CN111233653A - Economical and efficient perfluoronitrile and perfluoroketone co-production process and device - Google Patents

Economical and efficient perfluoronitrile and perfluoroketone co-production process and device Download PDF

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CN111233653A
CN111233653A CN202010245249.4A CN202010245249A CN111233653A CN 111233653 A CN111233653 A CN 111233653A CN 202010245249 A CN202010245249 A CN 202010245249A CN 111233653 A CN111233653 A CN 111233653A
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reaction
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fixed bed
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吴健
丁德
陈殷
吴跃伟
白晓春
吕平海
郭安祥
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Central South University
Electric Power Research Institute of State Grid Shaanxi Electric Power Co Ltd
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Electric Power Research Institute of State Grid Shaanxi Electric Power Co Ltd
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Abstract

The invention discloses an economical and efficient perfluoronitrile and perfluoroketone co-production process and device, which comprises the following steps: reacting oxygen with asymmetric perfluoroolefin to generate two kinds of acyl fluoride gas or generate perfluoroketone gas and acyl fluoride gas; when two kinds of acyl fluoride gas are generated, the boiling point of the first acyl fluoride gas is higher than that of the second acyl fluoride gas, then the first acyl fluoride gas is contacted with ammonia gas for reaction to be converted into perfluoroamide, and the perfluoroamide is dehydrated to be converted into perfluoronitrile; mixing the second acyl fluoride gas with hexafluoropropylene to react to generate a perfluoroketone compound; when perfluoroketone gas and acyl fluoride gas are generated, separating the perfluoroketone gas from the acyl fluoride gas, condensing and collecting the perfluoroketone gas, carrying out contact reaction on the acyl fluoride gas and ammonia gas to convert the acyl fluoride gas into perfluoroamide, and dehydrating the perfluoroamide to convert the perfluoroamide into perfluoronitrile. The method can prepare perfluoronitrile and perfluoroketone simultaneously, and has the advantages of simple preparation conditions and high atom economy of a reaction route.

Description

Economical and efficient perfluoronitrile and perfluoroketone co-production process and device
Technical Field
The invention belongs to the field of insulating gas preparation, and particularly relates to an economical and efficient perfluoronitrile and perfluoroketone co-production process and device.
Background
With the development of global economy and population growth, various greenhouse gases generated by the combustion and industrial production of fossil fuelsThe impact on the environment is increasingly intensified. In order to cope with global climate change, reducing the emission of greenhouse gases is a dilemma faced by global economic development for a long time in the future. The greenhouse effect of sulfur hexafluoride insulating gas widely applied in the power industry at present is 23900 times that of carbon dioxide, and the sulfur hexafluoride insulating gas is extremely difficult to degrade, so that the greenhouse gas is reduced in use, the influence on the atmospheric environment is weakened, the natural environment in which human beings rely on to live is protected, and higher requirements are provided for the insulating gas. The perfluoroisobutyronitrile (C4) and the perfluoropenta-carbon ketone (C5) have low boiling point, high volatility, excellent electrical insulating property, short degradation time and far lower than SF6The green house effect and the like, and is considered as a new generation of SF substitute6The environment-friendly insulating gas.
The perfluoronitrile and the perfluoroketone can be applied to the field of electrical insulation, and can also be applied to the fields of refrigerants, foaming agents, cleaning agents, fire extinguishing agents and the like. However, in the prior art, the preparation conditions of perfluoronitrile and perfluoroketone are harsh, the production cost is always high, and the large-scale application of perfluoronitrile and perfluoroketone in the industry cannot be realized for a long time. The device and the process of the invention can be used for preparing various perfluoroketones and perfluoronitriles, have high atom economy, reduce the discharge of three industrial wastes, have relatively mild reaction conditions and are beneficial to large-scale industrial production.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides an economic and efficient perfluoronitrile and perfluoroketone co-production process and device, which have the advantages of simple preparation conditions, high atom economy of a reaction route, low production cost and easy realization of continuous and large-scale production. The method can effectively reduce the production cost of perfluoronitrile and perfluoroketone, particularly can realize the preparation of two key intermediates of acyl fluoride by one step through the thermal cracking of asymmetric perfluoroolefin, and effectively shortens the reaction steps.
In order to achieve the purpose, the invention adopts the following technical scheme:
an economical and efficient perfluoronitrile and perfluoroketone co-production process comprises the following steps:
mixing oxygen and asymmetric perfluoroolefin to react to generate two kinds of acyl fluoride gas or generate perfluoroketone gas and acyl fluoride gas;
when two kinds of acyl fluoride gas are generated, separating the two kinds of acyl fluoride gas according to the difference of the boiling points of the two kinds of acyl fluoride gas to obtain a first acyl fluoride gas and a second acyl fluoride gas, wherein the boiling point of the first acyl fluoride gas is higher than that of the second acyl fluoride gas, then contacting and reacting the first acyl fluoride gas with ammonia gas to convert the first acyl fluoride gas into perfluoroamide, and dehydrating the perfluoroamide to convert the perfluoroamide into perfluoronitrile; mixing the second acyl fluoride gas with hexafluoropropylene to react to generate a perfluoroketone compound;
when perfluoroketone gas and acyl fluoride gas are generated, separating the perfluoroketone gas from the acyl fluoride gas, condensing and collecting the perfluoroketone gas, carrying out contact reaction on the acyl fluoride gas and ammonia gas to convert the acyl fluoride gas into perfluoroamide, and dehydrating the perfluoroamide to convert the perfluoroamide into perfluoronitrile.
Further, the asymmetric perfluoroolefin is hexafluoropropylene dimer, hexafluoropropylene trimer, octafluoro-1-butene or other asymmetric perfluoroolefin.
Further, the reaction temperature of the oxygen and the asymmetric perfluoroolefin is 150-300 ℃, the molar ratio of the oxygen to the asymmetric perfluoroolefin is (0.5-2) to 1, and the contact time of the oxygen and the asymmetric perfluoroolefin is 60-300 s.
Further, the oxygen and the asymmetric perfluoroolefin are mixed and reacted to add the catalyst, and the catalyst used for the oxygen and the asymmetric perfluoroolefin comprises activated carbon or alumina-supported MoO3NiO or Ag2The load capacity of the catalyst used by O, oxygen and asymmetric perfluoroolefin is 5-50%.
Further, the preparation method of the catalyst comprises the following steps: weighing ammonium molybdate, nickel nitrate or silver nitrate to prepare 0.2-2mol/L aqueous solution, adding an activated carbon or alumina molecular sieve into the aqueous solution according to the specific gravity of the activated carbon or alumina molecular sieve of the catalyst, stirring for 0.5-3h, removing water by using a rotary evaporator, calcining and drying in a muffle furnace at 150-250 ℃ until the mass of the catalyst is unchanged to obtain the catalyst loaded with the activated carbon or alumina molecular sieve;
when nickel nitrate or silver nitrate is used for preparing the aqueous solution, NaOH solution with the same molar quantity as the nickel nitrate or silver nitrate is also required to be added into the aqueous solution.
Further, the reaction temperature of the second acyl fluoride gas and hexafluoropropylene is 100-250 ℃, and the contact reaction time of the second acyl fluoride gas and hexafluoropropylene is 10-600 s.
Further, a catalyst is added in the mixing reaction of the second acyl fluoride gas and hexafluoropropylene, and the catalyst used in the reaction of the second acyl fluoride gas and hexafluoropropylene is an alkali metal fluoride salt loaded by activated carbon or a composite catalyst of dimethylethanolamine, 2-morpholinoethanol and DABCO grafted on the surface of alumina.
Further, the preparation method of the alkali metal fluoride salt loaded on the activated carbon comprises the following steps: respectively preparing NaF, KF or CsF aqueous solution with the concentration of 0.2-2mol/L, adding activated carbon according to the activated carbon loading amount in the catalyst, stirring for 2h, removing water through a rotary evaporator, and placing in a muffle furnace to burn for 4h at 200 ℃;
the preparation method of the alumina composite catalyst comprises the following steps: surface treatment of alumina support with thionyl chloride or acid chloride followed by Me addition2NCH2CH2OH、O(CH2CH2)2NCH2CH2OH or N (CH)2CH2)3Carrying out contact reaction on N and an alumina loading agent, removing the solvent after the reaction is finished, washing for 6 times, and drying to obtain a catalyst used for the reaction of the second acyl fluoride gas and hexafluoropropylene; the second acyl fluoride gas is reacted with hexafluoropropylene using a catalyst having a loading of 5-25%.
Further, the reaction temperature of the first acyl fluoride gas and the reaction temperature of the ammonia gas are both 0-50 ℃, the reaction temperature of perfluoroamide dehydration is 0-50 ℃, and when the perfluoroamide is dehydrated by adopting a catalyst, the catalyst used by the perfluoroamide is WO loaded by active carbon3、Al2O3The loading amount of the catalyst used for the perfluoroamide is 10-80%; when the perfluoroamide is dehydrated by adopting a dehydrating agent, the dehydrating agent used by the perfluoroamide is trifluoroacetic acidAnhydride, phosphorus oxychloride, thionyl chloride or phosphorus pentoxide.
The invention also provides an economic and efficient perfluoronitrile and perfluoroketone co-production device, which comprises an oxygen cylinder, wherein the outlet of the oxygen cylinder is connected with the first inlet of a first gas mixer, the second inlet of the first gas mixer is connected with the outlet of a gasifier, the inlet of the gasifier is connected with the outlet of a liquid storage tank, asymmetric perfluoroolefin is filled in the liquid storage tank, the outlet of the first gas mixer is connected with the inlet of a first tubular fixed bed reactor, and the outlet of the first tubular fixed bed reactor is connected with a first low-temperature rectification tower;
the tower top condenser of the first cryogenic rectification tower is connected with a first inlet of a second gas mixer, a second inlet of the second gas mixer is connected with an outlet of a hexafluoropropylene gas tank, an outlet of the second gas mixer is connected with an inlet of a second tubular fixed bed reactor, an outlet of the second tubular fixed bed reactor is connected with the second cryogenic rectification tower, and the tower top condenser of the second cryogenic rectification tower is connected with an inlet of a perfluoroketone collection tank;
the tower kettle of the first cryogenic rectification tower is connected with a first inlet of the first kettle type reactor, a second inlet of the first kettle type reactor is connected with an outlet of the liquid ammonia tank, an outlet of the first kettle type reactor is connected with an inlet of the second kettle type reactor, an outlet of the second kettle type reactor is connected with a third cryogenic rectification tower, and a tower top condenser of the third cryogenic rectification tower is connected with a perfluoronitrile collecting tank.
