-oxidation of olefins with organic peroxides, such as the Halcon process, is in the range of from 50 to 120 c (US 3351635).
Since the co-oxidation reaction is exothermic, the heat of reaction is released as the co-oxidation reaction proceeds, resulting in a continuous 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 address this problem, there has been some research in the gas phase epoxidation of olefins. Klemm et al, IEC.Res. 2008,47,2086-2090, reported the study of propylene gas phase epoxidation, 50% (wt) hydrogen peroxide was vaporized by using a special glass vaporizer or a microchannel falling film evaporator, and a microchannel reactor with an internal coating of a TS-1 titanium silicalite molecular sieve catalyst was used to enhance heat transfer and avoid reaction hot spots. The experimental result that the selectivity of the propylene oxide is more than 90 percent and the yield of the propylene oxide is 1kg/kg catalyst/hr is obtained under the normal pressure and at the temperature of 140 ℃. The effective utilization rate of the hydrogen peroxide is more than 25 percent. Showing a certain industrialization prospect. In 2013, Ferrandez et al also conducted gas phase epoxidation studies using a fixed bed epoxidation reactor. IEC RES, 2013, 52, 10126 and 10132, but no data on the utilization rate of the hydrogen peroxide are found. Since the micro-reactor in the laboratory generally has the disadvantage of long gas phase residence time, and hydrogen peroxide is very easily decomposed at high temperature, a high hydrogen peroxide utilization rate cannot be obtained, which is not necessarily the result of the epoxidation reaction, and is more likely to be caused by thermal decomposition due to long residence time of reactants in a catalyst-free region.
Patent application CN201910515976.5 describes a process for gas-solid fluidization by the epoxidation of propylene with hydrogen peroxide gas phase. On the basis of a newly developed epoxidation catalyst, the reactor type is changed to obtain better heat transfer effect and reaction effect, but the thermal decomposition loss of hydrogen peroxide is inevitably caused due to the inherent defect of serious gas phase back mixing of a 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 retention time of reactants is long, the epoxidation reaction heat can not be utilized, and hydroperoxide can not completely react, the invention provides a method for gas phase epoxidation of olefin and hydroperoxide, which greatly reduces the production cost of epoxide.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a process for the gas phase epoxidation of an olefin with a hydroperoxide comprising the steps of:
a. proportioning olefin and hydroperoxide raw materials according to an epoxidation reaction;
b. preheating and gasifying olefin to 60-150 deg.c under 0.5-1.5 MPa;
c. spraying a hydroperoxide raw material into the gasified gas-phase olefin in a small droplet form to form a gas-liquid mixture flow;
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 reaction stream;
e. under the action of an epoxidation catalyst, carrying out epoxidation reaction on the gas-phase epoxidation reaction flow to form an epoxide discharge; the heat released by the epoxidation reaction is transferred by means of heat exchange;
f. and (d) the epoxide discharge is used for carrying out heat exchange with the gas-liquid mixture flow in the step (d), and then the epoxide discharge leaves an epoxidation reaction system for carrying out subsequent processes to obtain the propylene oxide.
As a further improvement of the invention: preheating the hydroperoxide feedstock sprayed in step (c) to a temperature of from 5 to 20 ℃ below the self-accelerating decomposition temperature of the peroxide SADT. This not only controls the thermal decomposition of the peroxide and reduces the amount of thermal decomposition, but also improves the gasification efficiency and the uniformity of the stream mixing. This temperature is slightly different for different peroxides.
As a further improvement of the invention: the flow rate of the olefin material gasified in the step (b) is 10-50 m/s.
As a preferred embodiment of the present invention: the flow rate of the olefin material gasified in the step (b) is 20-30 m/s.
Controlling the flow rate in the present invention allows control of the residence time and reaction time of the reactant stream in the reactor, and reducing the residence time and reaction time allows for a reduction in the rate of decomposition of the stream.
As a preferred embodiment of the present invention: the temperature of the vapor phase epoxidation reaction stream in step (d) is controlled at 160 ℃ to 200 ℃.
According to the invention, on the basis of controlling the flow rate of the material flow, the epoxidation reaction temperature is greatly increased, and the reaction rate can be greatly increased by increasing the reaction temperature in the reaction system, so that the conversion rate of the reaction and the selectivity of the product are increased. Therefore, a rapid reaction circulation process is formed in the system, and the decomposition rate of the hydroperoxide is greatly reduced because the retention time and the reaction time are completed in a very short time.
As a preferred embodiment of the present invention: the molar ratio of the olefin to the 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 the integrated reactor which is divided into two sections, wherein 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.
According to the invention, due to the increase of the epoxidation reaction temperature, the epoxidation reaction heat can be almost completely recovered through a heat exchange mode, and the recovered epoxidation reaction heat can be merged into a pipe network for the processes of separation and refining of propylene oxide and the like, so that the energy utilization rate is improved, and the economy of the epoxidation reaction is greatly improved.
The invention overcomes the problems that a large amount of low-temperature reaction heat of the existing olefin and hydroperoxide liquid-phase low-temperature reaction can not be utilized, the reaction retention time is too long, and the decomposition amount is large, innovatively designs a set of rapid and high-temperature reaction circulation process, reduces the decomposition amount of raw materials, improves the reaction rate and the conversion rate, and simultaneously improves the economy of epoxidation reaction.
Drawings
FIG. 1 is a process design of the present invention.
Detailed Description
In order to better understand the decomposition rate of the hydroperoxide in the high-speed and high-temperature system, and thus understand the advantages of the present invention, the present invention takes hydrogen peroxide as an example to perform the following experiments:
experiment 1: under normal pressure, using nitrogen as carrier gas, after 30% (wt) hydrogen peroxide is atomized and gasified at 100 ℃, the gas phase stays for 5 seconds, then the temperature is cooled to room temperature, and the decomposition rate of the hydrogen peroxide is tested, as shown in table 1:
| serial number | H2O2Concentration before gasification (%) | H2O2Concentration after gasification (%) | Amount of change in concentration | H2O2Decomposition 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 gas phase decomposition rate of hydrogen peroxide.
