CN114956950A - Method for synthesizing octafluorocyclobutane by using fluorine-chlorine exchange reaction - Google Patents
Method for synthesizing octafluorocyclobutane by using fluorine-chlorine exchange reaction Download PDFInfo
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- C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
- C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
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Abstract
The invention provides a method for synthesizing octafluorocyclobutane by using a fluorine-chlorine exchange reaction, which comprises the following steps of: the method comprises the steps of enabling hydrogen fluoride gas and 1,1,2,2,3, 4-hexafluoro-3, 4-dichlorocyclobutane gas to enter a reactor filled with a novel catalyst for reaction, enabling the molar ratio of the hydrogen fluoride gas to the 1,1,2,2,3, 4-hexafluoro-3, 4-dichlorocyclobutane to be 2-5: 1, enabling the reaction temperature to be 350-550 ℃ and the retention time to be 45-120s, absorbing a prepared octafluorocyclobutane crude product through alkali washing, rectifying, refining and adsorbing to obtain the high-purity octafluorocyclobutane. The method has the advantages of cheap raw materials, mild reaction conditions, low equipment loss rate, less energy loss, simple process flow and high production efficiency.
Description
Technical Field
The invention belongs to the technical field of chemical production, and particularly relates to a method for synthesizing octafluorocyclobutane by using a fluorine-chlorine exchange reaction.
Background
Octafluorocyclobutane is a green environment-friendly special gas with stable chemical property, good insulating property and zero ozone layer depletion potential (ODP value), and has good application prospect in the fields of high-voltage insulation, cleaning etching, plasma treatment and the like in recent years. Octafluorocyclobutane and N 2 、CO 2 Compared with SF 6 The gas has similar electric strength and insulating arc extinguishing capability and lower global warming potential, and is expected to become SF in gas insulated transformers, circuit breakers and power transmission and distribution pipelines 6 A substitute for gas. In recent years, with the upgrading of the semiconductor industry, higher fluorocarbon compounds are increasingly widely applied in the plasma dry etching process, and the published patent CN1967777A shows that the addition of octafluorocyclobutane helps to prevent the deterioration of the etching rate and helps to reduce the electrostatic discharge defects. The synthesis of high-purity octafluorocyclobutane plays an important role in promoting the development of the semiconductor industry.
Regarding the preparation method of octafluorocyclobutane, the currently known and published synthetic methods are mainly the following:
(1) olefin polymerization method: the method for producing octafluorocyclobutane by polymerizing tetrafluoroethylene was proposed in the previous 40 th century and is the most widely developed and applied method at present. A series of important fluorocarbon compounds such as octafluorocyclobutane, hexafluoropropylene, hexafluoroethane and the like can be simultaneously prepared by regulating and controlling the polymerization temperature, but monomers which are easy to self-polymerize when tetrafluoroethylene is used as a raw material are easy to self-polymerize and disproportionate at high temperature, and the synthesis of a large toxic compound perfluoroisobutylene can be accompanied.
(2) Electrolytic fluorination: the method for preparing octafluorocyclobutane by the 1,1,2, 2-tetrafluorocyclobutane electrolysis method is beneficial to reducing the formation of perfluoroisobutylene by-products and improving the safety of the reaction, but the higher the initial concentration of the electrolysis reaction product is, the lower the selectivity is, the breakage of carbon-carbon bonds occurs in the electrolysis process, and the difficulty of subsequent separation and purification is increased.
(3) And a tetrafluoroethylene waste liquid extraction method: patent publication CN101134710A reports that in the process of producing tetrafluoroethylene by cracking chlorodifluoromethane, accompanied by the production of octafluorocyclobutane, octafluorocyclobutane with a volume fraction of 99% can be obtained by extractive distillation of the rectified components from tetrafluoroethylene production, but the gas produced by this process is difficult to meet the demand of high purity electronics industry.
(4) The fluorine-chlorine cyclobutene fluorination addition method comprises the following steps: patent publication CN107721810B reports a scheme for synthesizing octafluorocyclobutane by performing addition reaction and substitution reaction on 1, 2-dichloro-3, 3,4, 4-tetrafluorocyclobutene, chlorine and hydrogen fluoride, wherein the method is relatively low in raw materials and relatively mild in reaction conditions, but chlorine is highly corrosive to metals, easily causes corrosion leakage of equipment, is high in toxicity and serious in environmental hazard, and limits the application of the method in industry.
The different preparation methods have advantages and disadvantages, and cannot fully meet the production requirements and quality requirements, so that a simple and efficient preparation method with good product quality needs to be designed.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a method for synthesizing octafluorocyclobutane by using a fluorine-chlorine exchange reaction, aiming at the defects of the prior art, and the method has the advantages of cheap raw materials, mild conditions, low equipment loss rate, low purification energy loss, simple process flow and high production efficiency.