Compared with the prior art, the invention has at least the following beneficial effects:
the method has the advantages of controllable process conditions, short reaction route, simple preparation conditions and high atom economy of the reaction route, particularly can realize the preparation of two key intermediate acyl fluorides in one step by the thermal cracking of asymmetric perfluoroolefin, effectively shortens the reaction steps, has larger boiling point difference of the two generated intermediate acyl fluorides, is easy to separate and purify, and is suitable for large-scale application in industrialization. The invention can prepare perfluoronitrile and perfluoroketone at the same time; starting from the cheap raw materials of asymmetric perfluoroolefin and oxygen, the industrial preparation of two novel environment-friendly insulating gases is realized with the atom economy of more than 95%. The process can greatly reduce the production cost and the discharge of three wastes in the production process, and provides powerful support for the large-scale application of the two compounds in the fields of insulating media, refrigerants, foaming agents, cleaning agents, fire extinguishing agents and the like. The catalyst used in the oxidative cracking and dehydration reaction in the process is cheap and efficient, and is beneficial to reducing the production cost. The co-production device not only can be used for producing perfluoroisobutyronitrile and perfluoropentacarbon, but also can be used for producing other types of perfluoroketone and perfluoronitrile. The method has the advantages of simple and efficient process route, most of reactants and products are gas-phase, the feeding components are stable, and the intermittent operation or the continuous operation can be adopted. In the oxidative cracking stage, a tubular fixed bed reactor is filled with a catalyst loaded by an activated carbon or alumina molecular sieve, so that the contact area between reactants and the catalyst is favorably increased, and the reaction efficiency is favorably improved.
Furthermore, the invention also provides an economic and efficient perfluoronitrile and perfluoroketone co-production device, which gasifies the liquid asymmetric perfluoroolefin, and the gasified asymmetric perfluoroolefin can fully contact with oxygen molecules due to the small molecular distance of liquid molecules, so that the reaction time can be shortened, and the efficiency of oxidative cracking can be improved. And the presence of more oxygen-contacted asymmetric perfluoroolefin may inhibit further cracking of the acyl fluoride gas produced by cracking, thereby reducing the introduction of other impurities.
Drawings
FIG. 1 is a schematic view of the construction of an environmentally friendly insulating gas cogeneration unit of the present invention;
FIG. 2 is a process diagram of the production of the environment-friendly insulating gas according to the present invention;
in the drawings: the system comprises a 1-oxygen cylinder, a 2-liquid storage tank, a 3-gasifier, a 4-first gas mixer, a 5-first tubular fixed bed reactor, a 6-first cryogenic rectification tower, a 7-tower top condenser, an 8-second gas mixer, a 9-hexafluoropropylene tank, a 10-second tubular fixed bed reactor, an 11-second cryogenic rectification tower, a 12-perfluoroketone collecting tank, a 13-first kettle type reactor, a 14-liquid ammonia tank, a 15-second kettle type reactor, a 16-third cryogenic rectification tower and a 17-perfluoronitrile collecting tank.
Detailed Description
The invention is further described with reference to the following figures and detailed description.
As shown in fig. 1 and fig. 2, the present invention provides an economical and efficient process for co-producing perfluoronitrile and perfluoroketone, comprising the following steps:
mixing oxygen and asymmetric perfluoroolefin to react to generate two kinds of acyl fluoride gas or generate perfluoroketone gas and acyl fluoride gas;
when two kinds of acyl fluoride gas are generated, separating the two kinds of acyl fluoride gas according to the difference of the boiling points of the two kinds of acyl fluoride gas to obtain a first acyl fluoride gas and a second acyl fluoride gas, wherein the boiling point of the first acyl fluoride gas is higher than that of the second acyl fluoride gas, then contacting and reacting the first acyl fluoride gas with ammonia gas to convert the first acyl fluoride gas into perfluoroamide, and dehydrating the perfluoroamide to convert the perfluoroamide into perfluoronitrile; mixing the second acyl fluoride gas with hexafluoropropylene to react to generate a perfluoroketone compound;
when perfluoroketone gas and acyl fluoride gas are generated, separating the perfluoroketone gas from the acyl fluoride gas, condensing and collecting the perfluoroketone gas, carrying out contact reaction on the acyl fluoride gas and ammonia gas to convert the acyl fluoride gas into perfluoroamide, and dehydrating the perfluoroamide to convert the perfluoroamide into perfluoronitrile.
Specifically, the specific steps of this embodiment are as follows:
1) carrying out oxidative cracking reaction on oxygen and asymmetric perfluoroolefin in a first tubular fixed bed reactor 5 under the condition of a catalyst or under the condition of no catalyst; two kinds of acyl fluoride gas are generated or perfluoroketone gas and acyl fluoride gas are generated.
2a) When two kinds of acyl fluoride gases are generated in the first tubular fixed bed reactor 5
21a) The effluent of the first tubular fixed bed reactor 5 mainly comprises two acyl fluoride gas mixtures with different boiling points, the ratio of the two acyl fluoride gas mixtures flowing out of the first tubular fixed bed reactor 5 is about 1:1, the difference of the boiling points is more than 20 ℃, the two acyl fluoride gas mixtures flow out and enter a first low-temperature rectifying tower 6 for separation,
22a) the separated acyl fluoride with low boiling point and Hexafluoropropylene (HFP) with 1-10 times of equivalent weight are mixed and enter a second tubular fixed bed reactor 10 to be contacted and reacted under the action of a catalyst to generate perfluoroketone, and then enter a second low-temperature rectifying tower 11 to be separated to obtain high-purity perfluoroketone;
acyl fluoride gas with high boiling point separated from the first cryogenic rectification tower 6 enters a first kettle type reactor 13 to react with ammonia gas to generate perfluoroamide and is separated out; the perfluoroamide enters a second kettle type reactor 15, is dehydrated by a dehydrating agent or is dehydrated by a catalyst to be converted into perfluoronitrile, and then enters a third low-temperature rectifying tower 16 to be separated to obtain the high-purity perfluoronitrile.
2b) When the perfluoroketone gas and the acyl fluoride gas are generated in the first tubular fixed-bed reactor 5
Perfluoroketone gas and acyl fluoride gas generated in the first tubular fixed bed reactor 5 are separated by a first cryogenic rectifier 6;
the perfluoroketone gas is directly condensed and separated by the first cryogenic rectification tower 6 and then condensed, liquefied and collected by a perfluoroketone liquid storage tank at the tower kettle of the first cryogenic rectification tower 6;
the acyl fluoride gas and ammonia gas are contacted and reacted in the first kettle type reactor 13 to be converted into perfluoroamide, the perfluoroamide enters the second kettle type reactor 15, and the perfluoroamide is dehydrated and converted into perfluoronitrile under the action of a dehydrating agent or a catalyst in the second kettle type reactor 15.
In a preferred embodiment of the invention, liquid asymmetric perfluoroolefin is gasified in step 1), and the molar ratio of oxygen to asymmetric perfluoroolefin is 1:1, the reaction temperature is 150-300 ℃, and the reaction time is 60-300 s. Because the distance between molecules of liquid molecules is smaller, the gasified asymmetric perfluoroolefin can be fully contacted with oxygen molecules, thereby shortening the reaction time and improving the efficiency of oxidative cracking. And the presence of more oxygen-contacted asymmetric perfluoroolefin may inhibit further cracking of the acyl fluoride gas produced by cracking, thereby reducing the introduction of other impurities.
Wherein the asymmetric perfluoroolefin is hexafluoropropylene dimer, hexafluoropropylene trimer, octafluoro-1-butene or other asymmetric perfluoroolefin.
As shown in fig. 1, the invention further provides an economic and efficient perfluoronitrile or perfluoroketone co-production device, which comprises an oxygen cylinder 1, an asymmetric perfluoroolefin tank 2, a vaporizer 3, a first tubular fixed bed reactor 5, a second tubular fixed bed reactor 10, a first cryogenic rectification tower 6, a second cryogenic rectification tower 11, a hexafluoropropylene tank 9, a perfluoroketone collection tank 12, a first kettle-type reactor 13, a second kettle-type reactor 15, a third cryogenic rectification tower 16, a perfluoronitrile collection tank 17, a first gas mixer 4 and a second gas mixer 8.
The oxygen cylinder 1 is connected with a first gas mixer 4 through a pipeline, the materials in the liquid storage tank 2 enter the first gas mixer 4 after being vaporized by a vaporizer 3, and the mixed materials enter a first tubular fixed bed reactor 5 through a pipeline and then undergo an oxidative cracking reaction; the effluent of the first tubular fixed bed reactor 5 enters a tower kettle of a first cryogenic rectification tower 6, an overhead condenser 7 and a hexafluoropropylene tank 9 of the first cryogenic rectification tower 6 are respectively connected to a second gas mixer 8, the materials are mixed by the second gas mixer 8 and then enter a second tubular fixed bed reactor 10, the effluent of the second tubular fixed bed reactor 10 enters a tower kettle of a second cryogenic rectification tower 11, and the effluent of the overhead condenser 7 of the second cryogenic rectification tower 11 flows into a perfluoroketone collecting tank 12;
the effluent of the tower bottom of the first cryogenic rectification tower 6 enters a first kettle type reactor 13, a liquid ammonia tank 14 is connected with the first kettle type reactor 13, the effluent of the first kettle type reactor 13 enters a second kettle type reactor 15, the effluent of the second kettle type reactor 15 enters the tower bottom of a third cryogenic rectification tower 16, and the effluent of the tower top condenser 7 of the third cryogenic rectification tower 16 enters a perfluoronitrile collecting tank 17.
