CN114573416B - Method for synthesizing 2-bromo-1, 3-tetrafluoropropene by gas phase method - Google Patents

Method for synthesizing 2-bromo-1, 3-tetrafluoropropene by gas phase method Download PDF

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CN114573416B
CN114573416B CN202210265694.6A CN202210265694A CN114573416B CN 114573416 B CN114573416 B CN 114573416B CN 202210265694 A CN202210265694 A CN 202210265694A CN 114573416 B CN114573416 B CN 114573416B
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CN114573416A (en
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卢北虎
胡棋威
隋鑫
何东
刘飞
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Wuhan Institute of Marine Electric Propulsion China Shipbuilding Industry Corp No 712 Institute CSIC
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    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/07—Preparation of halogenated hydrocarbons by addition of hydrogen halides
    • C07C17/087—Preparation of halogenated hydrocarbons by addition of hydrogen halides to unsaturated halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
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Abstract

The invention discloses a method for synthesizing 2-bromo-1, 3-tetrafluoropropene by a gas phase method, wherein the preparation method of the 2-bromo-1, 3-tetrafluoropropene comprises the following steps: (1) Taking tetrachlorotetrafluoropropane, and heating under the conditions of a catalyst and a protective gas to generate tetrafluoroallene; (2) And (3) heating the tetrafluoroallene and hydrogen bromide in the step (1) to react under the condition of a catalyst, so as to obtain the 2-bromo-1, 3-tetrafluoropropene. The invention has cheap raw materials and convenient sources; the catalyst has good stability and can be recycled; the invention has safe synthesis process and is suitable for industrial production.

Description

Method for synthesizing 2-bromo-1, 3-tetrafluoropropene by gas phase method
Technical Field
The invention belongs to the field of organic synthesis, and particularly relates to a method for synthesizing 2-bromo-1, 3-tetrafluoropropene by a gas phase method.
Background
The combustible gas is a substance that can be ignited and is in a gaseous state at normal temperature and pressure. Such as hydrogen, acetylene, ethylene, ammonia, hydrogen sulfide, and the like. The combustible gas is mixed in a certain proportion in the corresponding combustion-supporting medium, and can cause combustion or explosion under the action of the ignition source. Some combustible gases are toxic, such as carbon monoxide, hydrogen sulfide and the like, and when the combustible gases are inhaled excessively, the combustible gases cause serious harm to human bodies. Particularly, carbon monoxide is colorless and odorless, and carbon monoxide gas is often formed in industrial production and chemical plants, so that people are unknowingly involved in dangers. Thus, the hazard of flammable gases has created a significant problem in public safety for many years.
2-Bromo-1, 3-tetrafluoropropene is an important flammable gas explosion-suppressing agent capable of rapidly releasing bromine-containing free radicals, fluorine-containing free radicals, double bond free radicals, and the like, and rapidly terminating gas explosion by chain reaction, thereby achieving effective explosion suppression, but 2-bromo-1, 3-tetrafluoropropene has been less studied in the prior art.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for synthesizing 2-bromo-1, 3-tetrafluoropropene by a gas phase method. The preparation method has the advantages of low raw material cost, good catalyst stability and repeated recycling.
The aim of the invention is achieved by the following technical scheme:
a method for synthesizing 2-bromo-1, 3-tetrafluoropropene by a gas phase method, comprising the following steps:
(1) Taking tetrachlorotetrafluoropropane (CAS: 677-68-9, CF 2ClCCl2CF2 Cl), and heating under the condition of catalyst and protective gas to generate tetrafluoroallene (CAS: 461-68-7, CF 2=C=CF2);
(2) And (3) heating the tetrafluoroallene and hydrogen bromide in the step (1) to react under the condition of a catalyst, so as to obtain the 2-bromo-1, 3-tetrafluoropropene.
Preferably, the shielding gas in step (1) is nitrogen or an inert gas, more preferably nitrogen.
Preferably, the molar ratio of the tetrachlorotetrafluoropropane to the shielding gas is 1:0.1-4.
Preferably, the heating reaction time in the step (1) is 3-20 s.
Preferably, the temperature of the heating reaction in the step (1) is 100-300 ℃.
Preferably, the catalyst in the step (1) is at least one of gamma-Al 2O3, molecular sieve and active carbon.
