CN111925273B - Production method of high-purity cis-1-chloro-3, 3, 3-trifluoropropene - Google Patents

Production method of high-purity cis-1-chloro-3, 3, 3-trifluoropropene Download PDF

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CN111925273B
CN111925273B CN202011099733.7A CN202011099733A CN111925273B CN 111925273 B CN111925273 B CN 111925273B CN 202011099733 A CN202011099733 A CN 202011099733A CN 111925273 B CN111925273 B CN 111925273B
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trifluoropropene
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CN111925273A (en
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庆飞要
郭勤
张呈平
贾晓卿
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Shaanxi Yuji New Material Technology Co.,Ltd.
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Beijing Yuji Science and Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/125—Halogens; Compounds thereof with scandium, yttrium, aluminium, gallium, indium or thallium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/132—Halogens; Compounds thereof with chromium, molybdenum, tungsten or polonium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/138—Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/35—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction
    • C07C17/358—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction by isomerisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
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    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
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    • C07B2200/09—Geometrical isomers

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Abstract

The invention discloses a production method of high-purity cis-1-chloro-3, 3, 3-trifluoropropene, which comprises the steps of separating and purifying mixed gas generated by fluorinating 1,1,1,3, 3-pentachloropropane to obtain trans-1-chloro-3, 3, 3-trifluoropropene, then obtaining cis-trans mixed products through catalytic isomerization reaction, and separating and purifying again to obtain the high-purity cis products. The invention adopts metal fluorine chloride or fluorine chlorine oxide as an isomerization catalyst, separates components in mixed gas step by step, and realizes the production of high-purity cis-form products by adopting a method of combining rectification and adsorption. The method has the characteristics of high reaction conversion rate, good selectivity, easy control of reaction and the like in the isomerization reaction stage, and has the characteristics of high product purity, thorough separation and the like in the separation and purification process; the whole method has simple process flow operation and low requirement on equipment, can continuously and stably run, and is suitable for industrial large-scale production and application.

Description

Production method of high-purity cis-1-chloro-3, 3, 3-trifluoropropene
Technical Field
The invention relates to a method for producing a high-purity product Z-1-chloro-3, 3, 3-trifluoropropene (HCFO-1233 zd (Z)) in a gas phase, in particular to a method for producing HCFO-1233zd (Z)) by using E-1-chloro-3, 3, 3-trifluoropropene (HCFO-1233 zd (E)) as a raw material and carrying out isomerization reaction in the presence of a metal chlorofluoride or metal chlorofluoroxide catalyst, and separating, purifying and collecting the generated mixed gas to obtain the high-purity product HCFO-1233zd (Z).
Background
1-chloro-3, 3, 3-trifluoropropene (hereinafter referred to as "1233 zd") is recognized as an environmentally friendly CFC substitute, and has a wide range of uses. US2008/0098755 and US 2008/0207788 and US 6362383 report examples of the use of 1233zd as a heat transfer medium, refrigerant and solvent, respectively.
1233zd there are two isomers (E) and (Z) with different physical properties. For example, E-1233zd has a boiling point of 19 ℃ and Z-1233zd has a boiling point of 38 ℃. In practice, it is desirable to use pure E-1233zd, pure Z-1233zd, a mixture of the (E) and (Z) isomers in specific ratios, or a mixture of one or both with one or more additional compounds in order to control solution properties. In applications where higher boiling points are desired, pure HCFO-1233zd (Z) may be a more desirable material.
Currently, HCFO-1233zd (Z) is produced by HCFO-1233zd (E) or 2-chloro-3, 3, 3-trifluoropropene (HCFO-1233 xf) isomerization. HCFO-1233xf via CrF is reported in patent US2013/3106143The isomerization reaction was catalyzed and the collected feed components included 49.9% HCFO-1233xf, 32.5% HCFO-1233zd (E), and 16.2% HCFO-1233zd (Z). The raw materials of the route are not easy to obtain, and the selectivity of the reaction is low. AlF is reported in patent CN102245548B3As a catalyst, the yield of HCFO-1233zd (Z) was 10.8% at 300 ℃; fluorinated Cr is also reported2O3As a catalyst, when operated at 250 ℃ for 10 hours, the conversion of HCFO-1233zd (E) was 9.59%, the selectivity of HCFO-1233zd (Z) was 90.6%, and when operated at 300 ℃ for 10 hours, the conversion of HCFO-1233zd (E) was 12.55%, and the selectivity of HCFO-1233zd (Z) was 80.6%. Patent CN108689796 reports that HCFO-1233zd (E) is isomerized at 450 ℃ at high temperature, the conversion rate can reach 14% at most, and the selectivity is 95-97%. In patent CN 104603089B, Cl is reported2In the presence of the catalyst, the HCFO-1233zd (E) is subjected to isomerization reaction to generate HCFO-1233zd (Z), and the conversion rate is 13-16% and the selectivity is about 91% in the temperature range of 350-450 ℃.
