CN112745194A - Process for continuously producing hexafluoroisopropanol by using hexafluoropropylene oxide as raw material - Google Patents
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Abstract
The invention relates to a fluorine chemical technology, in particular to a process method for continuously producing hexafluoroisopropanol by taking hexafluoropropylene oxide as a raw material. The process method for continuously producing hexafluoroisopropanol by taking hexafluoropropylene oxide as a raw material comprises the following steps: firstly, adding hexafluoropropylene oxide into a fixed bed reactor A filled with a catalyst A, and carrying out isomerization reaction to prepare hexafluoroacetone; filling the catalyst B into a fixed bed reactor B, introducing mixed hydrogen and nitrogen gas and hexafluoroacetone, and carrying out reduction reaction to obtain a hexafluoroisopropanol crude product; finally, separating and purifying the product to obtain high-purity hexafluoroisopropanol; catalyst A is fluorine-containing Al2O3Mixing with fluoridated ZSM-5 molecular sieve; the catalyst B is a palladium-carbon catalyst. The process method for continuously producing hexafluoroisopropanol by using hexafluoropropylene oxide as a raw material is economical, efficient, safe and capable of realizing continuous production, and overcomes the defects of high cost, complex process and difficult purification of the existing method.
Description
Technical Field
The invention relates to a fluorine chemical technology, in particular to a process method for continuously producing hexafluoroisopropanol by taking hexafluoropropylene oxide as a raw material.
Background
Hexafluoroisopropanol (HFIP) is an important fluorine-containing fine chemical and can be used for preparing various fluorine-containing chemicals such as a fluorine-containing surfactant, a fluorine-containing emulsifier, a fluorine-containing medicine and the like. Hexafluoroisopropanol (HFIP) is also a strongly polar solvent. Colorless transparent liquids, which are miscible with water or most organic solvents in any proportion, but insoluble in long-chain alkanes, are thermally stable and have good transparency to ultraviolet light, which makes them ideal solvents for many polymeric systems, including polyamides, polyesters, polyacrylonitriles, polyacetals and hydrolyzed polyvinyl esters. HFIP is also used as an end point for viscosity testing, molecular weight determination, etc. of polymer solutions, for example crystalline polymers such as PET and nylon, when subjected to SEC (size-exclusion chromatography) tests, HFIP can be an effective solvent because HFIP can dissolve most of them at room temperature, thus allowing a reasonable molecular weight distribution to be obtained. In addition, HFIP has excellent surface tension, can well disperse and dissolve certain dyes and organic pigments, and can be used as a high-grade cleaning agent for manufacturing and cleaning tip instrument equipment. HFIP also dissolves amino acid macromolecules well and causes far less damage to protein natural fibers than other solvents, and thus is also used as a spinning solvent for regenerated silk. HFIP is used as a medical intermediate, and is an advanced production raw material of inhalation anesthetic sevoflurane.
Currently, hexafluoroisopropanol is mostly prepared by liquid-phase catalytic hydrogenation of hexafluoroacetone, and then purified by rectification, for example, patents CN1962589, CN102557874A, JP2002275107, JP6184025 and US4564716 all use hexafluoroacetone hydrate as a raw material, and noble metal catalysts such as palladium, ruthenium, nickel, copper, etc. as catalysts, and perform hydrogenation reduction to prepare hexafluoroisopropanol.
In patent CN101323558A, hexafluoroisopropanol is prepared by putting hexafluoroacetone trihydrate into a reactor, introducing hydrogen gas first, then introducing a mixture of hexafluoroacetone and hydrogen gas, and finally introducing only hydrogen gas in the presence of a palladium-carbon catalyst and a cocatalyst. According to the method, 30% of hexafluoroacetone trihydrate is added, so that the addition of water is limited to the maximum extent, but the participation of water is not completely avoided, a large amount of heat energy is wasted in the rectification process, the concentration of the generated hexafluoroisopropanol is only 80%, the conversion rate is low, and the use of highly toxic hexafluoroacetone has high risk.