In order to solve the technical problems, the invention adopts the technical scheme that: a method for synthesizing octafluorocyclobutane by using a fluorine-chlorine exchange reaction is characterized by comprising the following steps of:
s1 preparation of activated carbon-supported Cr 2 O 3 -a NiO catalyst;
s2, carrying out catalyst fluorination: introducing hydrogen fluoride gas into a reactor filled with the catalyst prepared in S1 for fluorination, wherein the reaction temperature is 100 ℃ and 200 ℃, the residence time of the hydrogen fluoride is 50-80S, and the fluorination time of the catalyst is 3 h; after the fluorination is finished, N is switched on 2 Purging for 1 h;
s3, synthesis reaction: introducing hydrogen fluoride gas and 1,1,2,2,3, 4-hexafluoro-3, 4-dichlorocyclobutane gas into a reactor for completing catalyst fluorination in an S2 according to the molar ratio of 2-5: 1, reacting at the temperature of 350 ℃ for 550 ℃ for 45-120S, and performing alkaline washing absorption to obtain a crude product of octafluorocyclobutane;
s4, refining: and (2) carrying out alkaline washing on the octafluorocyclobutane crude product obtained by S3 to remove hydrogen fluoride, rectifying, purifying and removing high-boiling-point substances, removing low-boiling-point substances, and finally introducing into an adsorption tower filled with an adsorbent, wherein the adsorption temperature is 0-40 ℃, the retention time is 20-80S, and finally obtaining the high-purity octafluorocyclobutane gas.
Preferably, the activated carbon-supported Cr is prepared in S1 2 O 3 The specific steps of the NiO catalyst are:
s101, preparing a 0.5-5 mol/L chromium chloride solution, and adding 0.1-1% of nickel chloride into the chromium chloride solution to prepare a chromium-nickel immersion liquid;
s102, adding activated carbon into another beaker, adding a chromium-nickel immersion liquid until the activated carbon is just saturated, and immersing for 4 hours at 40-60 ℃;
s103, roasting the reaction solid mixture at 300-500 ℃ for 24 hours, and repeating the operations of soaking and roasting for one to three times;
s104, adding 1% of glycerol into the product obtained by soaking and roasting in the step S103, and pressing under the pressure of 5MPa to obtain a cylindrical catalyst finished product with the diameter of 3mm and the height of 5 mm.
Preferably, the adsorbent in S4 is an X-type molecular sieve, an a-type molecular sieve, activated carbon or silica gel, and the adsorbent is subjected to heat treatment and steam treatment before use.
Preferably, the reactors used in S2 and S3 are nickel tubular reactors having a diameter of 40mm and a length of 900mm, and the cylindrical catalyst is fixed above a 200 mesh nickel mesh sheet at the bottom of the reactor to prevent the catalyst from falling into the reaction lines and causing the line blockage.
Compared with the prior art, the invention has the following advantages:
1. the invention can effectively increase the boiling point difference between the reactant and the product, reduce the difficulty of rectification and purification and reduce the energy consumption in the production process of the high-purity octafluorocyclobutane.
2. Compared with a catalyst with a single component, the nickel metal doped catalyst has higher conversion efficiency, the plasticity of the catalyst is improved by adding the glycerol, the adsorption effect on the 1,1,2,2,3, 4-hexafluoro-3, 4-dichlorocyclobutane is improved, and the catalyst is easy to fill in a reactor.
3. The method is simple and scientific, has strong practicability, high production efficiency, high product quality and low production cost, and can be popularized and used.
The present invention will be described in further detail with reference to the accompanying drawings and examples.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
Example 1
As shown in fig. 1, the present embodiment includes the following steps:
s1 preparation of activated carbon-supported Cr 2 O 3 -NiO catalyst: 133g of chromium chloride and 0.65g of nickel chloride are weighed, water is added to prepare 1L of chromium chloride impregnation liquid with the nickel content of 1 percent of the chromium content and the nickel content of 0.5mol/L, another beaker is taken, 100g of active carbon is added, the impregnation liquid is added until the impregnation liquid is just adsorbed and saturated by the active carbon, no free flowing liquid exists in the reaction mixture, and the mixture is impregnated for 4 hours at the temperature of 40 ℃. The reacted solid mixture was calcined at 300 ℃ for 24 h. 1.2g of glycerin was added to the obtained catalyst, and the catalyst was pressed into a cylindrical catalyst # 1 having a diameter of 3mm and a height of 5mm by using an electric tablet press under a pressure of 5 MPa.