Preferably, the ratio of the catalyst of step (1) to the addition of tetrachlorotetrafluoropropane is 1mL:0.001 to 0.003g.
Preferably, the molar ratio of tetrafluoroallene to hydrogen bromide in step (2) is 1:1.1 to 3.0.
Preferably, the heating reaction time in the step (2) is 3-20 s.
Preferably, the temperature of the heating reaction in the step (2) is 100-400 ℃.
Preferably, the catalyst in the step (2) is at least one of Mg, cr, fe, cu, zn and Al, or a composite formed by at least one of Mg, cr, fe, cu, zn and Al and at least one of Bi, ti and Ni.
Preferably, the volume ratio of the catalyst to the tetrafluoropropadiene in the step (2) is 3-6:1.
The chemical reaction formula of the invention is as follows:
Compared with the prior art, the invention has the beneficial effects that:
1. The invention has cheap raw materials and convenient sources.
2. The catalyst has good stability and can be recycled.
3. The solvent can be recycled.
4. The invention adopts gas phase catalysis, the yield of the product is higher, and the boiling point distinction is very large; the product is simple to separate and purify.
5. The synthesis process is safe and suitable for industrial production.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
(1) The first step of reaction:
10 ml gamma-alumina catalyst was charged into a fixed bed reactor which was heated with an open tube furnace. The catalyst was first dried at 10 c/min to 300 c under nitrogen protection at a flow rate of 300ml/min for 10 hours and then reduced to 100 c. This completes the drying process of the catalyst. The specific surface area measured by the BET method was 320.0m 2/g.
Under the catalysis of gamma-alumina, the reactor is heated to 150 ℃, and a peristaltic pump is adopted to uniformly mix tetrachlorotetrafluoropropane (the purity is 95 percent; the speed is 0.1 g/min) and nitrogen (the feeding speed is 20 ml/min) together in a mixing cavity (the reaction time is 15 s). Then, the mixture was passed through a reactor to a buffer bottle, a water washing bottle, a concentrated alkali absorber and a cooling collector. After the end of the experiment, the product was mainly distributed in the cooling collector. The collected product was subjected to GC analysis. The GC results showed that the collected product contained 35% (mole ratio) of tetrafluoropropadiene.
(2) And the second step of reaction:
CrCl 3,CuCl2,FeCl3,ZnCl2 solution (35 wt% concentration) in a molar ratio of 70:5:5:20 was mixed, 30wt% aqueous ammonia was added dropwise to the mixed solution, and ph=8.0 was adjusted. Filtering the precipitate, washing with deionized water, drying, and compression molding to obtain a catalyst precursor Cr-Cu-Fe-Zn;
The 50ml precursor catalyst Cr-Cu-Fe-Zn was placed in a fixed bed reactor, which was heated with an open tube furnace. The catalyst was dried under nitrogen (rate 100 ml/min) at 1 c/min to 400 c for 10 hours and then reduced to 200 c, thus completing the drying process.
The reactor was heated to 200℃and the catalyst was activated by the introduction of nitrogen (rate 100 ml/min) and hydrogen fluoride (rate 100 ml/min) for 10 hours; the temperature is increased to 500 ℃, and hydrogen fluoride (the speed is 100 ml/min) is introduced to activate the catalyst for 10 hours, thus completing the activation process of the Cr-Cu-Fe-Zn catalyst.
Under the catalysis of Cr-Cu-Fe-Zn catalyst, the reactor is heated to 160 ℃, and tetrafluoropropadiene (purity 95 percent; speed is 50 ml/min) and hydrogen bromide (speed is 50 ml/min) gas are fed into a mixing cavity together by a mass flowmeter and are mixed uniformly (reaction time is 15 s). Then, the mixture was passed through a reactor to a buffer bottle, a water washing bottle, a concentrated alkali absorber and a cooling collector. After the end of the experiment, the product was mainly distributed in the cooling collector. The collected product was subjected to GC analysis. GC results showed 65% (mole ratio) of 2-bromo-1, 3-tetrafluoropropene in the collected product.
Example 2
(1) The first step of reaction:
10ml of the activated carbon catalyst was charged into a fixed bed reactor, which was heated with an open tube furnace. The catalyst was first heated to 500 c at 10 c/min under nitrogen at 300 ml c/min, dried at this temperature for 10 hours, and then cooled to 100 c. This completes the drying process of the catalyst. The specific surface area measured by the BET method was 752.0m 2/g.