Patent CN102056879A provides a continuous process for the production of hexafluoroisopropanol by contacting hexafluoroacetone with hexafluoroisopropanol, hydrogen to produce a liquid feed stream, then introducing the liquid feed stream into a reactor containing an immobilized hydrogenation catalyst to convert said hexafluoroacetone to hexafluoroisopropanol and provide a product stream, and finally recovering a portion of the hexafluoroisopropanol from the product stream. Although the method has high conversion rate, the process is complex, the reaction pressure is high, and the reaction speed is slow.
The method for synthesizing and purifying hexafluoroisopropanol has the advantages of complex process, high cost, low yield, difficult realization of high yield, economy, safety, environmental friendliness and low cost in the conventional production process. The present invention has been made in view of the above drawbacks.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a process method for continuously producing hexafluoroisopropanol by taking hexafluoropropylene oxide as a raw material, which is efficient, economic, safe and capable of realizing continuous production and overcomes the defects of high cost, complex process and difficult purification of the existing method.
The invention discloses a process method for continuously producing hexafluoroisopropanol by taking hexafluoropropylene oxide as a raw material, which comprises the following steps:
(1) adding hexafluoropropylene oxide into a fixed bed reactor A filled with a catalyst A, and carrying out isomerization reaction to prepare hexafluoroacetone;
(2) filling the catalyst B into a fixed bed reactor B, introducing a hydrogen-nitrogen mixed gas with the hydrogen volume fraction of 40%, and introducing hexafluoroacetone to perform a reduction reaction to obtain a hexafluoroisopropanol crude product;
(3) and (3) separating and purifying the hexafluoroisopropanol crude product to obtain the high-purity hexafluoroisopropanol.
In the step (1), the catalyst A is Al containing 5-60 wt% of fluorine2O3And mixing with the fluorided ZSM-5 molecular sieve according to the mass ratio of 2:8-7: 3.
Preferably, catalyst A is 35 wt% Al containing fluorine2O3And the fluorided ZSM-5 molecular sieve are mixed according to the mass ratio of 4: 6.
The fluorination method of the ZSM-5 molecular sieve comprises the following steps:
ZSM-5 molecular sieve with the silicon-aluminum ratio of 20-100 is dried for 1-3h at the temperature of 60-250 ℃, then is put into a tube furnace, nitrogen is introduced, the temperature is raised to 400 ℃ of 180-2F2And (3) fluorinating for 2-6h, and finally introducing nitrogen for cooling to obtain the fluorinated ZSM-5 molecular sieve.
Preferably, the ZSM-5 molecular sieve is fluorinated by the following steps:
drying ZSM-5 molecular sieve with silica-alumina ratio of 50 at 150 deg.C for 2 hr, placing into a tubular furnace, introducing nitrogen gas, heating to 300 deg.C, introducing CCl2F2And (4) fluorinating for 4 hours, and finally introducing nitrogen for cooling to obtain the fluorinated ZSM-5 molecular sieve.
In the step (1), the reaction temperature of the isomerization reaction is 10-110 ℃, the reaction pressure is normal pressure, and the reaction space velocity is 150--1。
Preferably, the reaction temperature of the isomerization reaction is 20-60 ℃, and the reaction is carried outThe pressure is normal pressure, the reaction space velocity is 200--1。
In the step (2), the catalyst B is a 5% palladium-carbon catalyst.
The preparation method of the palladium-carbon catalyst comprises the following steps:
firstly, performing microwave heat treatment on an activated carbon carrier, then uniformly mixing the precursor solution and the activated carbon subjected to the microwave heat treatment to obtain slurry, adjusting the pH of the slurry to 6-9 by using an alkali solution, adding a reducing agent, stirring for 1-3h at 50-150 ℃ for reduction treatment, and then filtering, washing and vacuum drying to obtain the palladium-carbon catalyst.
Preferably, the preparation method of the palladium-carbon catalyst comprises the following steps:
firstly, performing microwave heat treatment on an activated carbon carrier, then uniformly mixing a precursor solution and the activated carbon subjected to the microwave heat treatment to obtain slurry, adjusting the pH of the slurry to 6-9 by using an alkali solution, adding a reducing agent, stirring for 2 hours at 100 ℃ for reduction treatment, and then filtering, washing and drying in vacuum to obtain the palladium-carbon catalyst.
The microwave frequency of the microwave heat treatment is 2000-3000MHz, the power is 300-800w, the microwave heating is carried out to 100-180 ℃, and the heat preservation is carried out for 0.5-3 h.