The high-temperature isomerization in the above route does not adopt a catalyst, but the reaction temperature is higher (350-(ii) a By using AlF3Or fluorinated Cr2O3Catalyzing isomerization of HCFO-1233zd (E) to HCFO-1233zd (Z), with the disadvantage of lower selectivity for HCFO-1233zd (Z); the chlorine gas is adopted to generate Cl free radical to promote the isomerization of HCFO-1233zd (E), the reaction temperature is higher, the HCFO-1233zd (Z) has the defect of poor selectivity, and strong corrosion and high toxicity Cl is used2As a reaction raw material, it is not favorable for safe operation of the reaction.
In addition, few reports on the separation and purification of HCFO-1233zd (Z) exist at present, and particularly, no relevant report on the separation and purification method for realizing the production of HCFO-1233zd (Z) high-purity products exists. Chinese patent CN105189421 reports that in the process of preparing HCFO-1233zd (Z) by HCFO-1233zd (E) gas phase isomerization, the enrichment of HCFO-1233zd (Z) at the bottom of reactor is realized by using reactive distillation, and its purity can be up to 90-95%, and still has need of further separation and purification.
Therefore, the production method of the HCFO-1233zd (Z) product, which has the advantages of easy acquisition of raw materials, high conversion rate, good selectivity, easy control of reaction, convenient operation, simple process, safety, reliability, stable and continuous operation and high product purity, is provided, is particularly important, and has excellent application and market prospects.
Disclosure of Invention
The invention aims to solve the technical problems of overcoming the defects of the preparation technology of HCFO-1233zd (Z) in the background, filling the blank of the existing separation and purification of HCFO-1233zd (Z), and providing the production method of the HCFO-1233zd (Z) product, which has the advantages of easy acquisition of raw materials, high conversion rate, good selectivity, easy control of reaction, convenient operation, simple process, safety, reliability, stable and continuous operation and high product purity.
A method for producing a HCFO-1233zd (z) high purity product comprising the steps of:
(1) in the presence of a fluorination catalyst, carrying out gas-phase fluorination reaction on 1,1,1,3, 3-pentachloropropane (HCC-240 fa) in a fluorination reactor to generate HCFO-1233zd (E) crude product;
(2) separating light-component impurities of 1,3,3, 3-tetrafluoropropene and HCl from the crude product of HCFO-1233zd (E) through the top of a first degassing tower;
(3) the raw material in the tower bottom of the first degassing tower enters a first rectifying tower for rectification, HCFO-1233zd (E) and part of HF are extracted from the tower top, and unreacted HCC-240fa is recycled from the tower bottom to participate in the reaction;
(4) the tower top produced material of the first rectifying tower passes through an HF separation tank, and HF components in the material produced at the top of the first rectifying tower are separated or circulated by a sulfuric acid absorption or phase separation method;
(5) in the presence of an isomerization catalyst, HCFO-1233zd (E) obtained by an HF separation tank is subjected to isomerization reaction in an isomerization reactor to generate HCFO-1233zd (Z) crude product;
(6) separating 1,3,3, 3-tetrafluoropropene, HCFO-1233zd (E) and HF light components from the crude HCFO-1233zd (Z) through the top of a second degassing tower, and recycling unreacted HCFO-1233zd (E) to continuously participate in isomerization reaction;
(7) the raw material in the tower bottom of the second degassing tower enters a second rectifying tower for rectification, and the HCFO-1233zd (Z) product is collected from the tower top, wherein the content of organic impurities is controlled below 0.1%;
(8) the HCFO-1233zd (Z) product collected from the top of the rectification tower is treated by an adsorption tower to remove water and inorganic acid in the product.
The isomerization catalyst is at least one or more of aluminum fluorochloride, magnesium fluorochloride, chromium fluorochloride and chromium fluorochloride.