Under the catalysis of activated carbon, the reactor is heated to 200 ℃, and a peristaltic pump is adopted to uniformly mix tetrachlorotetrafluoropropane (the purity is 95 percent; the flow rate is 0.1 g/min) and nitrogen (the speed is 20 ml/min) together in a mixing cavity (the reaction time is 10 s). Then, the mixture was passed through a reactor to a buffer bottle, a water washing bottle, a concentrated alkali absorber and a cooling collector. After the end of the experiment, the product was mainly distributed in the cooling collector. The collected product was subjected to GC analysis. GC results showed that the product collected contained 23% tetrafluoropropadiene.
(2) And the second step of reaction:
CrCl 3,CuCl2 solution (35 wt% concentration) in a molar ratio of 70:30 was mixed, 30% wt% aqueous ammonia was added dropwise to the mixed solution, and ph=9.0 was adjusted. Filtering the precipitate, washing with deionized water, drying, and compression molding to obtain a catalyst precursor Cr-Cu;
50 ml of Cr-Cu precursor of the catalyst is fed into a fixed bed reactor, and the fixed bed reactor is heated by an open type tube heating furnace. The catalyst was dried at 1 c/min to 400 c under nitrogen protection at a rate of 100ml c/min for 10 hours and then reduced to 200 c, thus completing the drying process of the catalyst.
The reactor was heated to 200℃and the catalyst was activated by the introduction of nitrogen (rate 100 ml/min) and hydrogen fluoride (rate 100 ml/min) for 10 hours; the temperature was raised to 500℃and hydrogen fluoride (rate 100 ml/min) was introduced to activate the catalyst for 10 hours. Thus, the activation process of the Cr-Cu catalyst was completed.
Under the catalysis of Cr-Cu catalyst, the reactor is heated to 230 ℃, and tetrafluoropropadiene (with the purity of 88 percent, the speed of 50 ml/min) and hydrogen bromide (with the speed of 50 ml/min) are fed into a mixing cavity to be uniformly mixed together by adopting a mass flowmeter (the reaction time is 10 s). Then, the mixture was passed through a reactor to a buffer bottle, a water washing bottle, a concentrated alkali absorber and a cooling collector. After the end of the experiment, the product was mainly distributed in the cooling collector. The collected product was subjected to GC analysis. GC results showed that the collected product contained 46% (mole ratio) of 2-bromo-1, 3-tetrafluoropropene.
Example 3
(1) The first step of reaction:
10 ml gamma-alumina catalyst was charged into a fixed bed reactor which was heated with an open tube furnace. The catalyst was first dried at 10 c/min to 700 c under nitrogen at 300ml/min, at which temperature it was dried for 10 hours, and then cooled to 100 c. This completes the drying process of the catalyst. The specific surface area was 253.0 m 2/g as measured by the BET method.
Under the catalysis of gamma-alumina, the reactor is heated to 150 ℃, and a peristaltic pump is adopted to uniformly mix tetrachlorotetrafluoropropane (the purity is 95 percent; the speed is 0.1 g/min) and nitrogen (the speed is 20 ml/min) together in a mixing cavity (the reaction time is 20 s). Then, the mixture was passed through a reactor to a buffer bottle, a water washing bottle, a concentrated alkali absorber and a cooling collector. After the end of the experiment, the product was mainly distributed in the cooling collector. The collected product was subjected to GC analysis. The GC results showed that the collected product contained 46% (mole ratio) of tetrafluoropropadiene.
(2) And the second step of reaction:
FeCl 3,ZnCl2,Ni(NO3)3 solutions (35 wt% concentration) were mixed in a molar ratio of 70:25:5, 30wt% aqueous ammonia was added dropwise to the mixed solution, and pH=9.0 was adjusted. Filtering the precipitate, washing with deionized water, drying, and compression molding to obtain a catalyst precursor Fe-Zn-Ni;
50 ml of Fe-Zn-Ni precursor of the catalyst is fed into a fixed bed reactor, and the fixed bed reactor is heated by an open type tube heating furnace. The catalyst was dried at 1 c/min to 400 c under nitrogen protection at 100ml c/min for 10 hours and then reduced to 200 c, thus completing the drying process of the catalyst.