Preferably, the microwave frequency of the microwave heat treatment is 23000MHz, the power is 500w, the microwave is heated to 120 ℃, and the temperature is kept for 1 h.
The precursor solution is prepared by dissolving a soluble palladium compound in water; the soluble palladium compound is selected from one or more of chloropalladic acid, palladium chloride and sodium chloropalladite, and is preferably chloropalladite.
The reducing agent is selected from one or more of sodium hypophosphite, hydrazine hydrate, formaldehyde, sodium formate, sodium borohydride and formic acid, and hydrazine hydrate is preferred.
In the step (2), the molar ratio of hydrogen to hexafluoroacetone is 3-20:1, preferably 7-10: 1.
In the step (2), the reaction temperature of the reduction reaction is 150-350 ℃, and the reaction time is 1-3 h.
Preferably, the reaction temperature of the reduction reaction is 150-200 ℃, and the reaction time is 1-2 h.
And (3) in the step (3), the hexafluoroisopropanol crude product enters a post-treatment recovery unit and a rectification unit for product separation and purification, and the high-purity hexafluoroisopropanol is obtained.
The post-treatment recovery unit comprises a normal-temperature water absorption device (used for recovering unreacted extremely small amount of hexafluoroacetone), a low-temperature collection device (used for recovering hexafluoropropylene oxide) and a normal-temperature collection device (used for obtaining a product hexafluoroisopropanol) which are connected in sequence.
The rectifying unit is a rectifying tower connected with a condenser in series and is used for rectifying and purifying the collected hexafluoroisopropanol.
Compared with the prior art, the invention has the following beneficial effects:
(1) the process method can directly use the intermediate hexafluoroacetone with high toxicity for product synthesis without separate storage, thereby reducing the danger;
(2) the process method has high conversion rate and selectivity, less three wastes, continuous operation, reduced pollution, improved productivity, recycle of raw materials, elimination of waste of raw materials and products, improved utilization rate and reduced cost;
(3) the method has the advantages that the microwave method is used for treating the activated carbon, the heating efficiency is high, the time is short, the method is green and energy-saving, compared with the common activated carbon treatment method, the method has the characteristic of high desulfurization efficiency, the catalyst poisoning caused by sulfur is avoided, the palladium-carbon catalyst prepared by the method has long service life, can be used for multiple times, reduces the cost, is green and environment-friendly, and has high hydrogenation reduction selectivity and high conversion rate;
(4) the whole reaction system of the invention avoids the participation of water, the product is simple and convenient to separate, the rectification efficiency and the product purity are effectively improved, and the energy consumption is reduced.
Detailed Description
The present invention is further illustrated by the following examples, but the scope of the invention is not limited thereto.
The catalyst a used in the examples was prepared as follows:
drying 20g of ZSM-5 molecular sieve with the silica-alumina ratio of 50 at 150 ℃ for 2h, then putting the molecular sieve into a tube furnace, introducing nitrogen, heating to 30 ℃, and replacing CCl2F2Fluorination for 4hThen introducing nitrogen gas to reduce the temperature to obtain a fluorided ZSM-5 molecular sieve, and introducing Al containing 35% of fluorine2O3And the fluorinated ZSM-5 molecular sieve are mixed according to the mass ratio of 4:6 to be used as a catalyst A.
The catalyst B used in the examples was prepared as follows:
carrying out microwave heating treatment on 10g of activated carbon carrier, wherein the heating temperature is 120 ℃, the time is 1h, the microwave frequency is 2200MH, and the power is 500w, so as to obtain pretreated activated carbon; dissolving 0.88g of chloropalladate in 15ml of water to prepare a precursor solution; uniformly mixing the precursor solution and the pretreated activated carbon to obtain slurry, adjusting the pH of the slurry to 8.5 by using 1% sodium hydroxide alkali liquor, adding 5g of hydrazine hydrate, stirring at 100 ℃ for 2h for reduction treatment, and then filtering, washing and vacuum drying to obtain a 5% palladium-carbon catalyst serving as a catalyst B.