The preparation method of the isomerization catalyst comprises the following steps of; dissolving metal soluble salt in water, dropwise adding concentrated ammonia water for precipitation, adjusting pH value to 7.5, aging for 12 hours, washing with water, filtering, and drying in an oven at 80-150 deg.C for 12-48 hours; then roasting for 5-20 hours at the temperature of 300-500 ℃ under the protection of nitrogen; and finally, at the temperature of 300 ℃ and 500 ℃, introducing the substances in a mass ratio of 1: 4, activating the mixed gas consisting of the halogenated methane and the nitrogen for 4 to 20 hours, and stopping introducing the mixed gas to prepare metal fluorochlorides or metal fluorochloroxyls; wherein the metal soluble salt is at least one or more of chlorides or nitrates of Al, Mg, Cr, Fe, Co, Ni and Zn, and the halogenated methane is one or more of difluorodichloromethane, chlorodifluoromethane and dichlorofluoromethane.
The preparation method of the isomerization catalyst comprises the following steps of; dissolving metal soluble salt in water, dropwise adding concentrated ammonia water for precipitation, adjusting the pH value to 7.5, then aging for 12 hours, washing with water, filtering, and drying in an oven at 120 ℃ for 12 hours; then roasting for 12 hours at 350 ℃ under the protection of nitrogen; finally, at the temperature of 400 ℃, the mass ratio of the introduced substances is 1: 4, activating the mixed gas consisting of the halogenated methane and the nitrogen for 6 hours, and stopping introducing the mixed gas to prepare metal fluorochlorides or metal fluorochloroxyls; wherein the metal soluble salt is at least one or more of chloride or nitrate of Cr, Al, Mg, Fe and Zn, and the halogenated methane is one or more of difluorodichloromethane, chlorodifluoromethane and dichlorofluoromethane.
The isomerization reaction conditions are as follows: in the presence of an isomerization catalyst, the reaction pressure is 0.01-0.5MPa, the reaction temperature is 150-350 ℃, and the contact time of the E-1-chloro-3, 3, 3-trifluoropropene is 20-100 s.
The isomerization reaction conditions are as follows: in the presence of a catalyst, the reaction pressure is 0.1-0.5MPa, the reaction temperature is 200-300 ℃, and the contact time of the E-1-chloro-3, 3, 3-trifluoropropene is 20-70 s.
The first degassing tower is filled with ceramic rings, glass springs, wire meshes, Raschig rings, metal pall rings or metal structured packing, the working pressure of the degassing tower is 0.2-0.4 MPa, the temperature of a tower kettle is 70-90 ℃, the temperature of circulating cooling water at the top of the tower is 5-25 ℃, and the temperature at the top of the tower is 30-40 ℃.
The first rectifying tower is filled with metal Intel rock filler, metal pall ring filler or metal regular filler, the working pressure of the rectifying tower is 0.1-0.3 MPa, the temperature of the tower kettle is preferably 70-90 ℃, the temperature of circulating cooling water at the top of the tower is 5-25 ℃, and the temperature at the top of the tower is 45-55 ℃.
The packing of the second degassing tower is ceramic ring, glass spring, metal wire mesh, Raschig ring, metal pall ring or metal regular packing, the working pressure of the degassing tower is 0.2-0.4 MPa, the temperature of the tower kettle is 75-95 ℃, the temperature of the circulating cooling water at the top of the tower is 5-35 ℃, and the temperature at the top of the tower is 30-50 ℃.
The working pressure of the second degassing tower is preferably 0.2-0.3MPa, the temperature of the tower bottom is more preferably 75-85 ℃, the temperature of circulating cooling water at the tower top is preferably 15-35 ℃, and the temperature of the tower top is preferably 40-50 ℃.
The second rectifying tower is filled with metal Intel rock filler, metal pall ring filler or metal regular filler, the working pressure of the rectifying tower is 0.1-0.3 MPa, the temperature of the tower kettle is 60-80 ℃, the temperature of circulating cooling water at the top of the tower is 5-35 ℃, and the temperature at the top of the tower is 50-70 ℃.
The working pressure of the second rectifying tower is preferably 0.1-0.2MPa, the temperature of the tower kettle is preferably 60-70 ℃, the temperature of circulating cooling water at the top of the tower is more preferably 15-35 ℃, and the temperature at the top of the tower is 50-60 ℃.
The filler of the adsorption tower is preferably an A-type molecular sieve, activated carbon, silica gel or activated alumina, and the working pressure of the adsorption tower is preferably 0.05-0.15 MPa.