Particularly, when the asymmetric olefin is subjected to oxidative cracking in the first tubular fixed bed reactor 5 to generate a mixture of perfluoroketone and acyl fluoride, the mixture is fractionated by the first cryogenic rectification tower 6 to realize the separation of perfluoroketone and acyl fluoride; the perfluoroketone obtained by separation can be directly condensed and collected, the acyl fluoride compound obtained by separation enters the first kettle type reactor 13 through a feeding pipeline, and the liquid ammonia tank 14 is connected with the first kettle type reactor 13 through a feeding pipeline and is connected with the first kettle type reactor 13Ammonia gas is subjected to ammoniation reaction to obtain perfluoroamide, the perfluoroamide enters a second kettle-type reactor 15 and then is subjected to dehydration reaction under the action of a catalyst and high temperature to be converted into a perfluoroisobutyronitrile crude product, the crude product enters a third low-temperature rectifying tower 15 for further purification, the effluent of a tower top condenser 7 enters a perfluoronitrile collecting tank 17 through a pipeline, the perfluoroamide generated in the first kettle-type reactor is separated and dried and then enters the second kettle-type reactor, the perfluoroamide is subjected to dehydration reaction under the action of the catalyst to be converted into perfluoronitrile, and the catalyst used by the second kettle-type reactor is WO supported by active carbon3、Al2O3The load is 10-80%, and the reaction time is 0.5-2 h; the dehydrating agent is trifluoroacetic anhydride, phosphorus pentoxide, phosphorus oxychloride or thionyl chloride, and the mass ratio of the dehydrating agent to the perfluoroamide is as follows: 1-7:1, the dehydration reaction time is as follows: 1-4h, the reaction temperature in the first kettle-type reactor and the second kettle-type reactor is: 0 to 50 ℃.
The material of the kettle type reactor or the tubular fixed bed reactor is stainless steel or nickel alloy and other metal materials with good corrosion resistance and heat conductivity, and the first tubular fixed bed reactor 5 does not use catalyst or uses activated carbon or alumina loaded MoO3NiO or Ag2O catalyst (Cat 1) with a catalyst loading of 5-50%, and the catalyst (Cat 2) used in the second tubular fixed bed reactor 10 comprises an alkali metal fluoride salt supported on activated carbon, or dimethylethanolamine (Me) grafted on the surface of alumina2NCH2CH2OH), 2-morpholinoethanol (O (CH)2CH2)2NCH2CH2OH) and DABCO (N (CH)2CH2)3N) is used as a composite catalyst. The reaction temperature of the second tubular fixed bed reactor 10 is 100-250 ℃, and the reaction time of the acyl fluoride gas and the hexafluoropropylene in the second tubular fixed bed reactor 10 is 10-600 s.
Preparation of catalyst Cat 1 of the first tubular fixed-bed reactor 5: weighing ammonium molybdate, nickel nitrate or silver nitrate to prepare 0.2-2mol/L aqueous solution, adding activated carbon or alumina molecular sieve into the aqueous solution according to the proportion of activated carbon or alumina in the catalyst, stirring for 0.5-3h, removing water by a rotary evaporator, calcining and drying in a muffle furnace at the temperature of 150-250 ℃ to constant weight, namely obtaining the catalyst loaded with the activated carbon or alumina molecular sieve, if the nickel nitrate or silver nitrate solution is adopted, adding NaOH solution with the same molar weight as the nickel nitrate or silver nitrate solution.
Carrying out contact reaction on oxygen and asymmetric perfluoroolefin in a first tubular fixed bed reactor 5 under the condition of a catalyst or without the catalyst, wherein the reaction temperature is 150-: 1, the contact time of the oxygen and the asymmetric perfluoroolefin in the first tubular fixed bed reactor 5 is 60 to 300 s.
The preparation method of the alkali metal fluoride salt supported by the activated carbon of the catalyst in the second tubular fixed bed reactor 10 is as follows: respectively preparing NaF, KF or CsF aqueous solution with the concentration of 0.2-2mol/L, adding activated carbon according to the activated carbon loading amount in the catalyst, stirring for 2h, removing water through a rotary evaporator, and placing in a muffle furnace to burn for 4h at 200 ℃; step 21) the preparation method of the alumina composite catalyst comprises the following steps: surface treatment of alumina support with thionyl chloride or acid chloride followed by Me addition2NCH2CH2OH、O(CH2CH2)2NCH2CH2OH or N (CH)2CH2)3Carrying out contact reaction on N and an alumina loading agent, removing the solvent after the reaction is finished, washing for 6 times, and drying to obtain a second catalyst; the loading of the second catalyst is 5-25%.
After the mixed gas product flowing out of the first tubular fixed bed reactor 5 is separated by the first cryogenic rectification tower 6, the low molecular weight acyl fluoride gas collected by the tower top condenser 7 of the first cryogenic rectification tower 6 is mixed with 1-10 times equivalent of HFP and then enters the second tubular fixed bed reactor to be contacted and reacted under the action of a catalyst to obtain a crude product of perfluoroketone, the reaction time is 10-600s, the reaction temperature is 100-250 ℃, and the separated acyl fluoride crude product with low boiling point enters the second cryogenic rectification tower 11 for further purification.
Acyl fluoride gas with high boiling point flows into the first kettle type reactor 13 from the tower kettle of the first low-temperature rectifying tower 6, and is subjected to ammoniation reaction with ammonia gas to obtain perfluoroamide, the perfluoroamide enters the second kettle type reactor 15, is subjected to dehydration reaction under the action of a catalyst and high temperature to be converted into a perfluoroisobutyronitrile crude product, and the crude product enters the third low-temperature rectifying tower 16 for further purification.
The perfluoroamide produced in the first kettle-type reactor 13 is separated and dried, then enters the second kettle-type reactor 15, is subjected to dehydration reaction under the action of a catalyst and is converted into perfluoronitrile, and the catalyst used in the second kettle-type reactor 15 is WO loaded by active carbon3、Al2O3The load is 10-80%, and the reaction time is 0.5-2 h; the dehydrating agent is trifluoroacetic anhydride, phosphorus pentoxide, phosphorus oxychloride or thionyl chloride, and the mass ratio of the dehydrating agent to the perfluoroamide is as follows: 1:1-7:1, and the dehydration reaction time is as follows: for 1-4h, the reaction temperature in the first kettle-type reactor 13 and the second kettle-type reactor 16 is: 0 to 50 ℃.
Example 1
The length of the first tubular fixed bed reactor 5 is 80cm, the pipe diameter is 1 inch, the reaction temperature is 150 ℃, silver oxide with 5 percent of activated carbon loading is used as a catalyst, the filling proportion of the catalyst in the first tubular fixed bed reactor 5 is 75 percent, and O is added2And hexafluoropropylene dimer in a molar ratio of 0.5: 1 is led into a first tubular fixed bed reactor 5 for reaction, the reaction pressure is 3bar, and the reaction time is 60 s. Through gas chromatography detection, the total fluorine isobutyryl fluoride accounts for 15.5 percent and the trifluoroacetyl fluoride accounts for 16.3 percent of the product composition;
the length of the second tubular fixed bed reactor 10 is 80cm, the pipe diameter is 1 inch, the reaction temperature is 100 ℃, CsF with 5% of activated carbon loading is used as a catalyst, the filling proportion of the catalyst in the second tubular fixed bed reactor 10 is 75%, the obtained trifluoroacetyl fluoride and hexafluoropropylene are introduced into the second tubular fixed bed reactor 10 according to the molar ratio of 1:1, the reaction pressure is 4bar, and the reaction time is 10 s. The product is perfluoro-penta-carbon ketone, and the yield is 46.2%;
the volume of the first kettle-type reactor 13 and the second kettle-type reactor 15 is 3L, the perfluoro isobutyryl fluoride obtained by separation and liquid ammonia in a liquid ammonia tank are put into the first kettle-type reactor 13 according to the molar ratio of 1:1.2, electric stirring is started, the stirring speed is 300 r/min, the reaction temperature of the first kettle-type reactor 13 is set to be 0 ℃, the reaction pressure is 10bar, the reaction pressure is kept for 0.5h, the obtained product is transferred to the second kettle-type reactor 15, then trifluoroacetic anhydride with equivalent weight is added into the second kettle-type reactor 15 as a dehydrating agent, the reaction temperature is 0 ℃, the reaction time is 1h, the gas flowing out of the second kettle-type reactor 15 is purified by a third low-temperature rectifying tower 16, the product is perfluoro isobutyronitrile, the purity is 99.3%, and the total reaction yield is 66.4%.
Example 2
The length of the first tubular fixed bed reactor 5 is 80cm, the pipe diameter is 1 inch, the reaction temperature is 150 ℃, silver oxide with 5 percent of activated carbon loading is used as a catalyst, the filling proportion of the catalyst in the first tubular fixed bed reactor 5 is 75 percent, and O is added2And hexafluoropropylene dimer in a molar ratio of 1:1 is led into a first tubular fixed bed reactor 5 for reaction, the reaction pressure is 3bar, and the reaction time is 60 s. Gas chromatography detection shows that the product composition contains 21.3% of perfluoroisobutyryl fluoride and 23.8% of trifluoroacetyl fluoride;
the length of the second tubular fixed bed reactor 10 is 80cm, the pipe diameter is 1 inch, the reaction temperature is 100 ℃, CsF with 5% of activated carbon loading is used as a catalyst, the filling proportion of the catalyst in the second tubular fixed bed reactor 10 is 75%, the obtained trifluoroacetyl fluoride and hexafluoropropylene are introduced into the second tubular fixed bed reactor 10 according to the molar ratio of 1:1, the reaction pressure is 4bar, and the reaction time is 10 s. The product is perfluoro-penta-carbon ketone, and the yield is 46.2%;
the volume of the first kettle-type reactor 13 and the second kettle-type reactor 15 is 3L, the perfluoro isobutyryl fluoride obtained by separation and liquid ammonia in a liquid ammonia tank are put into the first kettle-type reactor 13 according to the molar ratio of 1:1.2, electric stirring is started, the stirring speed is 300 r/min, the reaction temperature of the first kettle-type reactor 13 is set to be 10 ℃, the reaction pressure is 10bar, the reaction pressure is kept for 0.5h, the obtained product is transferred to the second kettle-type reactor 15, then trifluoroacetic anhydride with equivalent weight is added into the second kettle-type reactor 15 as a dehydrating agent, the reaction temperature is 10 ℃, the reaction time is 1h, the gas flowing out from the second kettle-type reactor 15 is purified by a third low-temperature rectifying tower 16, the product is perfluoro isobutyronitrile, the purity is 99.3%, and the total reaction yield is 66.4%.