Example 1
Filling the catalyst A into a fixed bed reactor A, wherein the reaction pressure is normal pressure, the reaction temperature is 20 ℃, and the reaction space velocity is 300h-1Carrying out isomerization reaction to generate hexafluoroacetone, storing a reaction product in a buffer tank, pressing the reaction product to a fixed bed reactor B, preparing hexafluoroisopropanol through gas phase hydrogenation reduction, filling a catalyst B in the fixed bed reactor B, introducing a hydrogen-nitrogen mixed gas with the hydrogen content of 40%, wherein the molar ratio of hydrogen to hexafluoroacetone is 10:1, the reduction temperature is 150 ℃, the reduction time is 2 hours, introducing a very small amount of unreacted hexafluoroacetone after the reaction is finished into a normal-temperature water absorption device for recovery, collecting hexafluoropropylene oxide at low temperature, introducing a hexafluoroisopropanol crude product into a rectifying tower for rectification to obtain a high-purity hexafluoroisopropanol product, wherein the conversion rate is 98.5%, the selectivity is 99%, and the purity is 99.6%.
Example 2
Filling the catalyst A into a fixed bed reactor A, wherein the reaction pressure is normal pressure, the reaction temperature is 60 ℃, and the reaction space velocity is 200h-1Carrying out isomerization reaction to generate hexafluoroacetone, storing the reaction product in a buffer tank, then pressing the reaction product to a fixed bed reactor B, preparing hexafluoroisopropanol through gas phase hydrogenation reduction, filling a catalyst B in the fixed bed reactor B, and introducingHydrogen-nitrogen mixed gas with the hydrogen content of 40 percent, the molar ratio of hydrogen to hexafluoroacetone is 10:1, the reduction temperature is 150 ℃, the reduction time is 2 hours, a very small amount of unreacted hexafluoroacetone after the reaction is finished is led into a normal-temperature water absorption device for recovery, hexafluoropropylene oxide is collected at low temperature, a hexafluoroisopropanol crude product is led into a rectifying tower for rectification to obtain a high-purity hexafluoroisopropanol product, the conversion rate is 97.4 percent, the selectivity is 98.6 percent, and the purity is 99.5 percent.
Example 3
Filling the catalyst A into a fixed bed reactor A, wherein the reaction pressure is normal pressure, the reaction temperature is 20 ℃, and the reaction space velocity is 400h-1Carrying out isomerization reaction to generate hexafluoroacetone, storing a reaction product in a buffer tank, pressing the reaction product to a fixed bed reactor B, preparing hexafluoroisopropanol through gas phase hydrogenation reduction, filling a catalyst B in the fixed bed reactor B, introducing a hydrogen-nitrogen mixed gas with the hydrogen content of 40%, wherein the molar ratio of hydrogen to hexafluoroacetone is 10:1, the reduction temperature is 150 ℃, the reduction time is 2 hours, introducing a very small amount of unreacted hexafluoroacetone after the reaction is finished into a normal-temperature water absorption device for recovery, collecting hexafluoropropylene oxide at low temperature, introducing a hexafluoroisopropanol crude product into a rectifying tower for rectification to obtain a high-purity hexafluoroisopropanol product, wherein the conversion rate is 98.5%, the selectivity is 99.2%, and the purity is 99.8%.
Example 4
Filling the catalyst A into a fixed bed reactor A, wherein the reaction pressure is normal pressure, the reaction temperature is 20 ℃, and the reaction space velocity is 300h-1Carrying out isomerization reaction to generate hexafluoroacetone, storing a reaction product in a buffer tank, pressing the reaction product to a fixed bed reactor B, preparing hexafluoroisopropanol through gas phase hydrogenation reduction, filling a catalyst B in the fixed bed reactor B, introducing a hydrogen-nitrogen mixed gas with the hydrogen content of 40%, wherein the molar ratio of hydrogen to hexafluoroacetone is 7:1, the reduction temperature is 200 ℃, the reduction time is 1h, introducing a very small amount of unreacted hexafluoroacetone after the reaction is finished into a normal-temperature water absorption device for recovery, collecting hexafluoropropylene oxide at low temperature, introducing a hexafluoroisopropanol crude product into a rectifying tower for rectification to obtain a high-purity hexafluoroisopropanol product, wherein the conversion rate is 99.6%, the selectivity is 100%, and the purity is 99.8%.