The adsorption tower packing is more preferably a type a molecular sieve.
The isomerization catalyst used in the present invention, metal fluorochlorides or metal fluorochlorohlorides, can be obtained by controlling the flow rate of methyl halide and the activation time and temperature of the catalyst. For example, increasing the flow rate of methyl halide, extending the activation time, and increasing the activation temperature all favor the formation of metal fluorochlorides; the reduction of the flow rate of the halogenated methane, the shortening of the activation time and the slight reduction of the activation temperature are all beneficial to the generation of the metal fluorine-chlorine oxide.
The separation and purification process of the HCFO-1233zd (Z) crude product adopted by the invention can efficiently separate organic or inorganic impurities such as 1,3,3, 3-tetrafluoropropene, pentafluoropropane, water, acid and the like from the crude product to obtain the HCFO-1233zd (Z) product with the purity of more than 99.9%, and is beneficial to subsequent isomerization conversion and purification after isomerization.
The invention has the advantages that: the technical method for producing the HCFO-1233zd (Z) product provided by the invention has the advantages of easily obtained raw materials, high reaction conversion rate, good selectivity and easily controlled reaction, can realize stable and continuous operation, and is suitable for industrial large-scale production of the HCFO-1233zd (Z) high-purity product.
Drawings
FIG. 1 is a flow chart of a production process of a high-purity cis-1-chloro-3, 3, 3-trifluoropropene product.
Detailed Description
The invention will be further described in the following with reference to the accompanying drawings and examples, which are not intended to limit the invention, but which may be modified and varied by those skilled in the art in accordance with the spirit of the invention, the scope and spirit of the invention being indicated by the appended claims.
The raw material E-1-chloro-3, 3, 3-trifluoropropene can be prepared according to the methods provided by Chinese patents CN100361944C and CN102211974B, namely, carbon tetrachloride and chloroethylene undergo telomerization to obtain HCC-240 fa; then obtaining E-1-chloro-3, 3, 3-trifluoropropene (HCFO-1233 zd (E)) through fluorine-chlorine exchange reaction and dehydrochlorination reaction, namely obtaining HCFO-1233zd (E) crude product in the step (1) of the following steps.
A method for producing a HCFO-1233zd (z) high purity product comprising the steps of:
(1) in the presence of a fluorination catalyst, carrying out gas-phase fluorination reaction on 1,1,1,3, 3-pentachloropropane (HCC-240 fa) in a fluorination reactor to generate HCFO-1233zd (E) crude product;
(2) separating light-component impurities of 1,3,3, 3-tetrafluoropropene and HCl from the crude product of HCFO-1233zd (E) through the top of a first degassing tower;
(3) the raw material in the tower bottom of the first degassing tower enters a first rectifying tower for rectification, HCFO-1233zd (E) and part of HF are extracted from the tower top, and unreacted HCC-240fa is recycled from the tower bottom to participate in the reaction;
(4) the tower top produced material of the first rectifying tower passes through an HF separation tank, and HF components in the material produced at the top of the first rectifying tower are separated or circulated by a sulfuric acid absorption or phase separation method;
(5) in the presence of an isomerization catalyst, HCFO-1233zd (E) obtained by an HF separation tank is subjected to isomerization reaction in an isomerization reactor to generate HCFO-1233zd (Z) crude product;
(6) separating 1,3,3, 3-tetrafluoropropene, HCFO-1233zd (E) and HF light components from the crude HCFO-1233zd (Z) through the top of a second degassing tower, and recycling unreacted HCFO-1233zd (E) to continuously participate in isomerization reaction;
(7) the raw material in the tower bottom of the second degassing tower enters a second rectifying tower for rectification, and the HCFO-1233zd (Z) product is collected from the tower top, wherein the content of organic impurities is controlled below 0.1%;
(8) the HCFO-1233zd (Z) product collected from the top of the rectification tower is treated by an adsorption tower to remove water and inorganic acid in the product.
