CN211771013U - Device for continuously producing epoxy chloropropane by oxidizing chloropropene with titanium-silicon molecular sieve - Google Patents

Device for continuously producing epoxy chloropropane by oxidizing chloropropene with titanium-silicon molecular sieve Download PDF

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CN211771013U
CN211771013U CN202020084521.0U CN202020084521U CN211771013U CN 211771013 U CN211771013 U CN 211771013U CN 202020084521 U CN202020084521 U CN 202020084521U CN 211771013 U CN211771013 U CN 211771013U
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filter
separation tank
tubular reactor
outlet
catalyst
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黄家辉
张恒耘
于娜娜
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Dalian Institute of Chemical Physics of CAS
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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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/32—Separation; Purification
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/36—Use of additives, e.g. for stabilisation
    • 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
    • C07D303/08—Compounds containing oxirane rings with hydrocarbon radicals, substituted by halogen atoms, nitro radicals or nitroso radicals

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  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Epoxy Compounds (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The utility model discloses a device for continuously producing epichlorohydrin by oxidizing chloropropene with a titanium silicalite molecular sieve, which comprises a mixer, a tubular reactor, a separation tank and a filter; the bottom of the separation tank is provided with a slurry outlet; a clear liquid discharge hole is formed in the upper part of the separation tank; the filter is arranged at the clear liquid outlet; the outlet of the mixer is communicated with the feed inlet of the tubular reactor through a pipeline; and the outlet of the tubular reactor is communicated with the feed inlet of the separation tank. In the continuous production process, the catalyst is not required to be recovered, and the gas phase part is condensed and refluxed by a condenser at the top of the separation tank. The device has the characteristics of simple process flow, no need of separation of the catalyst, low requirement on mechanical strength of the catalyst, high effective utilization rate of hydrogen peroxide and high yield of epoxy chloropropane, and can be used in industrial production.