S2, catalyst fluorination: introducing hydrogen fluoride gas into a reactor filled with the catalyst prepared in S1 for fluorination, wherein the reaction temperature is 100 ℃, and the hydrogen fluoride gas isThe retention time is 50s, the fluorination time of the catalyst is 3h, and N is introduced after the fluorination is finished 2 And purging for 1 h.
S3, synthesis reaction: introducing hydrogen fluoride gas and 1,1,2,2,3, 4-hexafluoro-3, 4-dichlorocyclobutane gas into a reactor for completing catalyst fluorination in an S2 according to the molar ratio of 2:1, reacting at the temperature of 350 ℃ for 100S, and performing alkaline washing absorption to obtain a crude product of octafluorocyclobutane. On-line analysis by gas chromatography showed that under these reaction conditions, the conversion of 1,1,2,2,3, 4-hexafluoro-3, 4-dichlorocyclobutane was 45.8% with a selectivity of 61.3%.
S4, refining: and (3) carrying out alkaline washing on the octafluorocyclobutane crude product obtained in the step (S3) to remove hydrogen fluoride, rectifying and purifying to remove high-boiling-point substances, removing low-boiling-point substances, and finally introducing into an adsorption tower filled with an adsorbent, wherein the adsorption temperature is 20 ℃, the adsorption time is 280S, and the octafluorocyclobutane gas with the purity of 99.99% is finally obtained.
Example 2
The embodiment comprises the following steps:
s1 preparation of activated carbon-supported Cr 2 O 3 -NiO catalyst: 266g of chromium chloride and 1.29g of nickel chloride are weighed and added with water to prepare 1L of chromium chloride impregnation liquid with the nickel content of 1mol/L of the chromium content, another beaker is taken, 100g of active carbon is added, the impregnation liquid is added until the impregnation liquid is just adsorbed and saturated by the active carbon, no free flowing liquid exists in the reaction mixture, and the mixture is impregnated for 4 hours at the temperature of 60 ℃. The reacted solid mixture was calcined at 400 ℃ for 24 h. The impregnation firing operation was repeated three times. 1.2g of glycerin was added to the obtained catalyst, and the catalyst was pressed into a cylindrical catalyst # 2 having a diameter of 3mm and a height of 5mm by using an electric tablet press under a pressure of 5 MPa.
S2, catalyst fluorination: introducing hydrogen fluoride gas into a reactor filled with the catalyst prepared in S1 for fluorination, wherein the reaction temperature is 200 ℃, the retention time of the hydrogen fluoride gas is 80S, the fluorination time of the catalyst is 3h, and introducing N after the fluorination is finished 2 And purging for 1 h.
S3, synthesis reaction: introducing hydrogen fluoride gas and 1,1,2,2,3, 4-hexafluoro-3, 4-dichlorocyclobutane gas into a reactor for completing catalyst fluorination in an S2 according to the molar ratio of 3:1, reacting at the temperature of 500 ℃ for 120S, and performing alkaline washing absorption to obtain a crude product of octafluorocyclobutane. On-line analysis by gas chromatography showed that under the reaction conditions, the conversion of 1,1,2,2,3, 4-hexafluoro-3, 4-dichlorocyclobutane was 80.2% and the selectivity was 85.1%.
S4, refining: and (3) carrying out alkaline washing on the octafluorocyclobutane crude product obtained in the step (S3) to remove hydrogen fluoride, rectifying and purifying to remove high-boiling-point substances, removing low-boiling-point substances, and finally introducing into an adsorption tower filled with an adsorbent, wherein the adsorption temperature is 10 ℃, the adsorption time is 60S, and the octafluorocyclobutane gas with the purity of 99.99% is finally obtained.
Example 3
The embodiment comprises the following steps:
s1, preparing activated carbon-loaded Cr 2 O 3 -NiO catalyst: 266g of chromium chloride and 1.29g of nickel chloride are weighed and added with water to prepare 1L of chromium chloride impregnation liquid with the nickel content of 1mol/L of the chromium content, another beaker is taken, 100g of active carbon is added, the impregnation liquid is added until the impregnation liquid is just adsorbed and saturated by the active carbon, no free flowing liquid exists in the reaction mixture, and the mixture is impregnated for 4 hours at the temperature of 60 ℃. The reacted solid mixture was calcined at 400 ℃ for 24 h. The impregnation-baking operation was repeated three times. 1.2g of glycerin was added to the obtained catalyst, and the catalyst was pressed into a cylindrical catalyst # 2 having a diameter of 3mm and a height of 5mm by using an electric tablet press under a pressure of 5 MPa.