Example 1
Introducing the HCFO-1233zd (E) crude product into a first degassing tower, wherein the filler is a metal pall ring, the pressure of the first degassing tower is 0.30MPa, the temperature of a tower kettle is 80 ℃, the temperature of circulating cooling water at the top of the tower is 20 ℃, the temperature of the top of the tower is 38 ℃, light components in the HCFO-1233zd (E) crude product are extracted from the top of the first degassing tower and enter a front fraction tank, and the content of the light components in the tower kettle material is 0.03%. The material in the first degassing tower enters a first rectifying tower, the filler is a metal pall ring, the pressure of the first rectifying tower is 0.20MPa, the temperature of the tower bottom is 82 ℃, the temperature of circulating cooling water at the top of the tower is 20 ℃, the temperature at the top of the tower is 54 ℃, HCFO-1233zd (E) and HF components are extracted from the top of the tower, and the GC analysis purity is 99.6%. The material extracted from the top of the first rectifying tower passes through an HF absorption tank to separate HF components by concentrated sulfuric acid, and the content of HF in the product HCFO-1233zd (E) is controlled at 9.2 ppm. And unreacted raw material HCC-240fa in the tower bottom of the first rectifying tower is recycled.
Example 2
Introducing the HCFO-1233zd (E) crude product into a first degassing tower, wherein the filler is a metal pall ring, the pressure of the first degassing tower is 0.30MPa, the temperature of a tower kettle is 80 ℃, the temperature of circulating cooling water at the top of the tower is 20 ℃, the temperature of the top of the tower is 40 ℃, light components in the HCFO-1233zd (E) crude product are extracted from the top of the first degassing tower and enter a front fraction tank, and the content of the light components in the tower kettle material is 0.03%. The material in the first degassing tower enters a first rectifying tower, the filler is a metal pall ring, the pressure of the first rectifying tower is 0.22MPa, the temperature of the tower bottom is 82 ℃, the temperature of circulating cooling water at the top of the tower is 20 ℃, the temperature at the top of the tower is 55 ℃, HCFO-1233zd (E) and HF components are extracted from the top of the tower, and the GC analysis purity is 99.8%. The material extracted from the top of the first rectifying tower passes through an HF absorption tank to separate HF components by concentrated sulfuric acid, and the content of HF in the product HCFO-1233zd (E) is controlled to be 8.7 ppm. And unreacted raw material HCC-240fa in the tower bottom of the first rectifying tower is recycled.
Example 3
Introducing the HCFO-1233zd (E) crude product into a first degassing tower, wherein the filler is a metal pall ring, the pressure of the first degassing tower is 0.28MPa, the temperature of a tower kettle is 81 ℃, the temperature of circulating cooling water at the top of the tower is 25 ℃, the temperature of the top of the tower is 37 ℃, light components in the HCFO-1233zd (E) crude product are extracted from the top of the first degassing tower and enter a front fraction tank, and the content of the light components in the tower kettle material is 0.03%. The material in the first degassing tower enters a first rectifying tower, the filler is a metal structured filler, the pressure of the first rectifying tower is 0.20MPa, the temperature of the tower bottom is 81 ℃, the temperature of circulating cooling water at the top of the tower is 25 ℃, the temperature at the top of the tower is 54 ℃, HCFO-1233zd (E) and HF components are extracted from the top of the tower, and the GC analysis purity is 99.8%. The material extracted from the top of the first rectifying tower passes through an HF absorption tank to separate HF components by concentrated sulfuric acid, and the content of HF in the product HCFO-1233zd (E) is controlled to be 8.1 ppm. And unreacted raw material HCC-240fa in the tower bottom of the first rectifying tower is recycled.
The preparation method of the isomerization catalyst comprises the following steps: dissolving metal soluble salt in water, adding concentrated ammonia water for precipitation, adjusting pH value to 7.5, aging for 12 hours, washing with water, filtering, and drying in an oven at 120 ℃ for 12 hours; then roasting for 10 hours at 350 ℃ under the protection of nitrogen; finally, at the temperature of 400 ℃, the mass ratio of the introduced substances is 1: 4 and reducing the nitrogen proportion gradually until the nitrogen proportion is 0, and obtaining the metal chlorofluoride or the metal chlorofluoroxy compound after 72 hours of activation. Wherein the metal soluble salt is chloride of Cr, Al, Mg, Fe and Zn.
Example 4
A800L tubular reactor was charged with 750L of AlF, an isomerization catalyst prepared as described abovexCly（x>0,y>0, and x + y = 3) or AlFmClnOp（m>0,n>0,p>0, and m + n +2p = 3). The reaction conditions are as follows: the reaction temperature was 270 ℃, the contact time of HCFO-1233zd (E) was 60s, and the reaction pressure was 0.25 MPa. And (4) taking gas phase samples at an inlet and an outlet of the reactor for GC analysis. The reaction result is: conversion of HCFO-1233zd (E) was 12.5%, selectivity to Z-1-chloro-3, 3, 3-trifluoropropene was 97.1%, and selectivity to E-1,3,3, 3-tetrafluoropropene was 97.1%The content was 1.5%.