The reactor was heated to 200℃and the catalyst was activated by the introduction of nitrogen (rate 100 ml/min) and hydrogen fluoride (rate 100 ml/min) for 10 hours; the temperature was raised to 500℃and hydrogen fluoride (rate 100 ml/min) was introduced to activate the catalyst for 10 hours, thus completing the activation process of the Fe-Zn-Ni catalyst.
Under the catalysis of Fe-Zn-Ni catalyst, the reactor is heated to 310 ℃, and tetrafluoropropadiene (with the purity of 96 percent; the speed of 50 ml/min) and hydrogen bromide (with the speed of 50 ml/min) are fed into a mixing cavity to be uniformly mixed together by adopting a mass flowmeter (the reaction time is 20 s). Then, the mixture was passed through a reactor to a buffer bottle, a water washing bottle, a concentrated alkali absorber and a cooling collector. After the end of the experiment, the product was mainly distributed in the cooling collector. The collected product was subjected to GC analysis. GC results showed that the collected product contained 62 mole percent 2-bromo-1, 3-tetrafluoropropene.
Example 4
(1) The first step of reaction:
10 ml molecular sieve (purchased from Henan Corp. Environmental protection technology Co., ltd., model FZS 0002) catalyst was charged into a fixed bed reactor, and the fixed bed reactor was heated with an open tube furnace. The catalyst was dried at 10 c/min to 600 c under nitrogen protection at 300 ml/min for 10 hours and then reduced to 100 c, thus completing the drying process of the catalyst. The specific surface area measured by the BET method was 452.0 m 2/g.
Under the catalysis of molecular sieve, the reactor is heated to 250 ℃, and a peristaltic pump is adopted to uniformly mix tetrachlorotetrafluoropropane (the purity is 95 percent; the speed is 0.1 g/min) and nitrogen (the speed is 20 ml/min) together in a mixing cavity (the reaction time is 12 s). Then, the mixture was passed through a reactor to a buffer bottle, a water washing bottle, a concentrated alkali absorber and a cooling collector. After the end of the experiment, the product was mainly distributed in the cooling collector. The collected product was subjected to GC analysis. The GC results showed that the collected product contained 26 mole percent tetrafluoropropadiene.
(2) And the second step of reaction:
MgCl 2,ZnCl2,Bi(NO3)3 solutions (35 wt% concentration) in a molar ratio of 70:15:15 were mixed and 30wt% aqueous ammonia was added dropwise to the mixed solution, adjusting pH=9.0. Filtering the precipitate, washing with deionized water, drying, and compression molding to obtain catalyst precursor Mg-Zn-Bi;
50 ml of the catalyst Mg-Zn-Bi precursor is fed into a fixed bed reactor, and the fixed bed reactor is heated by an open type tube heating furnace. The catalyst was dried at 1 c/min to 400 c under nitrogen protection at a flow rate of 100ml c/min for 10 hours and then reduced to 200 c, thus completing the drying process of the catalyst.
The reactor was heated to 200℃and the catalyst was activated by the introduction of nitrogen (flow rate 100 ml/min) and hydrogen fluoride (flow rate 100 ml/min) for 10 hours; the temperature was raised to 500℃and the catalyst was activated with hydrogen fluoride (flow rate 100 ml/min) for 10 hours. Thus completing the activation process of the Mg-Zn-Bi catalyst.
Under the catalysis of a Mg-Zn-Bi catalyst, the reactor is heated to 290 ℃, and tetrafluoropropadiene (with the purity of 96 percent, the flow rate of 50 ml/min) and hydrogen bromide (with the flow rate of 50 ml/min) are fed into a mixing cavity to be uniformly mixed together by adopting a mass flowmeter (the reaction time is 12 s). Then, the mixture was passed through a reactor to a buffer bottle, a water washing bottle, a concentrated alkali absorber and a cooling collector. After the end of the experiment, the product was mainly distributed in the cooling collector. The collected product was subjected to GC analysis. GC results showed that the collected product contained 56 mole percent 2-bromo-1, 3-tetrafluoropropene.
The above-described embodiments of the present invention do not limit the scope of the present invention. Any other corresponding changes and modifications made in accordance with the technical idea of the present invention shall be included in the scope of the claims of the present invention.