Description

Device for continuously producing epoxy chloropropane by oxidizing chloropropene with titanium-silicon molecular sieve
Technical Field
The utility model relates to a device for continuous production epichlorohydrin of chloropropylene oxide of titanium silicon molecular sieve catalytic oxidation chloropropene belongs to the production facility field of chemical products.
Background
Epichlorohydrin is an important basic chemical raw material, and is also an organic synthetic raw material and an intermediate with extremely strong functionality, and the application is very wide. Is used for producing epoxy resin, chlorohydrin rubber, surfactant, etc. and is an important raw material for producing glycerin and glycidyl derivative. At present, the main methods for preparing epichlorohydrin comprise a chlorohydrin method and a glycerol method.
The main raw materials for producing epichlorohydrin by a chlorohydrination method are chlorine, propylene and lime, and the main production process comprises three parts of chlorohydrination, saponification and refining. The process is mature, the production is safe, but the production process has serious corrosion to equipment, consumes a large amount of chlorine, generates a large amount of waste water in the production and seriously pollutes the environment.
The glycerol method has the outstanding advantages of environmental protection, greatly reduced three wastes compared with the propylene high-temperature oxidation method, limited glycerol resources, import dependence and difficulty in treating wastewater and waste residues in the saponification process.
At present, because people pay more and more attention to environmental protection, the preparation method of the environmental-friendly epichlorohydrin is more and more paid more and more attention by researchers. Therefore, the environment-friendly green process for preparing the epichlorohydrin by directly epoxidizing the chloropropene is produced.
SUMMERY OF THE UTILITY MODEL
Based on above background art, the utility model provides a continuous production device for chloropropene direct epoxidation prepares epichlorohydrin has solved among the prior art problem such as the mechanical strength requirement height of process flow, catalyst, hydrogen peroxide effective utilization rate is low and the epichlorohydrin yield is not high, is favorable to the industrial continuous production of epichlorohydrin, specifically takes following technical scheme:
a continuous production device for preparing epichlorohydrin by direct epoxidation of chloropropene comprises a mixer, a tubular reactor, a separation tank and a filter; the bottom of the separation tank is provided with a slurry outlet; a clear liquid discharge hole is formed in the upper part of the separation tank; the filter is arranged at the clear liquid outlet; the outlet of the mixer is communicated with the feed inlet of the tubular reactor through a pipeline; and the outlet of the tubular reactor is communicated with the feed inlet of the separation tank.
Based on the technical scheme, preferably, the slurry outlet of the separator is communicated with the inlet of the tubular reactor.
Based on the above technical solution, preferably, the apparatus further comprises a condenser; the condenser is arranged at the top of the separator;
based on the technical scheme, the tubular reactor is preferably a metal hollow tube with a smooth inner wall, the inner diameter of the metal hollow tube is 10-500mm, and the length of the metal hollow tube is 1-100 m.
Based on the technical scheme, the filter is preferably a ceramic membrane filter element or a polytetrafluoroethylene filter element, and the pore size of the filter is 2-10 microns smaller than the particle size of the catalyst; the filter is connected with the clear liquid discharge port in a detachable pipeline manner.
Based on the technical scheme, the filter is preferably a polytetrafluoroethylene filter element; the pores of the polytetrafluoroethylene filter cores are 1-50 microns, the filter consists of 1-100 polytetrafluoroethylene filter cores, and the polytetrafluoroethylene filter cores are solid cylindrical.
Based on the technical scheme, preferably, the condenser and the tubular reactor are both provided with jacket heat exchange layers.
Using the apparatus described above; the specific reaction comprises the following steps:
(1) respectively conveying reaction raw materials of chloropropene, aqueous hydrogen peroxide, a solvent methanol and a catalyst to a first mixer through a metering pump, and uniformly mixing to obtain a raw material mixed solution, wherein the raw material mixed solution is in a homogeneous phase state, the raw material mixed solution is conveyed to a first tubular reactor for reaction, the reaction temperature of the first tubular reactor is set to be 20-70 ℃, and the retention time is 1-7 hours;
(2) the reaction material in the tubular reactor enters a separation tank through an outlet, and nitrogen is introduced into the separation tank to keep the pressure of the separation tank at 0.1-0.8 MPa; the gas phase product enters a first condenser for condensation and reflux, clear liquid containing the product is separated out through a filter at a clear liquid discharge hole, and the catalyst slurry enters a first mixer for recycling through a slurry outlet of a separation tank; the invention can add catalyst into the mixer, and also can add titanium-silicon molecular sieve catalyst into the separation tank at one time, and the titanium-silicon molecular sieve catalyst enters the mixer through a slurry outlet at the bottom of the separation tank;
the solid content percentage of the catalyst weight of the reaction liquid in the tubular reactor is 0.1-30%; the mol ratio of chloropropene to hydrogen peroxide is 1-8: 1;
the chloropropene mass concentration is more than 98%, the hydrogen peroxide aqueous solution mass concentration is 27% -70%, and the mass ratio of the solvent methanol to the chloropropene is 0.1-5: 1;
the raw materials of the method also comprise an additive M2CO3Or MHCO3M is K+、Na+、NH4 +。
Advantageous effects
(1) The device provided by the invention has the characteristics of simple process flow, no need of separation of the catalyst, low requirement on mechanical strength of the catalyst, high effective utilization rate of hydrogen peroxide and high yield of epoxy chloropropane, and can be used in industrial production.
(2) The catalyst can be arranged in the separation tank, namely the titanium silicalite molecular sieve catalyst is added into the separation tank at one time and enters the tubular reactor through a slurry outlet at the bottom of the separation tank. The catalyst is not required to be recovered in the continuous production process, and the gas phase part is condensed and refluxed by a condenser at the top of the buffer tank.
Drawings