S2, catalyst fluorination: introducing hydrogen fluoride gas into a reactor filled with the catalyst prepared in S1 for fluorination, wherein the reaction temperature is 150 ℃, the retention time of the hydrogen fluoride gas is 80S, the fluorination time of the catalyst is 3h, and introducing N after the fluorination is finished 2 And purging for 1 h.
S3, synthesis reaction: introducing hydrogen fluoride gas and 1,1,2,2,3, 4-hexafluoro-3, 4-dichlorocyclobutane gas into a reactor for completing catalyst fluorination in an S2 according to the molar ratio of 5:1, reacting at the temperature of 400 ℃ for 80S, and performing alkaline washing absorption to obtain a crude product of octafluorocyclobutane. On-line analysis by gas chromatography showed that under these reaction conditions, the conversion of 1,1,2,2,3, 4-hexafluoro-3, 4-dichlorocyclobutane was 65.9% and the selectivity was 91.0%.
S4, refining: and (3) carrying out alkali washing on the octafluorocyclobutane crude product obtained in the step (S3) to remove hydrogen fluoride, rectifying and purifying to remove high-boiling-point substances, removing low-boiling-point substances, and finally introducing into an adsorption tower filled with an adsorbent, wherein the adsorption temperature is 40 ℃, the adsorption time is 40S, and the octafluorocyclobutane gas with the purity of 99.99% is finally obtained.
Example 4
The embodiment comprises the following steps:
s1 preparation of activated carbon-supported Cr 2 O 3 -NiO catalyst: 1.33kg of chromium chloride and 0.65g of nickel chloride are weighed, water is added to prepare 1L of chromium chloride impregnation liquid with the nickel content of 0.1 percent of the chromium content and the concentration of 5mol/L, another beaker is taken, 100g of activated carbon is added, the impregnation liquid is added until the impregnation liquid is just adsorbed and saturated by the activated carbon, no free flowing liquid exists in the reaction mixture, and the mixture is impregnated for 4 hours at the temperature of 40 ℃. The reacted solid mixture was calcined at 400 ℃ for 24 h. The impregnation firing operation was repeated once. 1.2g of glycerin was added to the obtained catalyst, and the catalyst was pressed into a cylindrical catalyst # 3 having a diameter of 3mm and a height of 5mm by using an electric tablet press under a pressure of 5 MPa.
S2, catalyst fluorination: introducing hydrogen fluoride gas into a reactor filled with the catalyst prepared in S1 for fluorination, wherein the reaction temperature is 200 ℃, the retention time of the hydrogen fluoride gas is 80S, the fluorination time of the catalyst is 3h, and introducing N after the fluorination is finished 2 And purging for 1 h.
S3, synthesis reaction: introducing hydrogen fluoride gas and 1,1,2,2,3, 4-hexafluoro-3, 4-dichlorocyclobutane gas into a reactor for completing catalyst fluorination in an S2 according to the molar ratio of 3:1, reacting at the temperature of 500 ℃ for 45S, and performing alkaline washing absorption to obtain a crude product of octafluorocyclobutane. On-line analysis by gas chromatography showed that under the reaction conditions, the conversion of 1,1,2,2,3, 4-hexafluoro-3, 4-dichlorocyclobutane was 64.3% and the selectivity was 72.5%.
S4, refining: and (3) carrying out alkali washing on the octafluorocyclobutane crude product obtained in the step (S3) to remove hydrogen fluoride, rectifying and purifying to remove high-boiling-point substances, removing low-boiling-point substances, and finally introducing into an adsorption tower filled with an adsorbent, wherein the adsorption temperature is 30 ℃, the adsorption time is 20S, and the octafluorocyclobutane gas with the purity of 99.99% is finally obtained.
Example 5
The embodiment comprises the following steps:
s1 preparation of activated carbon-supported Cr 2 O 3 -NiO catalyst: 266g of chromium chloride and 0.65g of nickel chloride are weighed and added with water to prepare 1L of chromium chloride impregnation liquid with the nickel content of 0.5 percent of the chromium content and the concentration of 1mol/L, and another beaker is taken and added with 100g of active carbon, the impregnation liquid is added until the active carbon is just saturated, and the mixture is impregnated for 4 hours at the temperature of 50 ℃. The reacted solid mixture was calcined at 500 ℃ for 24 h. The impregnation firing operation was repeated three times. 1.2g of glycerin was added to the obtained catalyst, and the catalyst was pressed into a cylindrical catalyst # 4 having a diameter of 3mm and a height of 5mm by using an electric tablet press under a pressure of 5 MPa.