Example 5
A800L tubular reactor was charged with 750L of AlF, an isomerization catalyst prepared as described abovexCly（x>0,y>0, and x + y = 3) or AlFmClnOp（m>0,n>0,p>0, and m + n +2p = 3). The reaction conditions are as follows: the reaction temperature is 270 ℃, the contact time of the HCFO-1233zd (E) is 60s, and the reaction pressure is 0.30 MPa. And (4) taking gas phase samples at an inlet and an outlet of the reactor for GC analysis. The reaction result is: the conversion of HCFO-1233zd (E) was 13.1%, the selectivity to Z-1-chloro-3, 3, 3-trifluoropropene was 96.5%, and the selectivity to E-1,3,3, 3-tetrafluoropropene was 1.8%.
Example 6
A800L tubular reactor was charged with 750L of AlF, an isomerization catalyst prepared as described abovexCly（x>0,y>0, and x + y = 3) or AlFmClnOp（m>0,n>0,p>0, and m + n +2p = 3). The reaction conditions are as follows: the reaction temperature is 290 ℃, the contact time of the HCFO-1233zd (E) is 60s, and the reaction pressure is 0.33 MPa. And (4) taking gas phase samples at an inlet and an outlet of the reactor for GC analysis. The reaction result is: the conversion of HCFO-1233zd (E) was 14.2%, the selectivity to Z-1-chloro-3, 3, 3-trifluoropropene was 95.8%, and the selectivity to E-1,3,3, 3-tetrafluoropropene was 2.3%.
Example 7
A800L tubular reactor was charged with 750L of AlF, an isomerization catalyst prepared as described abovexCly（x>0,y>0, and x + y = 3) or AlFmClnOp（m>0,n>0,p>0, and m + n +2p = 3). The reaction conditions are as follows: the reaction temperature was 270 ℃, the contact time of HCFO-1233zd (E) was 30s, and the reaction pressure was 0.33 MPa. And (4) taking gas phase samples at an inlet and an outlet of the reactor for GC analysis. The reaction result is: the conversion of HCFO-1233zd (E) was 12.2%, the selectivity to Z-1-chloro-3, 3, 3-trifluoropropene was 98.1%, and the selectivity to E-1,3,3, 3-tetrafluoropropene was 1.2%.
Example 8
A800L tubular reactor was charged with 750L of AlF, an isomerization catalyst prepared as described abovexCly（x>0,y>0, and x + y = 3) or AlFmClnOp（m>0,n>0,p>0, and m + n +2p = 3). The reaction conditions are as follows: the reaction temperature is 290 ℃, the contact time of the HCFO-1233zd (E) is 30s, and the reaction pressure is 0.32 MPa. And (4) taking gas phase samples at an inlet and an outlet of the reactor for GC analysis. The reaction result is: the conversion of HCFO-1233zd (E) was 13.3%, the selectivity to Z-1-chloro-3, 3, 3-trifluoropropene was 97.9%, and the selectivity to E-1,3,3, 3-tetrafluoropropene was 2.0%.
Example 9
Introducing the HCFO-1233zd (Z) crude product into a second degassing tower, wherein the filler is a metal pall ring, the pressure of the second degassing tower is 0.25MPa, the temperature of a tower kettle is 80 ℃, the temperature of circulating cooling water at the top of the tower is 25 ℃, the temperature of the top of the tower is 45 ℃, light components in the HCFO-1233zd (Z) crude product are extracted from the top of the degassing tower and enter a front fraction tank, and the content of the light components in the tower kettle material is 0.03%. The material in the degassing tower enters a second rectifying tower, the filler is a metal pall ring, the pressure of the second rectifying tower is 0.12MPa, the temperature of the tower bottom is 65 ℃, the temperature of circulating cooling water at the top of the tower is 25 ℃, the temperature of the top of the tower is 55 ℃, and HCFO-1233zd (Z) pure product is extracted from the top of the rectifying tower, and the purity is 99.9%.
