CN107721810B - Method for synthesizing extinguishing agent octafluorocyclobutane - Google Patents
Method for synthesizing extinguishing agent octafluorocyclobutane Download PDFInfo
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- CN107721810B CN107721810B CN201711081489.XA CN201711081489A CN107721810B CN 107721810 B CN107721810 B CN 107721810B CN 201711081489 A CN201711081489 A CN 201711081489A CN 107721810 B CN107721810 B CN 107721810B
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- C—CHEMISTRY; METALLURGY
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- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
- C07C17/21—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms with simultaneous increase of the number of halogen atoms
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Abstract
The invention relates to a method for synthesizing a fire extinguishing agent octafluorocyclobutane, belonging to the field of organic chemical synthesis. The method for synthesizing octafluorocyclobutane is characterized by comprising the following steps: dichlorotetrafluorocyclobutene, hydrogen fluoride and chlorine are reacted in the presence of fluorination catalyst to produce octafluorocyclobutane.
Description
Technical Field
The invention belongs to the technical field of organic chemical synthesis, and particularly relates to a method for synthesizing a fire extinguishing agent octafluorocyclobutane.
Background
Octafluorocyclobutane has high industrial value and is a very important fluorine-containing fire extinguishing agent.
The synthesis research of octafluorocyclobutane has fewer related reports. A process for synthesizing octafluorocyclobutane by synthesizing octafluorocyclobutane from tetrafluoroethylene and water under high temperature and high pressure conditions is reported in the patent (US 6710215). However, the conditions of high temperature and high pressure limit the industrial production of the method. A process for the synthesis of octafluorocyclobutane by high temperature high pressure treatment of tetrafluoroethylene is reported in the patent (US 2404374). However, the disadvantages of this process are the high raw material cost, the danger of the high-pressure process and the low reaction yield. A process for the synthesis of octafluorocyclobutane by reacting hexafluorocyclobutane with vanadium pentafluoride is reported in the literature (Bardin, V.V.; Avramenko, A.A.; Furin, G.G.; Krasilnikov, V.A.; Karelin, A.I.; et al.; Journal of Fluorine Chemistry; vol.49; nb.3; (1990); p.385-400). The method has expensive raw materials, and limits the industrial production.
From the above, when preparing octafluorocyclobutane, the reaction conditions are harsh, and the raw materials are not easy to prepare, which all limit the industrial production of octafluorocyclobutane.
Disclosure of Invention
In order to solve the above problems, the present invention aims to provide a method for synthesizing the fire extinguishing agent octafluorocyclobutane.
In order to achieve the purpose, the method for synthesizing the octafluorocyclobutane provided by the invention comprises the step of carrying out gas-phase fluorination reaction on dichlorotetrafluorocyclobutene, hydrogen fluoride and chlorine serving as raw materials under the action of a fluorination catalyst to generate the octafluorocyclobutane.
The fluorination catalyst is at least one of Cr, Ni, Cu, Zn, Mg, Co and In.
The temperature of the gas phase fluorination reaction is 100-600 ℃.
The time of the gas phase fluorination reaction is 0.1 to 20 s.
The mol ratio of dichlorotetrafluorocyclobutene to hydrogen fluoride to chlorine is 1: 5-30: 2.5-5.
The method for synthesizing the fire extinguishing agent octafluorocyclobutane has the following beneficial effects:
1. the invention has cheap raw materials and convenient sources.
2. Less industrial three wastes.
3. High product yield and simple product separation and purification.
4. The synthesis process is safe and suitable for industrial production.
Detailed Description
The method for synthesizing the fire extinguishing agent octafluorocyclobutane provided by the invention is described in detail with reference to specific examples.
Example 1
(1) Preparation of fluorination catalyst: adopting a coprecipitation method, comprising the following steps: adding CrCl3、In(NO3)3、Zn(NO3)2Mixing the solution with a molar ratio of 90: 5 to obtain a mixed solution, adding 30 wt% ammonia water dropwise into the mixed solution, and adding p of the mixed solutionAdjusting the H value to 9.0, precipitating and aging for 24 hours, precipitating and filtering, washing with deionized water, drying, and pressing to form to obtain the Cr-In-Zn catalyst.
The drying process of the Cr-In-Zn catalyst comprises the following steps: 20ml of Cr-In-Zn catalyst was charged into a fixed bed reactor, which was then heated with an open tube furnace. Under the protection of 50m/min nitrogen, the Cr-In-Zn catalyst is firstly heated to 400 ℃ at the speed of 10 ℃/min and dried for 10 hours, and then the temperature is reduced to 200 ℃, thereby completing the drying process of the Cr-In-Zn catalyst.