Claims (4)

1. A method for synthesizing 2-bromo-1, 3-tetrafluoropropene by a gas phase method, which is characterized by comprising the following steps:
(1) The first step of reaction:
Loading a 10 ml gamma-alumina catalyst into a fixed bed reactor, and heating the fixed bed reactor by using an open type tube heating furnace; under the protection of nitrogen with the flow rate of 300 ml/min, the catalyst is firstly heated to 300 ℃ at the speed of 10 ℃/min, dried for 10 hours at the temperature, and then the temperature is reduced to 100 ℃, so that the drying process of the catalyst is completed;
under the catalysis of gamma-alumina, heating the reactor to 150 ℃, adding tetrachlorotetrafluoropropane and nitrogen into a mixing cavity by adopting a peristaltic pump, and uniformly mixing, wherein the reaction time is 15s, the purity of the tetrachlorotetrafluoropropane is 95%, and the speed is 0.1 g/min; the nitrogen rate is 20 ml/min; then, the mixture passes through a reactor until reaching a buffer bottle, a washing bottle, a concentrated alkali absorber and a cooling collector; after the experiment is finished, the product is mainly distributed in a cooling collector; subjecting the collected product to GC analysis; GC results showed that the product collected contained 35% tetrafluoropropadiene;
(2) And the second step of reaction:
Mixing CrCl 3,CuCl2,FeCl3,ZnCl2 solutions with the molar ratio of 70:5:20, wherein the concentration of the CrCl 3,CuCl2,FeCl3,ZnCl2 solutions is 35wt%; dropwise adding 30wt% ammonia water into the mixed solution, and adjusting the pH to be 8.0; filtering the precipitate, washing with deionized water, drying, and compression molding to obtain a catalyst precursor Cr-Cu-Fe-Zn;
Placing 50ml precursor catalyst Cr-Cu-Fe-Zn into a fixed bed reactor, and heating the fixed bed reactor by using an open type tube heating furnace; under the protection of nitrogen with the speed of 100 ml/min, the catalyst is firstly heated to 400 ℃ at the speed of 1 ℃/min, dried for 10 hours at the temperature, and then the temperature is reduced to 200 ℃, so that the drying process of the catalyst is completed;
Heating the reactor to 200 ℃, and introducing nitrogen and hydrogen fluoride to activate the catalyst for 10 hours, wherein the rates of the nitrogen and the hydrogen fluoride are 100 ml/min; raising the temperature to 500 ℃, and then introducing hydrogen fluoride at the rate of 100 ml/min to activate the catalyst for 10 hours, so that the activation process of the Cr-Cu-Fe-Zn catalyst is completed;
Heating a reactor to 160 ℃ under the catalysis of a Cr-Cu-Fe-Zn catalyst, adding tetrafluoroallene and hydrogen bromide gas into a mixing cavity by adopting a mass flowmeter, and uniformly mixing, wherein the reaction time is 15s, the purity of tetrafluoroallene is 95%, and the speed is 50 ml/min; the hydrogen bromide rate is 50 ml/min;
Thereafter, the reaction mixture was passed through a reactor until a buffer bottle, a water wash bottle, a concentrated alkali absorber, a cooling collector in which the product was mainly distributed.