Example 10
Introducing the HCFO-1233zd (Z) crude product into a second degassing tower, wherein the filler is a metal pall ring, the pressure of the second degassing tower is 0.27MPa, the temperature of a tower kettle is 82 ℃, the temperature of circulating cooling water at the top of the tower is 25 ℃, the temperature of the top of the tower is 50 ℃, light components in the Z-1233zd crude product are extracted from the top of the degassing tower and enter a front fraction tank, and the content of the light components in the tower kettle material is 0.02%. The material in the degassing tower enters a second rectifying tower, the filler is a metal pall ring, the pressure of the second rectifying tower is 0.10MPa, the temperature of the tower bottom is 66 ℃, the temperature of circulating cooling water at the top of the tower is 25 ℃, the temperature of the top of the tower is 60 ℃, and HCFO-1233zd (Z) pure product is extracted from the top of the rectifying tower, and the purity is 99.9%.
Example 11
Introducing the HCFO-1233zd (Z) crude product into a second degassing tower, wherein the filler is a metal pall ring, the pressure of the second degassing tower is 0.24MPa, the temperature of a tower kettle is 78 ℃, the temperature of circulating cooling water at the top of the tower is 20 ℃, the temperature of the top of the tower is 48 ℃, light components in the Z-HCFO-1233zd (Z) crude product are extracted from the top of the degassing tower and enter a front fraction tank, and the content of the light components in the tower kettle material is 0.03%. The material in the degassing tower enters a second rectifying tower, the filler is a metal pall ring, the pressure of the second rectifying tower is 0.12MPa, the temperature of the tower bottom is 66 ℃, the temperature of circulating cooling water at the top of the tower is 20 ℃, the temperature of the top of the tower is 59 ℃, and the purity of HCFO-1233zd (Z) is extracted from the top of the rectifying tower, and the purity is 99.9%.
Example 12
Introducing the HCFO-1233zd (Z) crude product into a second degassing tower, wherein the filler is a wire mesh, the pressure of the second degassing tower is 0.25MPa, the temperature of the tower bottom is 83 ℃, the temperature of circulating cooling water at the top of the tower is 24 ℃, the temperature of the top of the tower is 50 ℃, light components in the HCFO-1233zd (Z) crude product are extracted from the top of the degassing tower and enter a front fraction tank, and the content of the light components in the tower bottom material is 0.01%. The material in the degassing tower enters a second rectifying tower, the filler is a metal pall ring, the pressure of the second rectifying tower is 0.11MPa, the temperature of the tower bottom is 64 ℃, the temperature of the circulating cooling water at the top of the tower is 24 ℃, the temperature at the top of the tower is 56 ℃, and the HCFO-1233zd (Z) pure product is extracted from the top of the rectifying tower, and the purity is 99.9%.

Claims (5)

1. A method for producing a high-purity Z-1-chloro-3, 3, 3-trifluoropropene product, comprising the steps of:
(1) in the presence of a fluorination catalyst, carrying out gas-phase fluorination reaction on 1,1,1,3, 3-pentachloropropane in a fluorination reactor to generate a crude product of E-1-chloro-3, 3, 3-trifluoropropene;
(2) separating light component impurities of 1,3,3, 3-tetrafluoropropene and HCl from the crude product of E-1-chloro-3, 3, 3-trifluoropropene through the top of a first degassing tower;
(3) the raw material in the tower bottom of the first degassing tower enters a first rectifying tower for rectification, the E-1-chloro-3, 3, 3-trifluoropropene and part of HF are extracted from the tower top, and the unreacted 1,1,1,3, 3-pentachloropropane is recycled from the tower bottom to participate in the reaction;
(4) the tower top produced material of the first rectifying tower passes through an HF separation tank, and HF components in the material produced at the top of the first rectifying tower are separated or circulated by a sulfuric acid absorption or phase separation method;
(5) in the presence of an isomerization catalyst, carrying out isomerization reaction on E-1-chloro-3, 3, 3-trifluoropropene obtained by an HF separation tank in an isomerization reactor to generate a Z-1-chloro-3, 3, 3-trifluoropropene crude product;
(6) separating light components of the Z-1-chloro-3, 3, 3-trifluoropropene crude product, the E-1-chloro-3, 3, 3-trifluoropropene and the HF from the crude product through the top of a second degassing tower, wherein unreacted E-1-chloro-3, 3, 3-trifluoropropene circularly and continuously participates in the isomerization reaction;