S2, catalyst fluorination: introducing hydrogen fluoride gas into a reactor filled with the catalyst prepared in S1 for fluorination, wherein the reaction temperature is 200 ℃, the retention time of the hydrogen fluoride gas is 80S, the fluorination time of the catalyst is 3h, and introducing N after the fluorination is finished 2 And purging for 1 h.
S3, synthesis reaction: introducing hydrogen fluoride gas and 1,1,2,2,3, 4-hexafluoro-3, 4-dichlorocyclobutane gas into a reactor for completing catalyst fluorination in an S2 according to the molar ratio of 4:1, reacting at the temperature of 550 ℃ for 45S, and performing alkaline washing absorption to obtain a crude product of octafluorocyclobutane. On-line analysis by gas chromatography showed that under the reaction conditions, the conversion of 1,1,2,2,3, 4-hexafluoro-3, 4-dichlorocyclobutane was 76.9% and the selectivity was 86.7%.
S4, refining: and (3) carrying out alkali washing on the octafluorocyclobutane crude product obtained in the step (S3) to remove hydrogen fluoride, rectifying and purifying to remove high-boiling-point substances, removing low-boiling-point substances, and finally introducing into an adsorption tower filled with an adsorbent, wherein the adsorption temperature is 0 ℃, the adsorption time is 70S, and the octafluorocyclobutane gas with the purity of 99.99% is finally obtained.
Examples 1 to 5 are combined and summarized in Table 1
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any simple modification, change and equivalent changes of the above embodiments according to the technical essence of the invention are still within the protection scope of the technical solution of the invention.
Claims (3)
1. A method for synthesizing octafluorocyclobutane by using a fluorine-chlorine exchange reaction is characterized by comprising the following steps of:
s1 preparation of activated carbon-supported Cr 2 O 3 -a NiO catalyst;
s2, carrying out catalyst fluorination: introducing hydrogen fluoride gas into a reactor filled with the catalyst prepared in S1 for fluorination, wherein the reaction temperature is 100 ℃ and 200 ℃, the residence time of the hydrogen fluoride is 50-80S, and the fluorination time of the catalyst is 3 h; after the fluorination is finished, N is switched on 2 Purging for 1 h;
s3, synthesis reaction: introducing hydrogen fluoride gas and 1,1,2,2,3, 4-hexafluoro-3, 4-dichlorocyclobutane gas into a reactor for completing catalyst fluorination in an S2 according to the molar ratio of 2-5: 1, reacting at the temperature of 350 ℃ for 550 ℃ for 45-120S, and performing alkaline washing absorption to obtain a crude product of octafluorocyclobutane;
s4, refining: and (3) rectifying and purifying the octafluorocyclobutane crude product obtained in the step (S3) to remove high-boiling-point substances, removing low-boiling-point substances, and finally introducing into an adsorption tower filled with an adsorbent, wherein the adsorption temperature of the adsorption tower is 0-40 ℃, and the gas retention time is 20-80S, so that high-purity octafluorocyclobutane gas is finally obtained.
2. The method for synthesizing octafluorocyclobutane according to claim 1, wherein activated carbon-supported Cr is prepared in S1 2 O 3 The specific steps of the NiO catalyst are:
s101, preparing a 0.5-5 mol/L chromium chloride solution, and adding 0.1-1% of nickel chloride into the chromium chloride solution to prepare a chromium-nickel immersion liquid;
s102, adding activated carbon into another beaker, adding a chromium-nickel immersion liquid until the activated carbon is just saturated, and immersing for 4 hours at 40-60 ℃;
s103, roasting the activated carbon adsorbed with the chromium-nickel impregnation liquid prepared in the S102 step at 300-500 ℃ for 24 hours, and repeating the operations of impregnation and roasting for one to three times;
and S104, adding 1% by mass of glycerol into the product obtained by soaking and roasting in the step S103, setting the pressure of 5MPa by using an electric tablet press, and pressing the catalyst into a cylindrical catalyst finished product with the diameter of 3mm and the height of 5 mm.
3. The method for synthesizing octafluorocyclobutane according to claim 1, wherein the adsorbent in S4 is one or more mixed adsorbents selected from X-type molecular sieve, a-type molecular sieve, activated carbon and silica gel.
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| 付成刚,冯晓军: "八氟环丁烷的合成研究", 有机氟工业 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116212431A (en) * | 2023-04-28 | 2023-06-06 | 山东东岳化工有限公司 | Purification system and purification method of electronic grade octafluorocyclobutane |
| CN116212431B (en) * | 2023-04-28 | 2023-08-18 | 山东东岳化工有限公司 | Purification system and purification method of electronic grade octafluorocyclobutane |
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