Example 3
The length of the first tubular fixed bed reactor 5 is 80cm, the pipe diameter is 1 inch, the reaction temperature is 170 ℃, silver oxide with 5 percent of activated carbon loading is used as a catalyst, the filling proportion of the catalyst in the first tubular fixed bed reactor 5 is 75 percent, and O is added2And hexafluoropropylene dimer in a molar ratio of 1:1 is led into a first tubular fixed bed reactor 5 for reaction, the reaction pressure is 3bar, and the reaction time is 60 s. The gas chromatography detection shows that the product composition contains 26.2% of perfluoroisobutyryl fluoride and 27.6% of trifluoroacetyl fluoride;
the length of the second tubular fixed bed reactor 10 is 80cm, the pipe diameter is 1 inch, the reaction temperature is 120 ℃, CsF with 5% of activated carbon loading is used as a catalyst, the filling proportion of the catalyst in the second tubular fixed bed reactor 10 is 75%, the obtained trifluoroacetyl fluoride and hexafluoropropylene are introduced into the second tubular fixed bed reactor 10 according to the molar ratio of 1:1, the reaction pressure is 4bar, and the reaction time is 10 s. The product is perfluoro-penta-carbon ketone, and the yield is 55.8%;
the volume of the first kettle-type reactor 13 and the second kettle-type reactor 15 is 3L, the perfluoro isobutyryl fluoride obtained by separation and liquid ammonia in a liquid ammonia tank are put into the first kettle-type reactor 13 according to the molar ratio of 1:1.2, electric stirring is started, the stirring speed is 300 r/min, the reaction temperature of the first kettle-type reactor 13 is set to be 10 ℃, the reaction pressure is 10bar, the reaction pressure is kept for 0.5h, the obtained product is transferred to the second kettle-type reactor 15, 2 times of equivalent of trifluoroacetic anhydride is added into the second kettle-type reactor 15 as a dehydrating agent, the reaction temperature is 10 ℃, the reaction time is 1h, the gas flowing out of the second kettle-type reactor 15 is purified by a third low-temperature rectifying tower, the product is perfluoro isobutyronitrile, the purity is 99.3%, and the total reaction yield is 74.8%.
Example 4
The length of the first tubular fixed bed reactor 5 is 80cm, the pipe diameter is 1 inch, the reaction temperature is 170 ℃, silver oxide with 10 percent of activated carbon loading is used as a catalyst, the filling proportion of the catalyst in the first tubular fixed bed reactor 5 is 75 percent, and O is added2And hexafluoropropylene dimer in a molar ratio of 1:1 is led into a first tubular fixed bed reactor 5 for reaction, the reaction pressure is 3bar, and the reaction time is 60 s. The gas chromatography detection shows that the product composition contains 32.7 percent of perfluoroisobutyryl fluoride and 35.9 percent of trifluoroacetyl fluoride;
the length of the second tubular fixed bed reactor 10 is 80cm, the pipe diameter is 1 inch, the reaction temperature is 120 ℃, CsF with 6% of activated carbon loading is used as a catalyst, the filling proportion of the catalyst in the second tubular fixed bed reactor 10 is 75%, the obtained trifluoroacetyl fluoride and hexafluoropropylene are introduced into the second tubular fixed bed reactor 10 according to the molar ratio of 1:1, the reaction pressure is 4bar, and the reaction time is 10 s. The product is perfluoro-penta-carbon ketone, and the yield is 61.3%;
the volume of the first kettle-type reactor and the second kettle-type reactor 15 is 3L, the perfluoro isobutyryl fluoride obtained by separation and liquid ammonia in a liquid ammonia tank are put into the first kettle-type reactor according to the molar ratio of 1:1.2, electric stirring is started, the stirring speed is 300 r/min, the reaction temperature of the first kettle-type reactor is set to 10 ℃, the reaction pressure is 10bar, the reaction time is kept for 0.5h, the obtained product is transferred to the second kettle-type reactor 15, 2 times of equivalent of trifluoroacetic anhydride is added into the second kettle-type reactor 15 as dehydrating agent, the reaction temperature is 10 ℃, the dehydrating agent is used for 1h, the gas flowing out of the second kettle-type reactor 15 is purified by a third low-temperature rectifying tower, the product is perfluoro isobutyronitrile, the purity is 99.3%, and the total reaction yield is 80.3%.
Example 5
The length of the first tubular fixed bed reactor 5 is 80cm, the pipe diameter is 1 inch, the reaction temperature is 170 ℃, nickel oxide with 10 percent of activated carbon loading is used as a catalyst, the filling proportion of the catalyst in the first tubular fixed bed reactor 5 is 75 percent, and O is added2And hexafluoropropylene dimer in a molar ratio of 1:1 is led into a first tubular fixed bed reactor 5 for reaction, the reaction pressure is 3bar, and the reaction time is 60 s. The gas chromatography detection shows that the product composition contains 28.6 percent of perfluoroisobutyryl fluoride and 29.1 percent of trifluoroacetyl fluoride;
the length of the second tubular fixed bed reactor 10 is 80cm, the pipe diameter is 1 inch, the reaction temperature is 120 ℃, NaF with 6% of activated carbon loading is used as a catalyst, the filling proportion of the catalyst in the second tubular fixed bed reactor 10 is 75%, the obtained trifluoroacetyl fluoride and hexafluoropropylene are introduced into the second tubular fixed bed reactor 10 according to the molar ratio of 1:1, the reaction pressure is 4bar, and the reaction time is 10 s. The product is perfluoro-penta-carbon ketone, and the yield is 52.9%;
the volumes of the first kettle-type reactor and the second kettle-type reactor 15 are both 3L, the perfluoroisobutyryl fluoride obtained by separation and liquid ammonia in a liquid ammonia tank are put into the first kettle-type reactor according to the molar ratio of 1:1.2, electric stirring is started, the stirring speed is 300 r/min, the temperature of the first reactor is set to 10 ℃, the reaction pressure is 10bar, the reaction is kept for 0.5h, the obtained product is transferred to the second kettle-type reactor 15, 2 times of equivalent of phosphorus oxychloride is added into the second kettle-type reactor 15 as a dehydrating agent, the reaction temperature is 10 ℃, the reaction time is 1h, the gas flowing out of the second kettle-type reactor 15 is further purified by a low-temperature rectifying tower, the product is perfluoroisobutyronitrile, the purity is 99.2%, and the total reaction yield is 65.9%.
Example 6
The length of the first tubular fixed bed reactor 5 is 80cm, the pipe diameter is 1 inch, the reaction temperature is 170 ℃, silver oxide with 10 percent of activated carbon loading is used as a catalyst, the filling proportion of the catalyst in the first tubular fixed bed reactor 5 is 75 percent, and O is added2And hexafluoropropylene dimer in a molar ratio of 1:1 is introduced into a first tubular fixed bed reactor 5 for reaction, the reaction pressure is 3bar, and the reaction time is 120 s. Through gas chromatography detection, the total fluorine isobutyryl fluoride accounts for 38.3 percent and the trifluoroacetyl fluoride accounts for 39.7 percent in the product composition;
the length of the second tubular fixed bed reactor 10 is 80cm, the pipe diameter is 1 inch, the reaction temperature is 120 ℃, CsF with 6% of activated carbon loading is used as a catalyst, the filling proportion of the catalyst in the second tubular fixed bed reactor 10 is 75%, the obtained trifluoroacetyl fluoride and hexafluoropropylene are introduced into the second tubular fixed bed reactor 10 according to the molar ratio of 1:1, the reaction pressure is 4bar, and the reaction time is 60 s. The product is perfluoro-penta-carbon ketone, and the yield is 67.8%;
the volume of the first kettle-type reactor and the volume of the second kettle-type reactor are 3L, the perfluoro isobutyryl fluoride obtained by separation and liquid ammonia in a liquid ammonia tank are put into the first kettle-type reactor according to the molar ratio of 1:1.2, electric stirring is started, the stirring speed is 300 r/min, the reaction temperature of the first kettle-type reactor is set to 10 ℃, the reaction pressure is 10bar, the reaction time is kept for 0.75h, the obtained product is transferred to the second kettle-type reactor, 2 times of equivalent of trifluoroacetic anhydride is added into the second kettle-type reactor as a dehydrating agent, the reaction temperature is 10 ℃, the reaction time is 1.5h, the gas flowing out of the second kettle-type reactor is purified by a third low-temperature rectifying tower, the product is perfluoro isobutyronitrile, the purity of the perfluoro isobutyronitrile is 99.3%, and the total reaction yield is 83.5%.
Example 7
The length of the first tubular fixed bed reactor 5 is 80cm, the pipe diameter is 1 inch, the reaction temperature is 170 ℃, silver oxide with 10 percent of activated carbon loading is used as a catalyst, the filling proportion of the catalyst in the first tubular fixed bed reactor 5 is 75 percent, and O is added2And hexafluoropropylene dimer are introduced into the first tubular fixed bed reactor 5 for reaction according to the molar ratio of 2:1, the reaction pressure is 3bar, and the reaction time is 120 s. The gas chromatography detection shows that the product composition contains 37.7 percent of perfluoroisobutyryl fluoride and 38.4 percent of trifluoroacetyl fluoride;
the length of the second tubular fixed bed reactor 10 is 80cm, the pipe diameter is 1 inch, the reaction temperature is 120 ℃, CsF with 6% of activated carbon loading is used as a catalyst, the filling proportion of the catalyst in the second tubular fixed bed reactor 10 is 75%, the obtained trifluoroacetyl fluoride and hexafluoropropylene are introduced into the second tubular fixed bed reactor 10 according to the molar ratio of 1:1, the reaction pressure is 4bar, and the reaction time is 60 s. The product is perfluoro-penta-carbon ketone, and the yield is 67.8%;
the volume of the first kettle-type reactor and the volume of the second kettle-type reactor are 3L, the perfluoro isobutyryl fluoride obtained by separation and liquid ammonia in a liquid ammonia tank are put into the first kettle-type reactor according to the molar ratio of 1:1.2, electric stirring is started, the stirring speed is 300 r/min, the reaction temperature of the first kettle-type reactor is set to 10 ℃, the reaction pressure is 10bar, the reaction time is kept for 0.75h, the obtained product is transferred to the second kettle-type reactor, 2 times of equivalent of trifluoroacetic anhydride is added into the second kettle-type reactor as a dehydrating agent, the reaction temperature is 10 ℃, the reaction time is 1.5h, the gas flowing out of the second kettle-type reactor is purified by a third low-temperature rectifying tower, the product is perfluoro isobutyronitrile, the purity of the perfluoro isobutyronitrile is 99.3%, and the total reaction yield is 83.5%.