FIG. 1 is a schematic flow chart of the process for producing epichlorohydrin according to the present invention; wherein: 1. a tubular reactor, 2, a separation tank, 3, a reaction circulating pump, 4, a feeding pump, 5, a mixer, 6, a filter, 7 and a condenser.
The invention will be further described with reference to specific examples, but the scope of the invention is not limited to the examples.
Detailed Description
The catalyst used in the utility model is a titanium silicalite molecular sieve catalyst prepared by the method disclosed in 201711344416.5. The catalyst is synthesized by using a novel method which can inhibit the generation of amorphous six-coordinate non-skeleton titanium on TS-1 and can control the grain size to a certain extent, and the grain size is controlled by the method within a certain range.
Comparative example 1
The epichlorohydrin production process shown in figure 1 is carried out. 40kg of titanium silicalite molecular sieve catalyst is added into a separation tank 2 at one time, reaction raw materials of chloropropene, aqueous hydrogen peroxide and solvent methanol are respectively conveyed into a mixer 5 through a feed pump 4, the raw material mixed liquid is in a homogeneous phase state, and the reaction is carried out in a tubular reactor 1. When the reaction temperature reaches 35 ℃ and the pressure of the separation tank reaches 0.8MPa, continuous production is started. The mol ratio of chloropropene to hydrogen peroxide is 4: 1, the catalyst weight solids content is 10%, the feed rate is 5L/h, and the stirring speed of the mixer 5 is 250 rpm.
The reaction material is filtered to obtain clear liquid containing products through a filter 6 arranged in a separation tank 2, and the slurry containing the catalyst and the raw materials in the raw material proportioning tank which are not filtered are pumped into the tubular reactor 1 through a reaction circulating pump 3. In the continuous production process, the catalyst is not required to be recovered, and the gas phase part is condensed and refluxed by a condenser 7 at the top of the knockout drum 2. The reaction is exothermic reaction, and the jacketed heat exchange layers are arranged outside the condenser and the tubular reactor, and can exchange heat and take away heat generated by the reaction, so that the reaction temperature can be kept in a stable state.
The reaction was continued for 1000 hours, and the separated clear solution was analyzed to obtain the selectivity of epichlorohydrin and the conversion of hydrogen peroxide, as shown in table 1.
Table 1 partial reaction conditions and reaction results of comparative examples
Figure DEST_PATH_GDA0002679237010000031
Figure DEST_PATH_GDA0002679237010000041
Example 1
The epichlorohydrin production process shown in figure 1 is carried out. 40kg of titanium silicalite molecular sieve catalyst is added into a separation tank 2 at one time, reaction raw materials of chloropropene, aqueous hydrogen peroxide and solvent methanol are respectively conveyed into a mixer 5 through a feed pump 4, the raw material mixed liquid is in a homogeneous phase state, and the reaction is carried out in a tubular reactor 1. When the reaction temperature reaches 35 ℃ and the pressure of the separation tank reaches 0.8MPa, continuous production is started. The mol ratio of chloropropene to hydrogen peroxide is 4: 1, solid content of catalyst 10% by weight, additive (NH)4)2CO3The amount of (B) was 15ppm based on the amount of the mixed solution, the feed rate was 5L/h, and the stirring speed of the mixer 5 was 250 rpm.
The reaction material is filtered to obtain clear liquid containing products through a filter 6 arranged in a separation tank 2, and the slurry containing the catalyst and the raw materials in the raw material proportioning tank which are not filtered are pumped into the tubular reactor 1 through a reaction circulating pump 3. In the continuous production process, the catalyst is not required to be recovered, and the gas phase part is condensed and refluxed by a condenser 7 at the top of the knockout drum 2. The reaction is exothermic reaction, and the jacketed heat exchange layers are arranged outside the condenser and the tubular reactor, and can exchange heat and take away heat generated by the reaction, so that the reaction temperature can be kept in a stable state.
The reaction was continued for 1000 hours, and the separated clear solution was analyzed to obtain the selectivity of epichlorohydrin and the conversion of hydrogen peroxide, as shown in table 2.
Table 2 part of the reaction conditions and the results of the reaction of example 1
Figure DEST_PATH_GDA0002679237010000042
Figure DEST_PATH_GDA0002679237010000051
As can be seen from Table 2, additive (NH)4)2CO3The addition of the catalyst can improve the activity of the catalyst, the continuous reaction lasts for 1000 hours, the selectivity of the epichlorohydrin is kept about 98 percent, the highest value reaches 99.0 percent, and the selectivity is slightly improved compared with the case without the additive; the conversion rate of the hydrogen peroxide is kept about 96 percent, and the maximum value reaches 96.4 percent.
Example 2
The epichlorohydrin production process shown in figure 1 is carried out. 40kg of titanium silicalite molecular sieve catalyst is added into a separation tank 2 at one time, reaction raw materials of chloropropene, aqueous hydrogen peroxide and solvent methanol are respectively conveyed into a raw material mixer 5 through a metering pump, the raw material mixed liquid is in a homogeneous phase state, and the reaction is carried out in a tubular reactor 1. When the reaction temperature reaches 35 ℃ and the pressure of the separation tank reaches 0.8MPa, continuous production is started. The mol ratio of chloropropene to hydrogen peroxide is 3: 1, solid content of catalyst 10% by weight, additive (NH)4)2CO3The feed rate was 5L/h, and the stirring speed of the mixer 5 was 300 rpm.
The reaction materials are filtered to obtain clear liquid containing products through a filter 6 arranged in a separation tank 2, and slurry which is not filtered and contains catalyst and is not completely reacted and raw materials in a raw material proportioning tank are pumped into the first tubular reactor 1 through a reaction circulating pump 3. In the continuous production process, the catalyst is not required to be recovered, and the gas phase part is condensed and refluxed by a condenser 7 at the top of the slow separation tank 2. The reaction is exothermic reaction, and the jacketed heat exchange layers are arranged outside the condenser and the tubular reactor, and can exchange heat and take away heat generated by the reaction, so that the reaction temperature can be kept in a stable state.
The reaction was continued for 1000 hours, and the separated clear solution was analyzed to obtain the selectivity of epichlorohydrin and the conversion of hydrogen peroxide, as shown in table 3.
Table 3 part of the reaction conditions and the results of the reaction of example 2
Figure DEST_PATH_GDA0002679237010000052
Figure DEST_PATH_GDA0002679237010000061