2. A method for synthesizing 2-bromo-1, 3-tetrafluoropropene by a gas phase method, which is characterized by comprising the following steps:
(1) The first step of reaction:
loading 10ml of active carbon catalyst into a fixed bed reactor, heating the fixed bed reactor by an open type pipe heating furnace, heating the catalyst to 500 ℃ at 10 ℃/min under the protection of nitrogen at the speed of 300 ml/min, drying the catalyst at the temperature for 10 hours, and then reducing the temperature to 100 ℃, thereby completing the drying process of the catalyst;
Under the catalysis of activated carbon, heating the reactor to 200 ℃, adding tetrachlorotetrafluoropropane into a mixing cavity together by adopting a peristaltic pump, and uniformly mixing, wherein the reaction time is 10s, the purity of the tetrachlorotetrafluoropropane is 95%, and the flow rate is 0.1 g/min; the nitrogen rate is 20 ml/min; then, the mixture passes through a reactor until reaching a buffer bottle, a washing bottle, a concentrated alkali absorber and a cooling collector; after the experiment is finished, the product is mainly distributed in a cooling collector; GC analysis of the collected product shows that the collected product contains 23% of tetrafluoropropadiene;
(2) And the second step of reaction:
Mixing CrCl 3,CuCl2 solutions with the molar ratio of 70:30, wherein the concentration of the CrCl 3,CuCl2 solutions is 35wt%, dropwise adding 30 wt% ammonia water into the mixed solution, and adjusting the pH=9.0; filtering the precipitate, washing with deionized water, drying, and compression molding to obtain a catalyst precursor Cr-Cu;
Placing a 50ml catalyst Cr-Cu precursor into a fixed bed reactor, heating the fixed bed reactor by an open type pipe heating furnace, heating the catalyst to 400 ℃ at a speed of 1 ℃/min under the protection of nitrogen at a speed of 100 ml/min, drying the catalyst for 10 hours at the temperature, and then reducing the temperature to 200 ℃, thereby completing the drying process of the catalyst;
Heating the reactor to 200 ℃, and introducing nitrogen and hydrogen fluoride to activate the catalyst for 10 hours, wherein the rates of the nitrogen and the hydrogen fluoride are 100 ml/min; raising the temperature to 500 ℃, and then introducing hydrogen fluoride at the rate of 100 ml/min to activate the catalyst for 10 hours, so that the activation process of the Cr-Cu catalyst is completed;
Under the catalysis of a Cr-Cu catalyst, heating the reactor to 230 ℃, adding tetrafluoropropadiene and hydrogen bromide gas into a mixing cavity by adopting a mass flowmeter, and uniformly mixing, wherein the reaction time is 10s, the purity of the tetrafluoropropadiene is 88%, and the speed is 50 ml/min; the hydrogen bromide rate is 50 ml/min; thereafter, the reaction mixture was passed through a reactor until a buffer bottle, a water wash bottle, a concentrated alkali absorber, a cooling collector in which the product was mainly distributed.
3. A method for synthesizing 2-bromo-1, 3-tetrafluoropropene by a gas phase method, which is characterized by comprising the following steps:
(1) The first step of reaction:
loading a 10 ml gamma-alumina catalyst into a fixed bed reactor, heating the fixed bed reactor by an open type pipe heating furnace, heating the catalyst to 700 ℃ at a speed of 10 ℃/min under the protection of nitrogen at a speed of 300ml/min, drying the catalyst at the temperature for 10 hours, and then reducing the temperature to 100 ℃, thereby completing the drying process of the catalyst;
Under the catalysis of gamma-alumina, heating the reactor to 150 ℃, adding tetrachlorotetrafluoropropane and nitrogen into a mixing cavity by adopting a peristaltic pump, and uniformly mixing, wherein the reaction time is 20s, the purity of the tetrachlorotetrafluoropropane is 95%, and the flow rate is 0.1 g/min; the nitrogen rate is 20 ml/min; then, the mixture passes through a reactor until reaching a buffer bottle, a washing bottle, a concentrated alkali absorber and a cooling collector; after the experiment is finished, the product is mainly distributed in a cooling collector; subjecting the collected product to GC analysis; GC results showed 46% tetrafluoropropadiene in the collected product;
(2) And the second step of reaction:
Mixing FeCl 3,ZnCl2,Ni(NO3) 3 solutions with the molar ratio of 70:25:5, wherein the concentration of the FeCl 3,ZnCl2,Ni(NO3) 3 solution is 35wt%, dripping 30wt% ammonia water into the mixed solution, adjusting the pH to be 9.0, precipitating and filtering, washing with deionized water, drying, and pressing to form to obtain a catalyst precursor Fe-Zn-Ni;
Placing a 50ml catalyst Fe-Zn-Ni precursor into a fixed bed reactor, and heating the fixed bed reactor by using an open type tube heating furnace; under the protection of 100 ml/min nitrogen, the catalyst is firstly heated to 400 ℃ at 1 ℃/min, dried for 10 hours at the temperature, and then the temperature is reduced to 200 ℃, so that the drying process of the catalyst is completed;
Heating the reactor to 200 ℃, and introducing nitrogen and hydrogen fluoride to activate the catalyst for 10 hours, wherein the rates of the nitrogen and the hydrogen fluoride are 100 ml/min; raising the temperature to 500 ℃, and then introducing hydrogen fluoride at the rate of 100ml/min to activate the catalyst for 10 hours, so that the activation process of the Fe-Zn-Ni catalyst is completed;
Under the catalysis of an Fe-Zn-Ni catalyst, heating a reactor to 310 ℃, adding tetrafluoropropadiene and hydrogen bromide gas into a mixing cavity together by adopting a mass flowmeter, and uniformly mixing, wherein the reaction time is 20s, the purity of tetrafluoropropadiene is 96%, and the speed is 50 ml/min; the hydrogen bromide rate is 50 ml/min; thereafter, the reaction mixture was passed through a reactor until a buffer bottle, a water wash bottle, a concentrated alkali absorber, a cooling collector in which the product was mainly distributed.