Example 8
The length of the first tubular fixed bed reactor 5 is 80cm, the pipe diameter is 1 inch, the reaction temperature is 200 ℃, silver oxide with 15 percent of activated carbon loading is used as a catalyst, the filling proportion of the catalyst in the first tubular fixed bed reactor 5 is 75 percent, and O is added2And hexafluoropropylene dimer in a molar ratio of 1:1 is introduced into a first tubular fixed bed reactor 5 for reaction, the reaction pressure is 3bar, and the reaction time is 180 s. Gas chromatography detection shows that the product composition contains 50.9% of perfluoroisobutyryl fluoride and 49.1% of trifluoroacetyl fluoride;
the length of the second tubular fixed bed reactor 10 is 80cm, the pipe diameter is 1 inch, the reaction temperature is 150 ℃, CsF with 8% of activated carbon loading is used as a catalyst, the filling proportion of the catalyst in the second tubular fixed bed reactor 10 is 75%, the obtained trifluoroacetyl fluoride and hexafluoropropylene are introduced into the second tubular fixed bed reactor 10 according to the molar ratio of 1:1, the reaction pressure is 4bar, and the reaction time is 120 s. The product is perfluoro-penta-carbon ketone, and the yield is 79.5%;
the volume of the first kettle-type reactor and the volume of the second kettle-type reactor are 3L, the perfluoro isobutyryl fluoride obtained by separation and liquid ammonia in a liquid ammonia tank are put into the first kettle-type reactor according to the molar ratio of 1:1.2, electric stirring is started, the stirring speed is 300 r/min, the reaction temperature of the first kettle-type reactor is set to be 20 ℃, the reaction pressure is 10bar, the reaction time is kept for 1.0h, the obtained product is transferred to the second kettle-type reactor, then 3 times of equivalent of trifluoroacetic anhydride is added into the second kettle-type reactor as a dehydrating agent, the reaction temperature is 20 ℃, the reaction time is 2.0h, the gas flowing out of the second kettle-type reactor is purified by a third low-temperature rectifying tower, the product is perfluoro isobutyronitrile, the purity of the perfluoro isobutyronitrile is 99.2%, and the total reaction yield is 86.5%.
Example 9
The length of the first tubular fixed bed reactor 5 is 80cm, the pipe diameter is 1 inch, the reaction temperature is 230 ℃, silver oxide with 20 percent of activated carbon loading is used as a catalyst, the filling proportion of the catalyst in the first tubular fixed bed reactor 5 is 75 percent, and O is added2And hexafluoropropylene dimer in a molar ratio of 1:1 is led into a first tubular fixed bed reactor 5 for reaction, the reaction pressure is 3bar, and the reaction time is 210 s. The detection of gas chromatography shows that the product composition contains 56.3 percent of perfluoroisobutyryl fluoride43.7% trifluoroacetyl fluoride;
the length of the second tubular fixed bed reactor 10 is 80cm, the pipe diameter is 1 inch, the reaction temperature is 180 ℃, CsF with 10% of activated carbon loading is used as a catalyst, the filling proportion of the catalyst in the second tubular fixed bed reactor 10 is 75%, the obtained trifluoroacetyl fluoride and hexafluoropropylene are introduced into the second tubular fixed bed reactor 10 according to the molar ratio of 1:1, the reaction pressure is 4bar, and the reaction time is 180 s. The product is perfluoro-penta-carbon ketone, and the yield is 83.6%;
the volume of the first kettle-type reactor and the volume of the second kettle-type reactor are 3L, the perfluoro isobutyryl fluoride obtained by separation and liquid ammonia in a liquid ammonia tank are put into the first kettle-type reactor according to the molar ratio of 1:1.2, electric stirring is started, the stirring speed is 300 r/min, the reaction temperature of the first kettle-type reactor is set to be 25 ℃, the reaction pressure is 10bar, the reaction time is kept for 1.25h, the obtained product is transferred to the second kettle-type reactor, then 4 times of equivalent of trifluoroacetic anhydride is added into the second kettle-type reactor as a dehydrating agent, the reaction temperature is 25 ℃, the reaction time is 2.5h, the gas flowing out of the second kettle-type reactor is purified by a third low-temperature rectifying tower, the product is perfluoro isobutyronitrile, the purity of the perfluoro isobutyronitrile is 99.2%, and the total reaction yield is 88.9%.
Example 10
The length of the first tubular fixed bed reactor 5 is 80cm, the pipe diameter is 1 inch, the reaction temperature is 250 ℃, silver oxide with 25 percent of activated carbon loading is used as a catalyst, the filling proportion of the catalyst in the first tubular fixed bed reactor 5 is 75 percent, and O is added2And hexafluoropropylene dimer in a molar ratio of 1:1 is led into a first tubular fixed bed reactor 5 for reaction, the reaction pressure is 3bar, and the reaction time is 240 s. Gas chromatography detection shows that the product composition contains 61.8% of perfluoroisobutyryl fluoride and 38.2% of trifluoroacetyl fluoride;
the length of the second tubular fixed bed reactor 10 is 80cm, the pipe diameter is 1 inch, the reaction temperature is 200 ℃, CsF with 15% of activated carbon loading is used as a catalyst, the filling proportion of the catalyst in the second tubular fixed bed reactor 10 is 75%, the obtained trifluoroacetyl fluoride and hexafluoropropylene are introduced into the second tubular fixed bed reactor 10 according to the molar ratio of 1:1, the reaction pressure is 4bar, and the reaction time is 210 s. The product is perfluoro-penta-carbon ketone, and the yield is 85.1%;
the volumes of the first kettle-type reactor and the second kettle-type reactor are both 3L, the perfluoro isobutyryl fluoride obtained by separation and liquid ammonia in a liquid ammonia tank are put into the first kettle-type reactor according to the molar ratio of 1:1.2, electric stirring is started, the stirring speed is 300 r/min, the temperature of the first kettle is set to be 35 ℃, the reaction pressure is 10bar, the reaction is kept for 1.5h, the obtained product is transferred to the second kettle-type reactor, 5 times of equivalent of trifluoroacetic anhydride is added into the second kettle-type reactor as a dehydrating agent, the reaction temperature is 35 ℃, the reaction time is 3.0h, the gas flowing out of the second kettle-type reactor is further purified by a low-temperature rectifying tower, the product is perfluoro isobutyronitrile, the purity is 99.2%, and the total reaction yield is 87.6%.
Example 11
The length of the first tubular fixed bed reactor 5 is 80cm, the pipe diameter is 1 inch, the reaction temperature is 270 ℃, silver oxide with 35 percent of activated carbon loading is used as a catalyst, the filling proportion of the catalyst in the first tubular fixed bed reactor 5 is 75 percent, and O is added2And hexafluoropropylene dimer in a molar ratio of 1:1 is led into a first tubular fixed bed reactor 5 for reaction, the reaction pressure is 3bar, and the reaction time is 270 s. According to gas chromatography detection, the product composition contains 57.8% of perfluoroisobutyryl fluoride and 42.2% of trifluoroacetyl fluoride;
the length of the second tubular fixed bed reactor 10 is 80cm, the pipe diameter is 1 inch, the reaction temperature is 230 ℃, CsF with 20% of activated carbon loading is used as a catalyst, the filling proportion of the catalyst in the second tubular fixed bed reactor 10 is 75%, the obtained trifluoroacetyl fluoride and hexafluoropropylene are introduced into the second tubular fixed bed reactor 10 according to the molar ratio of 1:1, the reaction pressure is 4bar, and the reaction time is 300 s. The product is perfluoro-penta-carbon ketone, and the yield is 87.2%;
the volumes of the first kettle-type reactor and the second kettle-type reactor are both 3L, the perfluoro isobutyryl fluoride obtained by separation and liquid ammonia in a liquid ammonia tank are put into the first kettle-type reactor according to the molar ratio of 1:1.2, electric stirring is started, the stirring speed is 300 r/min, the temperature of the first reaction kettle is set to 45 ℃, the reaction pressure is set to 10bar, the reaction is kept for 1.75h, the obtained product is transferred to the second kettle-type reactor, 6 times of equivalent of trifluoroacetic anhydride is added into the second kettle-type reactor as a dehydrating agent, the reaction temperature is 45 ℃, the reaction time is 3.5h, the gas flowing out of the second kettle-type reactor is further purified by a low-temperature rectifying tower, the product is perfluoro isobutyronitrile, the purity is 99.2%, and the total reaction yield is 87.1%.
Example 12
The length of the first tubular fixed bed reactor 5 is 80cm, the pipe diameter is 1 inch, the reaction temperature is 300 ℃, silver oxide with the activated carbon loading of 45 percent is used as a catalyst, the filling proportion of the catalyst in the first tubular fixed bed reactor 5 is 75 percent, and O is added2And hexafluoropropylene dimer in a molar ratio of 1:1 is introduced into a first tubular fixed bed reactor 5 for reaction, the reaction pressure is 3bar, and the reaction time is 300 s. The gas chromatography detection shows that the product composition contains 45.3 percent of perfluoroisobutyryl fluoride and 54.7 percent of trifluoroacetyl fluoride;
the length of the second tubular fixed bed reactor 10 is 80cm, the pipe diameter is 1 inch, the reaction temperature is 250 ℃, CsF with 25% of activated carbon loading is used as a catalyst, the filling proportion of the catalyst in the second tubular fixed bed reactor 10 is 75%, the obtained trifluoroacetyl fluoride and hexafluoropropylene are introduced into the second tubular fixed bed reactor 10 according to the molar ratio of 1:1, the reaction pressure is 4bar, and the reaction time is 480 s. The product is perfluoro-penta-carbon ketone, and the yield is 84.9%;
the volumes of the first kettle-type reactor and the second kettle-type reactor are both 3L, the perfluoro isobutyryl fluoride obtained by separation and liquid ammonia in a liquid ammonia tank are put into the first kettle-type reactor according to the molar ratio of 1:1.2, electric stirring is started, the stirring speed is 300 r/min, the temperature of the first reaction kettle is set to be 50 ℃, the reaction pressure is 10bar, the reaction is kept for 2.0h, the obtained product is transferred to the second kettle-type reactor, 7 times of equivalent of trifluoroacetic anhydride is added into the second kettle-type reactor as a dehydrating agent, the reaction temperature is 50 ℃, the reaction time is 4.0h, the gas flowing out of the second kettle-type reactor is further purified by a low-temperature rectifying tower, the product is perfluoro isobutyronitrile, the purity is 99.2%, and the total reaction yield is 85.4%.
