CN111978273A - Continuous synthesis process of epoxy chloropropane by hydrogen peroxide method - Google Patents

Continuous synthesis process of epoxy chloropropane by hydrogen peroxide method Download PDF

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Publication number
CN111978273A
CN111978273A CN202010992565.8A CN202010992565A CN111978273A CN 111978273 A CN111978273 A CN 111978273A CN 202010992565 A CN202010992565 A CN 202010992565A CN 111978273 A CN111978273 A CN 111978273A
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hydrogen peroxide
reactor
methanol
catalyst
chloropropene
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Inventor
徐林
黄杰军
丁克鸿
徐志斌
李明
胡钦
黄文嵘
刘洋
李幸霏
徐文轩
钱赟
邓生才
胡金良
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Jiangsu Ruixiang Chemical Co Ltd
Jiangsu Yangnong Chemical Group Co Ltd
Jiangsu Ruisheng New Material Technology Co Ltd
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Jiangsu Ruixiang Chemical Co Ltd
Jiangsu Yangnong Chemical Group Co Ltd
Jiangsu Ruisheng New Material Technology Co Ltd
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Priority to CN202010992565.8A priority Critical patent/CN111978273A/en
Publication of CN111978273A publication Critical patent/CN111978273A/en
Priority to KR1020237013755A priority patent/KR20230092922A/en
Priority to PCT/CN2021/119424 priority patent/WO2022057931A1/en
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D301/00Preparation of oxiranes
    • C07D301/02Synthesis of the oxirane ring
    • C07D301/03Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/12Synthesis 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
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D303/00Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02Compounds containing oxirane rings
    • C07D303/08Compounds containing oxirane rings with hydrocarbon radicals, substituted by halogen atoms, nitro radicals or nitroso radicals

Abstract

The invention provides a continuous synthesis process of epoxy chloropropane by a hydrogen peroxide method, which comprises the steps of putting hydrogen peroxide, methanol, chloropropene and a catalyst into a reactor for epoxidation, wherein the reactor is a ring reactor, the catalyst is pre-loaded into the ring reactor, chloropropene and methanol form a chloropropene-methanol mixed solution in a mixing tank, and the chloropropene-methanol mixed solution is pumped into the ring reactor by a metering pump A, and hydrogen peroxide is pumped into the ring reactor by a metering pump B. The synthesis process disclosed by the invention is less in methanol consumption, long in service life of the catalyst and simple in process device, realizes continuous operation, and can obtain relatively stable hydrogen peroxide conversion rate and relatively high epichlorohydrin selectivity in a long-time continuous operation process.