The activation process of the Cr-In-Zn catalyst comprises the following steps: heating a fixed bed reactor to 200 ℃, and firstly, activating and catalyzing for 4 hours by using 100ml/min nitrogen and 20ml/min hydrogen fluoride; then activating and catalyzing for 4 hours by using 100ml/min nitrogen and 50ml/min hydrogen fluoride; then, 50ml/min nitrogen and 100ml/min hydrogen fluoride are used for activation and catalysis for 4 hours; then, pure hydrogen fluoride with the concentration of 100ml/min is used for activation and catalysis for 4 hours; the temperature was raised to 400 ℃ and finally activated and catalyzed with 100ml/min pure hydrogen fluoride for 4 hours, thereby completing the activation process of the Cr-In-Zn catalyst.
The fluorination catalyst participates in the reaction process: the mixed gas (the mol ratio of dichlorotetrafluorocyclobutene, hydrogen fluoride and chlorine is 1: 5: 3) is passed through a fixed bed reactor filled with Cr-In-Zn catalyst at 400 ℃ at the speed of 250 ml/min. Then, the concentrated alkali passes through a buffer bottle, a water washing bottle, a concentrated alkali absorber and a cooling collector. After the experiment was completed, the product was mainly distributed in the cooling accumulator. The product in the cold trap was collected and subjected to GC analysis. The GC results showed that the product collected contained 8% octafluorocyclobutane, 12% dichlorohexafluorocyclobutane, 16% trichloromonofluorocyclobutane, 62% dichlorotetrafluorocyclobutane.
Example 2
(1) Preparation of fluorination catalyst: adopting a coprecipitation method, comprising the following steps: adding CrCl3、Co(NO3)2、Mg(NO3)2Mixing the solutions at a molar ratio of 90: 5 to obtain a mixed solution, adding 30 wt% ammonia water dropwise into the mixed solution, adjusting pH to 9.0, precipitating and aging for 24 hr, precipitating and filteringWashing with deionized water, drying, and press forming to obtain the Cr-Co-Mg catalyst.
The drying process of the Cr-Co-Mg catalyst comprises the following steps: 20ml of Cr-Co-Mg catalyst was charged into a fixed bed reactor, which was then heated with an open tube furnace. Under the protection of 50m/min nitrogen, the Cr-Co-Mg catalyst is firstly heated to 400 ℃ at the speed of 10 ℃/min and dried for 10 hours, and then the temperature is reduced to 200 ℃, thereby completing the drying process of the Cr-Co-Mg catalyst.
The activation process of the Cr-Co-Mg catalyst comprises the following steps: heating a fixed bed reactor to 200 ℃, and firstly, activating and catalyzing for 4 hours by using 100ml/min nitrogen and 20ml/min hydrogen fluoride; then activating and catalyzing for 4 hours by using 100ml/min nitrogen and 50ml/min hydrogen fluoride; then, 50ml/min nitrogen and 100ml/min hydrogen fluoride are used for activation and catalysis for 4 hours; then, pure hydrogen fluoride with the concentration of 100ml/min is used for activation and catalysis for 4 hours; the temperature is raised to 400 ℃, and finally activation catalysis is carried out for 4 hours by using 100ml/min pure hydrogen fluoride, thereby completing the activation process of the Cr-Co-Mg catalyst.
The fluorination catalyst participates in the reaction process: the mixed gas (dichlorotetrafluorocyclobutene, hydrogen fluoride and chlorine in a molar ratio of 1: 20: 3) was passed through a 490 c fixed bed reactor packed with Cr-Co-Mg catalyst at a rate of 250 ml/min. Then, the concentrated alkali passes through a buffer bottle, a water washing bottle, a concentrated alkali absorber and a cooling collector. After the experiment was completed, the product was mainly distributed in the cooling accumulator. The product in the cold trap was collected and subjected to GC analysis. The GC results showed that the product collected contained 12% octafluorocyclobutane, 15% dichlorohexafluorocyclobutane, 21% trichloromonofluorocyclobutane, 45% dichlorotetrafluorocyclobutane.