Example 13
The length of the first tubular fixed bed reactor 5 is 80cm, the tube diameter is 1 inch, the reaction temperature is 300 ℃ toSilver oxide with the activated carbon loading of 45 percent is used as a catalyst, the filling proportion of the catalyst in the first tubular fixed bed reactor 5 is 75 percent, and O is added2And hexafluoropropylene dimer in a molar ratio of 1:1 is introduced into a first tubular fixed bed reactor 5 for reaction, the reaction pressure is 3bar, and the reaction time is 300 s. The gas chromatography detection shows that the product composition contains 45.3 percent of perfluoroisobutyryl fluoride and 54.7 percent of trifluoroacetyl fluoride;
the length of the second tubular fixed bed reactor 10 is 80cm, the pipe diameter is 1 inch, the reaction temperature is 250 ℃, CsF with 25% of activated carbon loading is used as a catalyst, the filling proportion of the catalyst in the second tubular fixed bed reactor 10 is 75%, the obtained trifluoroacetyl fluoride and hexafluoropropylene are introduced into the second tubular fixed bed reactor 10 according to the molar ratio of 1:1, the reaction pressure is 4bar, and the reaction time is 600 s. The product is perfluoro-penta-carbon ketone, and the yield is 84.0%;
the volumes of the first kettle-type reactor and the second kettle-type reactor are both 3L, the perfluoro isobutyryl fluoride obtained by separation and liquid ammonia in a liquid ammonia tank are put into the first kettle-type reactor according to the molar ratio of 1:1.2, electric stirring is started, the stirring speed is 300 r/min, the temperature of the first kettle is set to be 25 ℃, the reaction pressure is 10bar, the reaction is kept for 1.0h, the obtained product is transferred to the second kettle-type reactor, 2 times of equivalent of trifluoroacetic anhydride is added into the second kettle-type reactor as a dehydrating agent, the reaction temperature is 25 ℃, the reaction time is 4.0h, the gas flowing out of the second kettle-type reactor is further purified by a low-temperature rectifying tower, the product is perfluoro isobutyronitrile, the purity is 99.3%, and the total reaction yield is 89.7%.
Example 14
The length of the first tubular fixed bed reactor 5 is 80cm, the pipe diameter is 1 inch, the reaction temperature is 250 ℃, silver oxide with 20 percent of activated carbon loading is used as a catalyst, the filling proportion of the catalyst in the first tubular fixed bed reactor 5 is 75 percent, and O is added2And hexafluoropropylene dimer in a molar ratio of 1:1 is led into a first tubular fixed bed reactor 5 for reaction, the reaction pressure is 3bar, and the reaction time is 210 s. The gas chromatography detection shows that the product composition contains 65.8 percent of perfluoroisobutyryl fluoride and 34.2 percent of trifluoroacetyl fluoride;
the length of the second tubular fixed bed reactor 10 is 80cm, the pipe diameter is 1 inch, the reaction temperature is 250 ℃, CsF with 10% of activated carbon loading is used as a catalyst, the filling proportion of the catalyst in the second tubular fixed bed reactor 10 is 75%, the obtained trifluoroacetyl fluoride and hexafluoropropylene are introduced into the second tubular fixed bed reactor 10 according to the molar ratio of 1:1, the reaction pressure is 4bar, and the reaction time is 300 s. The product is perfluoro-penta-carbon ketone, and the yield is 89.3%;
the volumes of the first kettle-type reactor and the second kettle-type reactor are both 3L, the perfluoro isobutyryl fluoride obtained by separation and liquid ammonia in a liquid ammonia tank are put into the first kettle-type reactor according to the molar ratio of 1:1.2, electric stirring is started, the stirring speed is 300 r/min, the temperature of the first kettle is set to be 25 ℃, the reaction pressure is 10bar, the reaction is kept for 1.0h, the obtained product is transferred to the second kettle-type reactor, 2 times of equivalent of trifluoroacetic anhydride is added into the second kettle-type reactor as a dehydrating agent, the reaction temperature is 25 ℃, the reaction time is 2.0h, the gas flowing out of the second kettle-type reactor is further purified by a low-temperature rectifying tower, the product is perfluoro isobutyronitrile, the purity is 99.3%, and the total reaction yield is 89.7%.
Example 15
The length of the first tubular fixed bed reactor 5 is 80cm, the pipe diameter is 1 inch, the reaction temperature is 250 ℃, nickel oxide with 20 percent of activated carbon loading is used as a catalyst, the filling proportion of the catalyst in the first tubular fixed bed reactor 5 is 75 percent, and O is added2And hexafluoropropylene dimer in a molar ratio of 1:1 is led into a first tubular fixed bed reactor 5 for reaction, the reaction pressure is 3bar, and the reaction time is 210 s. The gas chromatography detection shows that the total fluorine isobutyryl fluoride accounts for 52.6 percent and the trifluoroacetyl fluoride accounts for 47.4 percent in the product composition;
the second tubular fixed bed reactor 10 has a length of 80cm, a tube diameter of 1 inch, a reaction temperature of 250 deg.C, and adopts N (CH)2CH2)3The load capacity of the N and alumina grafted composite catalyst is 10%, the filling proportion of the catalyst in the second tubular fixed bed reactor 10 is 75%, the obtained trifluoroacetyl fluoride and hexafluoropropylene are introduced into the second tubular fixed bed reactor 10 according to the molar ratio of 1:1, the reaction pressure is 4bar, and the reaction time is 300 s. The product is perfluoro-penta-carbon ketone, and the yield is 79.3 percent；
The volumes of the first kettle type reactor and the second kettle type reactor are both 3L, the perfluoro isobutyryl fluoride obtained by separation and liquid ammonia in a liquid ammonia tank are put into the first kettle type reactor according to the molar ratio of 1:1.2, electric stirring is started, the stirring speed is 300 r/min, the temperature of the first reaction kettle is set to be 25 ℃, the reaction pressure is set to be 10bar, the reaction time is kept to be 1.0h, the obtained product is transferred to the second kettle type reactor, 2 times of equivalent of phosphorus oxychloride is added into the second kettle type reactor to be used as a dehydrating agent, the reaction temperature is 25 ℃, the reaction time is 2.0h, the gas flowing out of the second kettle type reactor is further purified by a low-temperature rectifying tower, the product is perfluoro isobutyronitrile, the purity is 99.2%, and the total reaction yield is 72.5%.
Example 16
The length of the first tubular fixed bed reactor 5 is 80cm, the pipe diameter is 1 inch, the reaction temperature is 250 ℃, molybdenum oxide with 20 percent of activated carbon loading is used as a catalyst, the filling proportion of the catalyst in the first tubular fixed bed reactor 5 is 75 percent, and O is added2And hexafluoropropylene dimer in a molar ratio of 1:1 is led into a first tubular fixed bed reactor 5 for reaction, the reaction pressure is 3bar, and the reaction time is 210 s. The gas chromatography detection shows that the product composition contains 48.9% of perfluoroisobutyryl fluoride and 51.1% of trifluoroacetyl fluoride;
the second tubular fixed bed reactor 10 has a length of 80cm, a tube diameter of 1 inch, a reaction temperature of 250 deg.C, and adopts O (CH)2CH2)2NCH2CH2The load capacity of the OH and alumina grafted composite catalyst is 10%, the filling proportion of the catalyst in the second tubular fixed bed reactor 10 is 75%, the obtained trifluoroacetyl fluoride and hexafluoropropylene are introduced into the second tubular fixed bed reactor 10 according to the molar ratio of 1:1, the reaction pressure is 4bar, and the reaction time is 300 s. The product is perfluoro-penta-carbon ketone, and the yield is 77.5%;
the volumes of the first kettle-type reactor and the second kettle-type reactor are both 3L, the perfluoro isobutyryl fluoride obtained by separation and liquid ammonia in a liquid ammonia tank are put into the first kettle-type reactor according to the molar ratio of 1:1.2, electric stirring is started, the stirring speed is 300 r/min, the temperature of the first reaction kettle is set to be 25 ℃, the reaction pressure is set to be 10bar, the reaction is kept for 1.0h, the obtained product is transferred to the second kettle-type reactor, 2 times of equivalent weight of phosphorus pentoxide is added into the second kettle-type reactor as a dehydrating agent, the reaction temperature is 25 ℃, the reaction time is 2.0h, the gas flowing out of the second kettle-type reactor is further purified by a low-temperature rectifying tower, the product is perfluoro isobutyronitrile, the purity of the perfluoro isobutyronitrile is 99.2%, and the total reaction yield is 83.8%.