Description

Continuous synthesis process of epoxy chloropropane by hydrogen peroxide method
Technical Field
The invention belongs to the field of catalytic synthesis, relates to a method for synthesizing epichlorohydrin, and more particularly relates to a continuous synthesis process of epichlorohydrin by a hydrogen peroxide method.
Background
Epichlorohydrin is an important organic chemical raw material and fine chemical products, and because molecules of epichlorohydrin contain active epoxy groups and chlorine atoms, the epichlorohydrin is quite active in chemical property, becomes an important basic organic chemical raw material and intermediate, and is widely used for synthesizing epoxy resin, glycerol, alcohol rubber, medicines, pesticides, surfactants, glass fiber reinforced plastics, ion exchange resin, coatings, plasticizers and the like.
At present, domestic and foreign researches mainly focus on a process for preparing epoxy chloropropane by directly epoxidizing chloropropene by using hydrogen peroxide as an oxygen source, and the process route does not generate salt-containing wastewater, only generates water through reaction, and has high atom utilization rate and small pollution. CN101124044A discloses a process for producing epichlorohydrin, which uses a titanium-silicon molecular sieve as a catalyst, uses methanol as a solvent, directly epoxidizes chloropropene to prepare epichlorohydrin, fills the titanium-silicon molecular sieve into a fixed bed, prepares chloropropene, methanol and hydrogen peroxide into a homogeneous phase, and pumps the homogeneous phase into the fixed bed at a certain temperature for reaction, wherein the reaction requires the preparation of the homogeneous phase for the feeding, so that a large amount of methanol is required to be used, and the recovery energy consumption of methanol is high. CN102093313A describes a method for preparing epichlorohydrin, which comprises feeding hydrogen peroxide, methanol, chloropropene and a catalyst into a reaction kettle for direct epoxidation, and performing membrane separation on the liquid-solid mixture after the reaction to obtain a solid part and a liquid part, wherein the solid part is the catalyst, and the liquid part is separated and refined to obtain epichlorohydrin. The catalyst of the process has short service time, the catalyst needs to be regenerated in each reaction, the process is complex, and the energy consumption is high.
Disclosure of Invention
The invention aims to overcome the defects in the synthesis process of the epichlorohydrin and provides the epichlorohydrin synthesis process which is low in methanol consumption, simple in process device and capable of realizing continuous operation by adopting a ring reactor.
The purpose of the invention is realized by the following technical scheme: the method is characterized in that the reactor is a ring reactor, the catalyst is pre-loaded in the ring reactor, chloropropene and methanol form chloropropene and methanol mixed liquor in a mixing tank, the chloropropene and methanol mixed liquor is pumped into the ring reactor by a metering pump A, and meanwhile, hydrogen peroxide is pumped into the ring reactor by a metering pump B.
The catalyst is TS-1 catalyst and is packed in 1 section or more than 1 section.
The loop reactor is also connected with other components, and the other components comprise a forced circulation pump, a mixer, a settling tank or centrifugal equipment, a sampling valve and a reaction liquid collecting tank.
The outlet of the loop reactor is also connected to a filter, preferably a ceramic filter.
The mol ratio of chloropropene to hydrogen peroxide is 1-4: 1.
The molar ratio of the methanol to the hydrogen peroxide is 1-5: 1.
The concentration of the hydrogen peroxide is 10-70%.
The reaction temperature is 0-80 ℃.
The residence time of the reactants in the loop reactor is 0.1-10 h.
The reaction pressure is 0-1 MPa.
The invention provides a continuous synthesis process of epoxy chloropropane by a hydrogen peroxide method, which adopts a ring reactor and has the following advantages: the continuous operation is realized, the safety of the reaction process is high, and the control is accurate; secondly, a large amount of methanol is not needed, and the recovery of the methanol is reduced; the service life of the catalyst is longer, and the catalyst does not need to be separated; and fourthly, the process device is simple and is convenient for realizing industrialization. The chloropropene is oxidized by adopting the method, and the stable oxidant conversion rate and the high target oxidation product selectivity can be obtained in the long-time continuous operation process. Particularly, the method has high epoxide selectivity, thereby reducing the difficulty of subsequent separation and purification.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention.
FIG. 1 is a flow chart of the continuous synthesis process of epichlorohydrin by hydrogen peroxide method.
Detailed Description
The following detailed description further describes the present invention for the purpose of illustrating the technical solutions and objects of the present invention.
The loop reactor of the invention uses jacket circulating water to control the temperature.
The forced circulation pump is positioned in the annular reactor, so that the catalyst is uniformly mixed with the chloropropene methanol mixed liquid and hydrogen peroxide.
The mixer is positioned between the metering pump and the inlet of the ring reactor and is used for uniformly mixing the chloropropene methanol mixed solution and hydrogen peroxide.
The settling tank or the centrifugal equipment is common or unusual equipment for settling or centrifuging, is positioned between the mixer and the inlet of the loop reactor, and is connected in series or in parallel by one or more than one stage to prevent mechanical impurities or particles in a reaction system from entering the loop reactor.
The filter of the present invention is connected to the outlet of the loop reactor to prevent the passage of the catalyst solids residue having the smallest particle size, resulting in catalyst loss.
The ring reactor of the invention is used for washing and activating the catalyst firstly, and has the specific operation that after the catalyst is filled in the reactor and the reactor is installed, deionized water is pumped in to fill the whole ring reactor, a circulating water bath is started, a forced circulating pump is started, deionized water is continuously injected into the reactor through a metering pump to wash and wet the catalyst, deionized water is drained, methanol is continuously injected into the reactor through the metering pump to wet and activate the catalyst, and methanol is drained.
[ example 1 ]
(1) Filling a TS-1 catalyst into a reactor according to the figure 1, filling sections I-III, installing the reactor, pumping deionized water to fill the whole loop reactor, starting a circulating water bath at the water temperature of 0 ℃, and starting a forced circulating pump. Injecting deionized water into the system continuously through a metering pump for 4 hours to wash the wet catalyst, and discharging the deionized water completely; and continuously injecting methanol into the system through a metering pump for 4 hours to wet and activate the catalyst, and discharging the methanol.