(7) the raw material in the tower kettle of the second degassing tower enters a second rectifying tower for rectification, and the Z-1-chloro-3, 3, 3-trifluoropropene product is collected from the tower top, wherein the content of organic impurities is controlled to be below 0.1%;
(8) the Z-1-chloro-3, 3, 3-trifluoropropene product collected at the top of the rectifying tower is treated by an adsorption tower to remove water and inorganic acid in the product;
the first degassing tower is filled with metal pall rings, the working pressure of the degassing tower is 0.28-0.3 MPa, the temperature of a tower kettle is 80-90 ℃, the temperature of circulating cooling water at the top of the tower is 5-25 ℃, and the temperature at the top of the tower is 37-40 ℃;
the first rectifying tower is filled with metal pall ring or metal regular packing, the working pressure of the rectifying tower is 0.2-0.22 MPa, the temperature of the tower bottom is 81-90 ℃, the temperature of circulating cooling water at the top of the tower is 5-25 ℃, the temperature at the top of the tower is 54-55 ℃,
the filler of the second degassing tower is a wire mesh or a metal pall ring, the working pressure of the degassing tower is 0.24-0.27 MPa, the temperature of the tower bottom is 75-85 ℃, the temperature of the circulating cooling water at the top of the tower is 5-35 ℃, the temperature at the top of the tower is 48-50 ℃,
the second rectifying tower is filled with metal pall ring, the working pressure of the rectifying tower is 0.1-0.12 MPa, the temperature of the tower kettle is 60-66 ℃, the temperature of the circulating cooling water at the top of the tower is 5-35 ℃, the temperature at the top of the tower is 56-60 ℃,
the filler of the adsorption tower is A-type molecular sieve, activated carbon, silica gel or activated alumina, and the working pressure of the adsorption tower is 0.05-0.15 MPa;
the preparation method of the isomerization catalyst comprises the following steps: dissolving metal soluble salt in water, dropwise adding concentrated ammonia water for precipitation, adjusting pH value to 7.5, aging for 12 hours, washing with water, filtering, and drying in an oven at 80-150 deg.C for 12-48 hours; then roasting for 5-20 hours at the temperature of 300-500 ℃ under the protection of nitrogen; and finally, at the temperature of 300 ℃ and 500 ℃, introducing the substances in a mass ratio of 1: 4, activating the mixed gas consisting of the halogenated methane and the nitrogen for 4 to 20 hours, and stopping introducing the mixed gas to prepare metal fluorochlorides or metal fluorochloroxyls; wherein the metal soluble salt is at least one or more of chlorides or nitrates of Al, Mg, Cr, Fe, Co, Ni and Zn, and the halogenated methane is one or more of difluorodichloromethane, chlorodifluoromethane and dichlorofluoromethane;
the isomerization reaction conditions are as follows: in the presence of an isomerization catalyst, the reaction pressure is 0.01-0.5MPa, the reaction temperature is 150-350 ℃, and the contact time of the E-1-chloro-3, 3, 3-trifluoropropene is 20-100 s.
2. The production method according to claim 1, the isomerization catalyst is prepared by: dissolving metal soluble salt in water, dropwise adding concentrated ammonia water for precipitation, adjusting the pH value to 7.5, then aging for 12 hours, washing with water, filtering, and drying in an oven at 120 ℃ for 12 hours; then roasting for 12 hours at 350 ℃ under the protection of nitrogen; finally, at the temperature of 400 ℃, the mass ratio of the introduced substances is 1: 4, activating the mixed gas consisting of the halogenated methane and the nitrogen for 6 hours, and stopping introducing the mixed gas to prepare metal fluorochlorides or metal fluorochloroxyls; wherein the metal soluble salt is at least one or more of chloride or nitrate of Cr, Al, Mg, Fe and Zn, and the halogenated methane is one or more of difluorodichloromethane, chlorodifluoromethane and dichlorofluoromethane.
3. The production process according to claim 2, wherein the isomerization catalyst is at least one or more of aluminum fluorochloride, magnesium fluorochloride, chromium fluorochloride.
4. The production process according to claim 1, wherein the isomerization reaction conditions are: in the presence of an isomerization catalyst, the reaction pressure is 0.1-0.5MPa, the reaction temperature is 200-300 ℃, and the contact time of E-1-chloro-3, 3, 3-trifluoropropene is 20-70 s.
5. The production process according to claim 1, wherein the temperature of the circulating cooling water at the top of the second degassing tower is 15-35 ℃;
the filler of the adsorption tower is an A-type molecular sieve.
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CN112645793B (en) * 2020-12-18 2023-02-14 西安近代化学研究所 Process system and method for producing trans-1-chloro-3, 3-trifluoropropene
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