Claims (4)
1. A method for synthesizing a fire extinguishing agent octafluorocyclobutane is characterized by comprising the following steps: under the action of a fluorination catalyst, dichlorotetrafluorocyclobutene, hydrogen fluoride and chlorine gas generate octafluorocyclobutane; the catalyst is selected from Cr-In-Zn catalyst and Cr-Co-Mg catalyst, and is prepared, dried and activated by the following method:
preparation of Cr-In-Zn catalyst: adopting a coprecipitation method, comprising the following steps: adding CrCl3、In(NO3)3、Zn(NO3)2Mixing the solutions into a mixed solution according to a molar ratio of 90: 5, then dropwise adding ammonia water accounting for 30% of the mixed solution into the mixed solution, adjusting the pH value of the mixed solution to 9.0, precipitating, aging for 24 hours, precipitating, filtering, washing with deionized water, drying, and performing compression molding to obtain the Cr-In-Zn catalyst;
the drying process of the Cr-In-Zn catalyst comprises the following steps: 20ml of Cr-In-Zn catalyst is loaded into a fixed bed reactor, and then the fixed bed reactor is heated by an open type tube heating furnace; under the protection of 50ml/min nitrogen, the Cr-In-Zn catalyst is firstly heated to 400 ℃ at the speed of 10 ℃/min and dried for 10 hours, and then the temperature is reduced to 200 ℃, thereby completing the drying process of the Cr-In-Zn catalyst;
the activation process of the Cr-In-Zn catalyst comprises the following steps: heating a fixed bed reactor to 200 ℃, and firstly, activating and catalyzing for 4 hours by using 100ml/min nitrogen and 20ml/min hydrogen fluoride; then activating and catalyzing for 4 hours by using 100ml/min nitrogen and 50ml/min hydrogen fluoride; then, 50ml/min nitrogen and 100ml/min hydrogen fluoride are used for activation and catalysis for 4 hours; then, pure hydrogen fluoride with the concentration of 100ml/min is used for activation and catalysis for 4 hours; raising the temperature to 400 ℃, and finally, activating and catalyzing for 4 hours by using 100ml/min pure hydrogen fluoride, thereby completing the activation process of the Cr-In-Zn catalyst;
preparation of Cr-Co-Mg catalyst: adopting a coprecipitation method, comprising the following steps: adding CrCl3、Co(NO3)2、Mg(NO3)2Mixing the solutions into a mixed solution according to a molar ratio of 90: 5, then dropwise adding ammonia water accounting for 30% of the mixed solution into the mixed solution, adjusting the pH value of the mixed solution to 9.0, precipitating, aging for 24 hours, precipitating, filtering, washing with deionized water, drying, and performing compression molding to obtain the Cr-Co-Mg catalyst;
the drying process of the Cr-Co-Mg catalyst comprises the following steps: 20ml of Cr-Co-Mg catalyst is loaded into a fixed bed reactor, and then the fixed bed reactor is heated by an open type tube heating furnace; under the protection of 50ml/min nitrogen, the Cr-Co-Mg catalyst is firstly heated to 400 ℃ at the speed of 10 ℃/min and dried for 10 hours, and then the temperature is reduced to 200 ℃, thereby completing the drying process of the Cr-Co-Mg catalyst;
the activation process of the Cr-Co-Mg catalyst comprises the following steps: heating a fixed bed reactor to 200 ℃, and firstly, activating and catalyzing for 4 hours by using 100ml/min nitrogen and 20ml/min hydrogen fluoride; then activating and catalyzing for 4 hours by using 100ml/min nitrogen and 50ml/min hydrogen fluoride; then, 50ml/min nitrogen and 100ml/min hydrogen fluoride are used for activation and catalysis for 4 hours; then, pure hydrogen fluoride with the concentration of 100ml/min is used for activation and catalysis for 4 hours; the temperature is raised to 400 ℃, and finally activation catalysis is carried out for 4 hours by using 100ml/min pure hydrogen fluoride, thereby completing the activation process of the Cr-Co-Mg catalyst.
2. The method of claim 1, wherein: dichlorotetrafluorocyclobutene, hydrogen fluoride and chlorine gas generate octafluorocyclobutane under the action of a fluorination catalyst, and the reaction temperature is 100-600 ℃.
3. The method of claim 1, wherein: dichlorotetrafluorocyclobutene, hydrogen fluoride and chlorine gas generate octafluorocyclobutane under the action of a fluorination catalyst, and the contact time of the reaction is as follows: 0.1-20 s.
4. The method of claim 1, wherein: dichlorotetrafluorocyclobutene, hydrogen fluoride and chlorine are reacted to generate octafluorocyclobutane under the action of a fluorination catalyst, and the molar ratio of the materials in the reaction is as follows: dichlorotetrafluorocyclobutene: hydrogen fluoride: chlorine gas 1: 5-30: 2.5 to 5.
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