(2) Mixing chloropropene and methanol uniformly according to a molar ratio of 1: 1;
(3) meanwhile, a metering pump A, B is started, the mixer is fed with the materials, the mol ratio of chloropropene to hydrogen peroxide is controlled to be 1:1, and the solubility of hydrogen peroxide is controlled to be 50 wt%. Controlling the retention time of the materials in the ring reactor to be 2 hours;
(4) and measuring the hydrogen peroxide and gas spectrum of the produced material every 30min and quantifying until the content of the epichlorohydrin in the produced oil layer and the produced water layer reaches a stable value. And starting to stably run to realize continuous synthesis of the reaction.
(5) The operation was continued under the above-mentioned conditions, during which the composition of the reaction mixture output from the reactor was checked and the oxidant conversion, the epichlorohydrin selectivity, was calculated, wherein the results at reaction times of 2 hours, 500 hours, 1000 and 2000 hours are shown in table 1.
[ example 2 ]
(1) Filling a TS-1 catalyst into a reactor according to the figure 1, filling a section I, installing the reactor, pumping deionized water to fill the whole loop reactor, starting a circulating water bath at the water temperature of 10 ℃, and starting a forced circulating pump. Continuously injecting deionized water into the system through a metering pump for 6 hours to wash the wet catalyst, and discharging the deionized water; and continuously injecting methanol into the system through a metering pump for 8 hours to wet and activate the catalyst, and discharging the methanol.
(2) Mixing chloropropene and methanol uniformly according to a molar ratio of 2: 1;
(3) meanwhile, a metering pump A, B is started, the mixer is fed with the materials, the mol ratio of chloropropene to hydrogen peroxide is controlled to be 1:1, and the solubility of hydrogen peroxide is controlled to be 10 wt%. Controlling the retention time of the materials in the ring reactor to be 1 h;
(4) the same as in example 1.
(5) The same as in example 1.
[ example 3 ]
(1) Filling TS-1 catalyst into a reactor according to the figure 1, filling sections I-IV, installing the reactor, pumping deionized water to fill the whole loop reactor, starting a circulating water bath at the water temperature of 30 ℃, and starting a forced circulating pump. Injecting deionized water into the system continuously through a metering pump for 8 hours to wash the wet catalyst, and discharging the deionized water completely; and continuously injecting methanol into the system through a metering pump for 6 hours to wet and activate the catalyst, and discharging the methanol.
(2) Mixing chloropropene and methanol uniformly according to a molar ratio of 1: 1;
(3) meanwhile, a metering pump A, B is started, the mixer is fed with the materials, the mol ratio of chloropropene to hydrogen peroxide is controlled to be 3:1, and the solubility of hydrogen peroxide is controlled to be 70 wt%. Controlling the retention time of the materials in the ring reactor to be 0.1 h;
(4) the same as in example 1.
(5) The same as in example 1.
[ example 4 ]
(1) Filling a TS-1 catalyst into a reactor according to the figure 1, filling sections I and II, installing the reactor, pumping deionized water to fill the whole loop reactor, starting a circulating water bath at the water temperature of 80 ℃, and starting a forced circulating pump. Injecting deionized water into the system continuously through a metering pump for 10 hours to wash the wet catalyst, and discharging the deionized water completely; and continuously injecting methanol into the system through a metering pump for 24 hours to wet and activate the catalyst, and discharging the methanol.
(2) Mixing chloropropene and methanol uniformly according to a molar ratio of 5: 1;
(3) meanwhile, a metering pump A, B is started, the mixer is fed with the materials, the mol ratio of chloropropene to hydrogen peroxide is controlled to be 2:1, and the solubility of hydrogen peroxide is controlled to be 70 wt%. Controlling the retention time of the materials in the loop reactor to be 10 h;
(4) the same as in example 1.
(5) The same as in example 1.
[ example 5 ]
(1) Filling TS-1 catalyst into a reactor according to the figure 1, filling sections I-IV, installing the reactor, pumping deionized water to fill the whole loop reactor, starting a circulating water bath at the water temperature of 20 ℃, and starting a forced circulating pump. Injecting deionized water into the system continuously through a metering pump for 10 hours to wash the wet catalyst, and discharging the deionized water completely; and continuously injecting methanol into the system through a metering pump for 12h to wet and activate the catalyst, and discharging the methanol.
(2) Mixing chloropropene and methanol uniformly according to a molar ratio of 4: 3;
(3) meanwhile, a metering pump A, B is started, the mixer is fed with the materials, the mol ratio of chloropropene to hydrogen peroxide is controlled to be 4:1,
the solubility of hydrogen peroxide is 40 wt%. Controlling the retention time of the materials in the ring reactor to be 3 h;
(4) the same as in example 1.
(5) The same as in example 1.
[ example 6 ]
(1) Filling TS-1 catalyst into a reactor according to the figure 1, filling sections I-IV, installing the reactor, pumping deionized water to fill the whole loop reactor, starting a circulating water bath at the water temperature of 10 ℃, and starting a forced circulating pump. Injecting deionized water into the system continuously through a metering pump for 12 hours to wash the wet catalyst, and discharging the deionized water completely; and continuously injecting methanol into the system through a metering pump for 16h to wet and activate the catalyst, and discharging the methanol.
(2) Mixing chloropropene and methanol uniformly according to a molar ratio of 3: 5;
(3) meanwhile, a metering pump A, B is started, the mixer is fed with the materials, the mol ratio of chloropropene to hydrogen peroxide is controlled to be 3:1,
the solubility of hydrogen peroxide is 60 wt%. Controlling the retention time of the materials in the ring reactor to be 1 h;
(4) the same as in example 1.
(5) The same as in example 1.
Table 1 examples 1-6 continuous run results data
Figure BDA0002691245370000051
Figure BDA0002691245370000061
Comparative example 1
(1) Chloropropene, methanol, hydrogen peroxide and a catalyst in the same proportion as in example 5 are added into a reaction kettle, the temperature is raised to 42 ℃, and the reaction is carried out for 2 h.
(2) And (4) after the reaction is finished, detecting the hydrogen peroxide residue and the content of epoxy chloropropane in the reaction solution, and calculating the hydrogen peroxide conversion rate and the yield of the epoxy chloropropane. The catalyst is used for next batch of epoxidation reaction after being filtered.
The results are listed in table 2.
Table 2 data of catalyst application results of comparative examples
Figure BDA0002691245370000062
Figure BDA0002691245370000071
The invention is not limited to the embodiments of the invention described.
The structure and the implementation of the present invention are described herein by using specific examples, and the above description of the examples is only used to help understand the core idea of the present invention. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.