4. A method for synthesizing 2-bromo-1, 3-tetrafluoropropene by a gas phase method, which is characterized by comprising the following steps:
(1) The first step of reaction:
Loading a 10 ml type FZS0002 molecular sieve catalyst into a fixed bed reactor, heating the fixed bed reactor by an open type pipe heating furnace, heating the catalyst to 600 ℃ at a speed of 10 ℃/min under the protection of nitrogen at a speed of 300 ml/min, drying the catalyst for 10 hours at the temperature, and then reducing the temperature to 100 ℃, thereby completing the drying process of the catalyst;
Under the catalysis of a molecular sieve, heating the reactor to 250 ℃, adding tetrachlorotetrafluoropropane and nitrogen into a mixing cavity by adopting a peristaltic pump, and uniformly mixing, wherein the reaction time is 12s, the purity of the tetrachlorotetrafluoropropane is 95%, and the flow rate is 0.1 g/min; the nitrogen rate is 20 ml/min; then, the mixture passes through a reactor until reaching a buffer bottle, a washing bottle, a concentrated alkali absorber and a cooling collector; after the experiment is finished, the product is mainly distributed in a cooling collector; subjecting the collected product to GC analysis; GC results showed that the product collected contained 26% tetrafluoropropadiene;
(2) And the second step of reaction:
Mixing MgCl 2,ZnCl2,Bi(NO3)3 solution with the molar ratio of 70:15:15, wherein the concentration of the MgCl 2,ZnCl2,Bi(NO3)3 solution is 35wt%, dripping 30wt% ammonia water into the mixed solution, adjusting the pH to be 9.0, precipitating and filtering, washing with deionized water, drying, and pressing for forming to obtain a catalyst precursor Mg-Zn-Bi;
Placing 50ml of catalyst Mg-Zn-Bi precursor into a fixed bed reactor, and heating the fixed bed reactor by using an open type tube heating furnace; under the protection of nitrogen with the flow rate of 100 ml/min, the catalyst is firstly heated to 400 ℃ at the speed of 1 ℃/min, dried for 10 hours at the temperature, and then the temperature is reduced to 200 ℃, so that the drying process of the catalyst is completed;
Heating the reactor to 200 ℃, and introducing nitrogen and hydrogen fluoride to activate the catalyst for 10 hours, wherein the rates of the nitrogen and the hydrogen fluoride are 100 ml/min; raising the temperature to 500 ℃, and then introducing hydrogen fluoride at the rate of 100 ml/min to activate the catalyst for 10 hours, so that the activation process of the Mg-Zn-Bi catalyst is completed;
Under the catalysis of a Mg-Zn-Bi catalyst, heating a reactor to 290 ℃, adding tetrafluoropropadiene and hydrogen bromide gas into a mixing cavity together by adopting a mass flowmeter, and uniformly mixing, wherein the reaction time is 12s, the purity of tetrafluoropropadiene is 96%, and the speed is 50 ml/min; the hydrogen bromide rate is 50 ml/min; thereafter, the reaction mixture was passed through a reactor until a buffer bottle, a water wash bottle, a concentrated alkali absorber, a cooling collector in which the product was mainly distributed.
CN202210265694.6A 2022-03-17 2022-03-17 Method for synthesizing 2-bromo-1, 3-tetrafluoropropene by gas phase method Active CN114573416B (en)

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CN109847237A (en) * 2018-12-18 2019-06-07 湖南省湘电试研技术有限公司 A kind of halogenated hydrocarbon gas fire extinguishing system with safe additive
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