Example 5
Filling the catalyst A into a fixed bed reactor A, wherein the reaction pressure is normal pressure, the reaction temperature is 20 ℃, and the reaction space velocity is 300h-1Carrying out isomerization reaction to generate hexafluoroacetone, storing a reaction product in a buffer tank, pressing the reaction product to a fixed bed reactor B, preparing hexafluoroisopropanol through gas phase hydrogenation reduction, filling a catalyst B in the fixed bed reactor B, introducing a hydrogen-nitrogen mixed gas with the hydrogen content of 40%, wherein the molar ratio of hydrogen to hexafluoroacetone is 7:1, the reduction temperature is 180 ℃, the reduction time is 1.5h, introducing a very small amount of unreacted hexafluoroacetone after the reaction is finished into a normal-temperature water absorption device for recovery, collecting hexafluoropropylene oxide at low temperature, and introducing a hexafluoroisopropanol crude product into a rectifying tower for rectification to obtain a high-purity hexafluoroisopropanol product, wherein the conversion rate is 99.8%, the selectivity is 100%, and the purity is 99.92%.
Example 6
Filling the catalyst A into a fixed bed reactor A, wherein the reaction pressure is normal pressure, the reaction temperature is 20 ℃, and the reaction space velocity is 300h-1Carrying out isomerization reaction to generate hexafluoroacetone, storing a reaction product in a buffer tank, pressing the reaction product to a fixed bed reactor B, preparing hexafluoroisopropanol through gas phase hydrogenation reduction, filling a catalyst B in the fixed bed reactor B, introducing a hydrogen-nitrogen mixed gas with the hydrogen content of 40%, wherein the molar ratio of hydrogen to hexafluoroacetone is 8:1, the reduction temperature is 150 ℃, the reduction time is 1h, introducing a very small amount of unreacted hexafluoroacetone after the reaction is finished into a normal-temperature water absorption device for recovery, collecting hexafluoropropylene oxide at low temperature, introducing a hexafluoroisopropanol crude product into a rectifying tower for rectification to obtain a high-purity hexafluoroisopropanol product, wherein the conversion rate is 99.5%, the selectivity is 100%, and the purity is 99.9%.
Comparative example 1
Adding 500ml of 99% hexachloroacetone into a reaction kettle, introducing 250ml of anhydrous hydrogen fluoride, adding 4g of catalyst chromium sesquioxide, heating to 70 ℃, refluxing for 2h, and sampling chromatographic analysis to ensure that the contents of trichlorotrifluoroacetone and dichlorotetrafluoroacetone reach 51%. And (3) roughly distilling the product obtained in the first step in a rectifying tower at the temperature of 70-80 ℃, and collecting 103ml of trichlorotrifluoroacetone and dichlorotetrafluoroacetone. Adding a mixture of trichlorotrifluoroacetone and tetrafluorodichloroacetone into another reaction kettle, adding 2g of chromium trioxide and 2g of palladium chloride serving as catalysts, introducing 90ml of anhydrous hydrogen fluoride, heating to 350 ℃ for 50min, introducing water to obtain hexafluoroacetone trihydrate, and sampling and detecting after rectification in a rectifying tower to ensure that the hexafluoroacetone is up to 90% qualified. Putting the product of the last step, namely hexafluoroacetone trihydrate, into a new reaction kettle, introducing 20ml of hydrogen, raising the pressure to 0.4MPa, heating to 60-80 ℃, refluxing for 8 hours, passing a rectifying tower, sampling and testing, wherein the hexafluoroisopropanol content is 99.5 percent, and the product is qualified. The total hexafluoroisopropanol yield was 93%.
Comparative example 2
The comparative example adopts 5 percent Pd/C as a catalyst to prepare hexafluoroisopropanol by gas-phase catalytic hydrogenation of hexafluoroacetone, and specifically comprises the following steps:
filling a catalyst into a hydrogenation chamber, gasifying hexafluoroacetone hydrate at 110 ℃, introducing the gasified hexafluoroacetone hydrate and mixed gas of hydrogen and nitrogen into the hydrogenation chamber filled with the catalyst, wherein the reduction temperature of the hydrogen chamber is 200 ℃, the reduction time is 1-3h, and the molar ratio of hydrogen to hexafluoroacetone is 10: 1; after the reaction, the reaction product enters a product treatment unit for product separation, and the conversion rate is 92.3 percent, and the selectivity is 97.2 percent.