Implementation 2: 0.5MPa, using nitrogen as carrier gas, atomizing and gasifying 30% (wt) hydrogen peroxide at 140 ℃, keeping the gas phase for 1 second, then quenching to room temperature, and testing the decomposition rate of the hydrogen peroxide, as shown in Table 2:
| serial number | H2O2Concentration before gasification (%) | H2O2Concentration after gasification (%) | Amount of change in concentration | 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 gas phase decomposition rate table of hydrogen peroxide.
From this, it is found that the decomposition rate of hydrogen peroxide generated at a high temperature is small under the control of the residence time.
In order that the present invention may be more clearly understood, the following examples are provided to further illustrate the processes, features and advantages of the present invention.
Example 1, as shown in fig. 1, the equipment involved in the system is mainly an integrated reactor, in this example, the integrated reactor is divided into two sections, the lower section is a shell-and-tube heat exchange section, and the upper section is a tubular reaction section.
As shown in fig. 1, the present embodiment relates to a method for gas-phase epoxidation of propylene and hydrogen peroxide, which comprises the following specific steps: according to the mol ratio of 1: 6, the concentration of hydrogen peroxide is 30 percent (wt); under 1.0MPa, gasifying propylene and 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; hydrogen peroxide material flow is sprayed in propylene gas phase material flow in the form of micro liquid drops through an atomizing nozzle, so that most of hydrogen peroxide material flow is instantaneously gasified and enters a gas phase, 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 carried in most of the gasified propylene mixture material flow, the most of gasified hydrogen peroxide material flow enters a shell-and-tube heat exchange section E-104 tube array of the integrated reactor, the obtained product is discharged by epoxide entering a shell pass and is heated to 170 ℃, the liquid drops are completely gasified, uniform propylene and hydrogen peroxide gas phase material flow is formed, and the reaction temperature is determined according to different reaction systems and catalysts. Then the uniform propylene and hydrogen peroxide gas phase material flow enters a reaction tube of a tubular reaction section R-100, further epoxidation reaction is carried out under the action of an epoxidation catalyst to generate a reaction product flow rich in propylene oxide, and the reaction product flow leaves a reaction system to carry out subsequent separation and refining to obtain the propylene oxide. The shell side of the tubular reaction section removes reaction heat by a heat medium, wherein the heat medium can be water and steam or organic hydrocarbon, ester and other compounds with moderate phase change points or heat conducting oil or molten salt, and preferably water and steam. The catalyst used was a TS-1 catalyst or a catalyst described in patent application No. 201910515501.6.
In the embodiment, the gas phase reaction has a residence time of 0.6 second, and through detection and analysis, the ratio of propylene oxide in the product is 12.5% (wt), the selectivity of propylene oxide is more than 97%, the selectivity of impurities such as acrolein and acrylic acid is less than 2.5%, and hydrogen peroxide is effectively transferred to oxygen-containing compounds, especially propylene oxide.
The embodiments of the present invention are merely preferred embodiments of the present invention, and the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the scope of the present invention by substituting or changing the equivalent technical solution and the inventive concept of the present invention.
Claims (7)
1. A process for the gas-phase epoxidation of an olefin with a hydroperoxide, characterized by the steps of:
a. proportioning olefin and hydroperoxide raw materials according to an epoxidation reaction;
b. preheating and gasifying olefin to 60-150 deg.c under 0.5-1.5 MPa;
c. spraying a hydroperoxide raw material into the gasified gas-phase olefin in a small droplet form to form a gas-liquid mixture flow;
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 reaction stream;
e. under the action of an epoxidation catalyst, carrying out epoxidation reaction on the gas-phase epoxidation reaction flow to form an epoxide discharge; the heat released by the epoxidation reaction is transferred by means of heat exchange;
f. and (d) the epoxide discharge is used for carrying out heat exchange with the gas-liquid mixture flow in the step (d), and then the epoxide discharge leaves an epoxidation reaction system for carrying out subsequent processes to obtain the propylene oxide.
2. The process for the gas-phase epoxidation of claim 1 wherein the hydroperoxide feed sprayed in step (c) is preheated to a temperature of 5-20 ℃ below the self-accelerating decomposition temperature of the peroxide SADT.
3. The process for the gas-phase epoxidation reaction of claim 1, characterized in that: the flow rate of the olefin material gasified in the step (b) is 10-50 m/s.
4. The process for the gas-phase epoxidation reaction of claim 3, characterized in that: the flow rate of the olefin material gasified in the step (b) is 20-30 m/s.
5. The process for the gas-phase epoxidation reaction of claim 1 or 3, characterized in that: the temperature of the vapor phase epoxidation reaction stream in step (d) is controlled at 160 ℃ to 200 ℃.
6. The process for the gas-phase epoxidation reaction of claim 1, characterized in that: the molar ratio of the olefin to the hydroperoxide in the feed is 3-10: 1.
7. the process for the gas-phase epoxidation reaction of claim 1, characterized in that: the method is characterized in that an integrated reactor is arranged, 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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| CN113072522A (en) * | 2021-03-25 | 2021-07-06 | 浙江智英石化技术有限公司 | Method for removing ethylbenzene hydroperoxide in mixed organic phase |
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| 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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| 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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| CN113072522A (en) * | 2021-03-25 | 2021-07-06 | 浙江智英石化技术有限公司 | Method for removing ethylbenzene hydroperoxide in mixed organic phase |
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