Example 17
The length of the first tubular fixed bed reactor 5 is 80cm, the pipe diameter is 1 inch, the reaction temperature is 250 ℃, silver oxide with the aluminum oxide loading capacity of 20 percent is used as a catalyst, the filling proportion of the catalyst in the first tubular fixed bed reactor 5 is 75 percent, and O is added2And hexafluoropropylene dimer in a molar ratio of 1:1 is led into a first tubular fixed bed reactor 5 for reaction, the reaction pressure is 3bar, and the reaction time is 210 s. Gas chromatography detection shows that the product composition contains 63.4% of perfluoroisobutyryl fluoride and 37.6% of trifluoroacetyl fluoride;
the second tubular fixed bed reactor 10 has a length of 80cm, a tube diameter of 1 inch, a reaction temperature of 250 deg.C, and adopts Me2NCH2CH2The load capacity of the OH and alumina grafted composite catalyst is 10%, the filling proportion of the catalyst in the second tubular fixed bed reactor 10 is 75%, the obtained trifluoroacetyl fluoride and hexafluoropropylene are introduced into the second tubular fixed bed reactor 10 according to the molar ratio of 1:1, the reaction pressure is 4bar, and the reaction time is 300 s. The product is perfluoro-penta-carbon ketone, and the yield is 76.9%;
the volumes of the first kettle type reactor and the second kettle type reactor are both 3L, the perfluoro isobutyryl fluoride obtained by separation and liquid ammonia in a liquid ammonia tank are put into the first kettle type reactor according to the molar ratio of 1:1.2, electric stirring is started, the stirring speed is 300 r/min, the temperature of the first reaction kettle is set to be 25 ℃, the reaction pressure is set to be 10bar, the reaction time is kept to be 1.0h, the obtained product is transferred to the second kettle type reactor, then 2 times of equivalent of thionyl chloride is added into the second kettle type reactor to be used as a dehydrating agent, the reaction temperature is 25 ℃, the reaction time is 2.0h, the gas flowing out of the second kettle type reactor is further purified by a low-temperature rectifying tower, the product is perfluoro isobutyronitrile, the purity is 99.2%, and the total reaction yield is 79.8%.
Example 18
The length of the first tubular fixed bed reactor 5 is 80cm, the pipe diameter is 1 inch, the reaction temperature is 250 ℃, nickel oxide with the alumina loading of 20 percent is used as a catalyst, the filling proportion of the catalyst in the first tubular fixed bed reactor 5 is 75 percent, and O is added2And hexafluoropropylene dimer in a molar ratio of 1:1 is led into a first tubular fixed bed reactor 5 for reaction, the reaction pressure is 3bar, and the reaction time is 210 s. According to gas chromatography detection, the product composition contains 49.3% of perfluoroisobutyryl fluoride and 51.7% of trifluoroacetyl fluoride;
the length of the second tubular fixed bed reactor 10 is 80cm, the pipe diameter is 1 inch, the reaction temperature is 250 ℃, NaF with 10% of activated carbon loading is used as a catalyst, the filling proportion of the catalyst in the second tubular fixed bed reactor 10 is 75%, the obtained trifluoroacetyl fluoride and hexafluoropropylene are introduced into the second tubular fixed bed reactor 10 according to the molar ratio of 1:1, the reaction pressure is 4bar, and the reaction time is 300 s. The product is perfluoro-penta-carbon ketone, and the yield is 73.3%;
the volumes of the first kettle type reactor and the second kettle type reactor are both 3L, the perfluoro isobutyryl fluoride obtained by separation and liquid ammonia in a liquid ammonia tank are put into the first kettle type reactor according to the molar ratio of 1:1.2, electric stirring is started, the stirring speed is 300 r/min, the temperature of the first reaction kettle is set to be 25 ℃, the reaction pressure is 10bar, the reaction is kept for 1.0h, the obtained product is transferred to the second kettle type reactor, and then 2 times of equivalent of WO loaded by activated carbon is added into the second kettle type reactor3The catalyst has the loading capacity of 50 percent and the reaction temperature of 25 ℃ for 2.0h, the gas flowing out of the second kettle-type reactor is further purified by a low-temperature rectifying tower, the product is perfluoroisobutyronitrile, the purity of the perfluoroisobutyronitrile is 99.2 percent, and the total reaction yield is 82.5 percent.
Example 19
The length of the first tubular fixed bed reactor 5 is 80cm, the pipe diameter is 1 inch, the reaction temperature is 250 ℃, molybdenum oxide with the aluminum oxide loading capacity of 20 percent is used as a catalyst, the filling proportion of the catalyst in the first tubular fixed bed reactor 5 is 75 percent, and O is added2And hexafluoropropylene dimer in a molar ratio of 1:1 is led into a first tubular fixed bed reactor 5 for reaction, the reaction pressure is 3bar, and the reaction time is 210 s.The gas chromatography detection shows that the product composition contains 45.5% of perfluoroisobutyryl fluoride and 54.5% of trifluoroacetyl fluoride;
the length of the second tubular fixed bed reactor 10 is 80cm, the pipe diameter is 1 inch, the reaction temperature is 250 ℃, KF with 10% of activated carbon loading is used as a catalyst, the filling proportion of the catalyst in the second tubular fixed bed reactor 10 is 75%, the obtained trifluoroacetyl fluoride and hexafluoropropylene are introduced into the second tubular fixed bed reactor 10 according to the molar ratio of 1:1, the reaction pressure is 4bar, and the reaction time is 300 s. The product is perfluoropentacarbonone, and the yield is 74.7%;
the volumes of the first kettle type reactor and the second kettle type reactor are both 3L, the perfluoro isobutyryl fluoride obtained by separation and liquid ammonia in a liquid ammonia tank are put into the first kettle type reactor according to the molar ratio of 1:1.2, electric stirring is started, the stirring speed is 300 r/min, the temperature of the first reaction kettle is set to be 25 ℃, the reaction pressure is 10bar, the reaction is kept for 1.0h, the obtained product is transferred to the second kettle type reactor, and then 2 times of equivalent of Al loaded by activated carbon is added into the second kettle type reactor2O3The catalyst has the loading of 50 percent and the reaction temperature of 25 ℃ for 2.0h, the gas flowing out of the second kettle-type reactor is further purified by a low-temperature rectifying tower, the product is perfluoroisobutyronitrile, the purity of the perfluoroisobutyronitrile is 99.2 percent, and the total reaction yield is 69.5 percent.
Example 20
The length of the first tubular fixed bed reactor 5 is 80cm, the pipe diameter is 1 inch, the reaction temperature is 250 ℃, silver oxide with the aluminum oxide loading capacity of 5 percent is used as a catalyst, the filling proportion of the catalyst in the first tubular fixed bed reactor 5 is 75 percent, and O is added2And hexafluoropropylene dimer in a molar ratio of 1:1 is led into a first tubular fixed bed reactor 5 for reaction, the reaction pressure is 3bar, and the reaction time is 210 s. According to gas chromatography detection, the product composition contains 49.7% of perfluoroisobutyryl fluoride and 51.3% of trifluoroacetyl fluoride;
the second tubular fixed bed reactor 10 has a length of 80cm, a tube diameter of 1 inch, a reaction temperature of 250 deg.C, and adopts Me2NCH2CH2The load capacity of the OH and alumina grafted composite catalyst is 5 percent, and the filling proportion of the catalyst in the second tubular fixed bed reactor 10 is 75 percent, and introducing the obtained trifluoroacetyl fluoride and hexafluoropropylene into a second tubular fixed bed reactor 10 according to the molar ratio of 1:1, wherein the reaction pressure is 4bar, and the reaction time is 300 s. The product is perfluoro-penta-carbon ketone, and the yield is 68.1%;
the volumes of the first kettle type reactor and the second kettle type reactor are both 3L, the perfluoro isobutyryl fluoride obtained by separation and liquid ammonia in a liquid ammonia tank are put into the first kettle type reactor according to the molar ratio of 1:1.2, electric stirring is started, the stirring speed is 300 r/min, the temperature of the first reaction kettle is set to be 25 ℃, the reaction pressure is 10bar, the reaction is kept for 1.0h, the obtained product is transferred to the second kettle type reactor, and then 2 times of equivalent of WO loaded by activated carbon is added into the second kettle type reactor3The catalyst has the loading of 10 percent and the reaction temperature of 25 ℃ for 2.0h, the gas flowing out of the second kettle-type reactor is further purified by a low-temperature rectifying tower, the product is perfluoroisobutyronitrile, the purity of the perfluoroisobutyronitrile is 99.2 percent, and the total reaction yield is 46.5 percent.
Example 21
The length of the first tubular fixed bed reactor 5 is 80cm, the pipe diameter is 1 inch, the reaction temperature is 250 ℃, silver oxide with the aluminum oxide loading capacity of 10 percent is used as a catalyst, the filling proportion of the catalyst in the first tubular fixed bed reactor 5 is 75 percent, and O is added2And hexafluoropropylene dimer in a molar ratio of 1:1 is led into a first tubular fixed bed reactor 5 for reaction, the reaction pressure is 3bar, and the reaction time is 210 s. Gas chromatography detection shows that the product composition contains 50.8% of perfluoroisobutyryl fluoride and 49.2% of trifluoroacetyl fluoride;
the second tubular fixed bed reactor 10 has a length of 80cm, a tube diameter of 1 inch, a reaction temperature of 250 deg.C, and adopts Me2NCH2CH2The load capacity of the OH and alumina grafted composite catalyst is 6%, the filling proportion of the catalyst in the second tubular fixed bed reactor 10 is 75%, the obtained trifluoroacetyl fluoride and hexafluoropropylene are introduced into the second tubular fixed bed reactor 10 according to the molar ratio of 1:1, the reaction pressure is 4bar, and the reaction time is 300 s. The product is perfluoro-penta-carbon ketone, and the yield is 69.2%;
the volumes of the first kettle type reactor and the second kettle type reactor are both 3L, and the separated perfluoro isobutyryl fluoride arePutting liquid ammonia in a liquid ammonia tank into a first kettle type reactor according to a molar ratio of 1:1.2, starting electric stirring, setting the stirring speed to 300 revolutions per minute, setting the temperature of the first reaction kettle to be 25 ℃ and the reaction pressure to be 10bar, keeping the temperature for 1.0 hour, transferring the obtained product to a second kettle type reactor, and then adding 2 times of equivalent of Al loaded by activated carbon into the second kettle type reactor2O3The catalyst has the loading of 10 percent and the reaction temperature of 25 ℃ for 2.0h, the gas flowing out of the second kettle-type reactor is further purified by a low-temperature rectifying tower, the product is perfluoroisobutyronitrile, the purity of the perfluoroisobutyronitrile is 99.2 percent, and the total reaction yield is 41.8 percent.