Claims (7)

1. A device for continuously producing epichlorohydrin by oxidizing chloropropene with a titanium silicalite molecular sieve is characterized by comprising a mixer, a tubular reactor, a separation tank and a filter; the bottom of the separation tank is provided with a slurry outlet; a clear liquid discharge hole is formed in the upper part of the separation tank; the filter is arranged at the clear liquid outlet; the outlet of the mixer is communicated with the feed inlet of the tubular reactor through a pipeline; and the outlet of the tubular reactor is communicated with the feed inlet of the separation tank.
2. The apparatus of claim 1, wherein the slurry outlet of the knockout drum is in communication with the inlet of the pipe reactor.
3. The apparatus of claim 1, further comprising a condenser; the condenser is arranged at the top of the separation tank.
4. The apparatus of claim 1, wherein the tubular reactor is a metal hollow tube with smooth inner wall, inner diameter of 10-500mm and length of 1-100 m.
5. The apparatus of claim 1, wherein the filter is a ceramic membrane filter or a polytetrafluro filter, and the pore size of the filter is 2-10 μm smaller than the particle size of the catalyst; the filter is connected with the clear liquid discharge port in a detachable pipeline manner.
6. The device of claim 1, wherein said filter is a teflon filter element; the pores of the polytetrafluoroethylene filter cores are 1-50 microns, the filter consists of 1-100 polytetrafluoroethylene filter cores, and the polytetrafluoroethylene filter cores are solid cylindrical.
7. The apparatus of claim 3 wherein the condenser and the tubular reactor are each externally provided with a jacketed heat exchange layer.
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CN115197171A (en) * 2021-04-13 2022-10-18 中国石油化工股份有限公司 Method and system for producing propylene oxide
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CN101747297B (en) * 2008-12-22 2011-11-02 中国石油化工股份有限公司 Method for continuously producing epoxy chloropropane
CN101747296B (en) * 2008-12-22 2011-11-02 中国石油化工股份有限公司 Production method of epoxy chloropropane
CN102093313A (en) * 2010-12-21 2011-06-15 湘潭大学 Method for preparing epoxy chloropropane
CN103159703B (en) * 2011-12-16 2014-09-03 中国科学院大连化学物理研究所 Method of continuously producing epichlorohydrin by directly epoxidizing chloropropene
JP2013082678A (en) * 2012-07-23 2013-05-09 Sumitomo Chemical Co Ltd Method and device for catalytic vapor-phase oxidation of propylene
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CN109912541B (en) * 2019-02-26 2022-08-30 山东凯泰科技股份有限公司 Continuous industrial production method for directly producing ECH (ethylene-co-olefin) by using phase transfer catalyst

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