Claims (10)

1. A continuous synthesis process of epoxy chloropropane by hydrogen peroxide is characterized in that hydrogen peroxide, methanol, chloropropene and a catalyst are put into a reactor for epoxidation, the reactor is a ring reactor, the catalyst is pre-loaded into the ring reactor, chloropropene and methanol form a chloropropene-methanol mixed solution in a mixing tank, the chloropropene-methanol mixed solution is pumped into the ring reactor by a metering pump A, and hydrogen peroxide is pumped into the ring reactor by a metering pump B.
2. The continuous synthesis process of epichlorohydrin by hydrogen peroxide method according to claim 1, wherein the catalyst is a TS-1 catalyst and is packed in 1 or more stages.
3. The continuous synthesis process of epichlorohydrin by hydrogen peroxide method according to claim 1, wherein the loop reactor is further connected with other components, and the other components comprise a forced circulation pump, a mixer, a settling tank or a centrifugal device, a production valve and a reaction liquid collecting tank.
4. The continuous synthesis process of epichlorohydrin by hydrogen peroxide method according to claim 3, wherein the outlet of the loop reactor is further connected with a filter, preferably a ceramic filter.
5. The continuous synthesis process of epoxy chloropropane by using a hydrogen peroxide method according to claim 1, characterized in that the molar ratio of chloropropene to hydrogen peroxide is 1-4: 1.
6. The continuous synthesis process of epichlorohydrin by a hydrogen peroxide method according to claim 1, wherein the molar ratio of methanol to hydrogen peroxide is 1-5: 1.
7. The continuous synthesis process of epichlorohydrin by using hydrogen peroxide as claimed in claim 1, wherein the concentration of hydrogen peroxide is 10-70%.
8. The process for the continuous synthesis of epichlorohydrin by hydrogen peroxide method according to claim 1, wherein the reaction temperature is 0-80 ℃.
9. The continuous synthesis process of epichlorohydrin by hydrogen peroxide method according to claim 1, wherein the residence time of the reactants in the loop reactor is 0.1-10 h.
10. The process for continuously synthesizing epichlorohydrin by a hydrogen peroxide method according to claim 1, wherein the reaction pressure is 0-1 MPa.
CN202010992565.8A 2020-09-21 2020-09-21 Continuous synthesis process of epoxy chloropropane by hydrogen peroxide method Pending CN111978273A (en)

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CN116514741A (en) * 2023-07-04 2023-08-01 山东民基新材料科技有限公司 Process for producing epoxy chloropropane by utilizing micro-interface reaction

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