Claims (10)
1. A process method for continuously producing hexafluoroisopropanol by taking hexafluoropropylene oxide as a raw material is characterized by comprising the following steps:
(1) adding hexafluoropropylene oxide into a fixed bed reactor A filled with a catalyst A, and carrying out isomerization reaction to prepare hexafluoroacetone;
(2) filling the catalyst B into a fixed bed reactor B, introducing mixed hydrogen and nitrogen gas and hexafluoroacetone, and carrying out reduction reaction to obtain a hexafluoroisopropanol crude product;
(3) separating and purifying the hexafluoroisopropanol crude product to obtain high-purity hexafluoroisopropanol;
wherein the catalyst A is Al containing 5-60 wt% of fluorine2O3Mixing with a fluorided ZSM-5 molecular sieve according to the mass ratio of 2:8-7: 3; the catalyst B is a palladium-carbon catalyst.
2. The process for continuously producing hexafluoroisopropanol as claimed in claim 1, wherein: the fluorination method of the ZSM-5 molecular sieve comprises the following steps:
ZSM-5 molecular sieve with the silicon-aluminum ratio of 20-100 is dried for 1-3h at the temperature of 60-250 ℃, then is put into a tube furnace, nitrogen is introduced, the temperature is raised to 400 ℃ of 180-2F2And (3) fluorinating for 2-6h, and finally introducing nitrogen for cooling to obtain the fluorinated ZSM-5 molecular sieve.
3. The process for continuously producing hexafluoroisopropanol as claimed in claim 1, wherein: the palladium loading capacity of the palladium-carbon catalyst is 5 wt%, and the preparation method of the palladium-carbon catalyst comprises the following steps:
firstly, performing microwave heat treatment on an activated carbon carrier, then uniformly mixing the precursor solution and the activated carbon subjected to the microwave heat treatment to obtain slurry, adjusting the pH of the slurry to 6-9 by using an alkali solution, adding a reducing agent, stirring for 1-3h at 50-150 ℃ for reduction treatment, and then filtering, washing and vacuum drying to obtain the palladium-carbon catalyst.
4. The process for continuously producing hexafluoroisopropanol as claimed in claim 3, wherein: the microwave frequency of the microwave heat treatment is 2000-3000MHz, the power is 300-800w, the microwave heating is carried out to 100-180 ℃, and the heat preservation is carried out for 0.5-3 h.
5. The process for continuously producing hexafluoroisopropanol as claimed in claim 3, wherein: the precursor solution is prepared by dissolving a soluble palladium compound in water, wherein the soluble palladium compound is selected from one or more of chloropalladic acid, palladium chloride and sodium chloropalladite.
6. The process for continuously producing hexafluoroisopropanol as claimed in claim 3, wherein: the reducing agent is selected from one or more of sodium hypophosphite, hydrazine hydrate, formaldehyde, sodium formate, sodium borohydride and formic acid.
7. The process for continuously producing hexafluoroisopropanol as claimed in claim 1, wherein: in the step (1), the reaction temperature of the isomerization reaction is 10-110 ℃, the reaction pressure is normal pressure, and the reaction space velocity is 150--1。
8. The process for continuously producing hexafluoroisopropanol as claimed in claim 1, wherein: in the step (2), the volume fraction of hydrogen in the hydrogen-nitrogen mixed gas is 40%.
9. The process for continuously producing hexafluoroisopropanol as claimed in claim 1, wherein: in the step (2), the molar ratio of hydrogen to hexafluoroacetone is 3-20: 1.
10. The process for continuously producing hexafluoroisopropanol as claimed in claim 1, wherein: in the step (2), the reaction temperature of the reduction reaction is 150-350 ℃, and the reaction time is 1-3 h.
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| CN114181060A (en) * | 2021-11-22 | 2022-03-15 | 浙江工业大学 | Preparation method of hexafluoroacetone trihydrate |
| CN115805087A (en) * | 2022-12-26 | 2023-03-17 | 上海华谊三爱富新材料有限公司 | Catalyst system, method for the production and use thereof |
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