Example 22
The length of the first tubular fixed bed reactor 5 is 80cm, the pipe diameter is 1 inch, the reaction temperature is 250 ℃, silver oxide with the aluminum oxide loading capacity of 15 percent is used as a catalyst, the filling proportion of the catalyst in the first tubular fixed bed reactor 5 is 75 percent, and O is added2And hexafluoropropylene dimer in a molar ratio of 1:1 is led into a first tubular fixed bed reactor 5 for reaction, the reaction pressure is 3bar, and the reaction time is 210 s. The gas chromatography detection shows that the total fluorine isobutyryl fluoride accounts for 52.4 percent and the trifluoroacetyl fluoride accounts for 47.6 percent of the product composition;
the second tubular fixed bed reactor 10 has a length of 80cm, a tube diameter of 1 inch, a reaction temperature of 250 deg.C, and adopts Me2NCH2CH2The load capacity of the OH and alumina grafted composite catalyst is 8%, the filling proportion of the catalyst in the second tubular fixed bed reactor 10 is 75%, the obtained trifluoroacetyl fluoride and hexafluoropropylene are introduced into the second tubular fixed bed reactor 10 according to the molar ratio of 1:1, the reaction pressure is 4bar, and the reaction time is 300 s. The product is perfluoro-penta-carbon ketone, and the yield is 73.5%;
the volumes of the first kettle type reactor and the second kettle type reactor are both 3L, the perfluoro isobutyryl fluoride obtained by separation and liquid ammonia in a liquid ammonia tank are put into the first kettle type reactor according to the molar ratio of 1:1.2, electric stirring is started, the stirring speed is 300 r/min, the temperature of the first reaction kettle is set to be 25 ℃, the reaction pressure is 10bar, the reaction is kept for 1.0h, the obtained product is transferred to the second kettle type reactor, and then 2 times of equivalent of activated carbon loaded active carbon is added into the second kettle type reactorWO3The catalyst has the loading capacity of 30 percent and the reaction temperature of 25 ℃ for 2.0h, the gas flowing out of the second kettle-type reactor is further purified by a low-temperature rectifying tower, the product is perfluoroisobutyronitrile, the purity of the perfluoroisobutyronitrile is 99.2 percent, and the total reaction yield is 51.5 percent.
Example 23
The length of the first tubular fixed bed reactor 5 is 80cm, the pipe diameter is 1 inch, the reaction temperature is 250 ℃, silver oxide with the aluminum oxide loading capacity of 25 percent is used as a catalyst, the filling proportion of the catalyst in the first tubular fixed bed reactor 5 is 75 percent, and O is added2And hexafluoropropylene dimer in a molar ratio of 1:1 is led into a first tubular fixed bed reactor 5 for reaction, the reaction pressure is 3bar, and the reaction time is 210 s. Gas chromatography detection shows that the product composition contains 53.5% of perfluoroisobutyryl fluoride and 47.5% of trifluoroacetyl fluoride;
the second tubular fixed bed reactor 10 has a length of 80cm, a tube diameter of 1 inch, a reaction temperature of 250 deg.C, and adopts Me2NCH2CH2The load capacity of the OH and alumina grafted composite catalyst is 15%, the filling proportion of the catalyst in the second tubular fixed bed reactor 10 is 75%, the obtained trifluoroacetyl fluoride and hexafluoropropylene are introduced into the second tubular fixed bed reactor 10 according to the molar ratio of 1:1, the reaction pressure is 4bar, and the reaction time is 300 s. The product is perfluoro-penta-carbon ketone, and the yield is 76.1%;
the volumes of the first kettle type reactor and the second kettle type reactor are both 3L, the perfluoro isobutyryl fluoride obtained by separation and liquid ammonia in a liquid ammonia tank are put into the first kettle type reactor according to the molar ratio of 1:1.2, electric stirring is started, the stirring speed is 300 r/min, the temperature of the first reaction kettle is set to be 25 ℃, the reaction pressure is 10bar, the reaction is kept for 1.0h, the obtained product is transferred to the second kettle type reactor, and then 2 times of equivalent of Al loaded by activated carbon is added into the second kettle type reactor2O3The catalyst has the loading of 30 percent and the reaction temperature of 25 ℃ for 2.0h, the gas flowing out of the second kettle-type reactor is further purified by a low-temperature rectifying tower, the product is perfluoroisobutyronitrile, the purity of the perfluoroisobutyronitrile is 99.2 percent, and the total reaction yield is 48.9 percent.
Example 24
The length of the first tubular fixed bed reactor 5 is 80cm, the pipe diameter is 1 inch, the reaction temperature is 250 ℃, silver oxide with the aluminum oxide loading capacity of 35 percent is used as a catalyst, the filling proportion of the catalyst in the first tubular fixed bed reactor 5 is 75 percent, and O is added2And hexafluoropropylene dimer in a molar ratio of 1:1 is led into a first tubular fixed bed reactor 5 for reaction, the reaction pressure is 3bar, and the reaction time is 210 s. Gas chromatography detection shows that the product composition contains 53.9% of perfluoroisobutyryl fluoride and 46.1% of trifluoroacetyl fluoride;
the second tubular fixed bed reactor 10 has a length of 80cm, a tube diameter of 1 inch, a reaction temperature of 250 deg.C, and adopts Me2NCH2CH2The load capacity of the OH and alumina grafted composite catalyst is 20%, the filling proportion of the catalyst in the second tubular fixed bed reactor 10 is 75%, the obtained trifluoroacetyl fluoride and hexafluoropropylene are introduced into the second tubular fixed bed reactor 10 according to the molar ratio of 1:1, the reaction pressure is 4bar, and the reaction time is 600 s. The product is perfluoro-penta-carbon ketone, and the yield is 75.9%;
the volumes of the first kettle type reactor and the second kettle type reactor are both 3L, the perfluoro isobutyryl fluoride obtained by separation and liquid ammonia in a liquid ammonia tank are put into the first kettle type reactor according to the molar ratio of 1:1.2, electric stirring is started, the stirring speed is 300 r/min, the temperature of the first reaction kettle is set to be 25 ℃, the reaction pressure is 10bar, the reaction is kept for 1.0h, the obtained product is transferred to the second kettle type reactor, and then 2 times of equivalent of WO loaded by activated carbon is added into the second kettle type reactor3The catalyst has the loading capacity of 60 percent, the reaction temperature of 25 ℃ and the reaction time of 2.0h, the gas flowing out of the second kettle-type reactor is further purified by a low-temperature rectifying tower, the product is perfluoroisobutyronitrile, the purity of the perfluoroisobutyronitrile is 99.2 percent, and the total reaction yield is 81.6 percent.
Example 25
The length of the first tubular fixed bed reactor 5 is 80cm, the pipe diameter is 1 inch, the reaction temperature is 250 ℃, silver oxide with the aluminum oxide loading capacity of 50 percent is used as a catalyst, the filling proportion of the catalyst in the first tubular fixed bed reactor 5 is 75 percent, and O is added2And hexafluoropropylene dimer in a molar ratio of 1:1 is introduced into a first tubular fixed bed reactor 5 for reaction at a reaction pressure of 3barThe response time was 210 s. The gas chromatography detection shows that the total fluorine isobutyryl fluoride accounts for 52.3 percent and the trifluoroacetyl fluoride accounts for 47.7 percent in the product composition;
the second tubular fixed bed reactor 10 has a length of 80cm, a tube diameter of 1 inch, a reaction temperature of 250 deg.C, and Me2NCH2CH2The load capacity of the OH and alumina grafted composite catalyst is 25%, the filling proportion of the catalyst in the second tubular fixed bed reactor 10 is 75%, the obtained trifluoroacetyl fluoride and hexafluoropropylene are introduced into the second tubular fixed bed reactor 10 according to the molar ratio of 1:1, the reaction pressure is 4bar, and the reaction time is 300 s. The product is perfluoro-penta-carbon ketone, and the yield is 75.5%;
the volumes of the first kettle type reactor and the second kettle type reactor are both 3L, the perfluoro isobutyryl fluoride obtained by separation and liquid ammonia in a liquid ammonia tank are put into the first kettle type reactor according to the molar ratio of 1:1.2, electric stirring is started, the stirring speed is 300 r/min, the temperature of the first reaction kettle is set to be 25 ℃, the reaction pressure is 10bar, the reaction is kept for 1.0h, the obtained product is transferred to the second kettle type reactor, and then 2 times of equivalent of Al loaded by activated carbon is added into the second kettle type reactor2O3The catalyst has the loading capacity of 60 percent, the reaction temperature of 25 ℃ and the reaction time of 2.0h, the gas flowing out of the second kettle-type reactor is further purified by a low-temperature rectifying tower, the product is perfluoroisobutyronitrile, the purity of the perfluoroisobutyronitrile is 99.2 percent, and the total reaction yield is 68.8 percent.
Example 26
The length of the first tubular fixed bed reactor 5 is 80cm, the pipe diameter is 1 inch, the reaction temperature is 250 ℃, silver oxide with 20 percent of active load capacity is used as a catalyst, the filling proportion of the catalyst in the first tubular fixed bed reactor 5 is 75 percent, and O is added2And hexafluoropropylene dimer in a molar ratio of 1:1 is led into a first tubular fixed bed reactor 5 for reaction, the reaction pressure is 3bar, and the reaction time is 210 s. The gas chromatography detection shows that the product composition contains 65.8 percent of perfluoroisobutyryl fluoride and 34.2 percent of trifluoroacetyl fluoride;
the length of the second tubular fixed bed reactor 10 is 80cm, the pipe diameter is 1 inch, the reaction temperature is 250 ℃, CsF with 10% of activated carbon loading is used as a catalyst, the filling proportion of the catalyst in the second tubular fixed bed reactor 10 is 75%, the obtained trifluoroacetyl fluoride and hexafluoropropylene are introduced into the second tubular fixed bed reactor 10 according to the molar ratio of 1:1, the reaction pressure is 4bar, and the reaction time is 300 s. The product is perfluoro-penta-carbon ketone, and the yield is 89.3%;
the volumes of the first kettle type reactor and the second kettle type reactor are both 3L, the perfluoro isobutyryl fluoride obtained by separation and liquid ammonia in a liquid ammonia tank are put into the first kettle type reactor according to the molar ratio of 1:1.2, electric stirring is started, the stirring speed is 300 r/min, the temperature of the first reaction kettle is set to be 25 ℃, the reaction pressure is 10bar, the reaction is kept for 1.0h, the obtained product is transferred to the second kettle type reactor, and then 2 times of equivalent of WO loaded by activated carbon is added into the second kettle type reactor3The catalyst has the loading of 70 percent and the reaction temperature of 25 ℃ for 2.0h, the gas flowing out of the second kettle-type reactor is further purified by a low-temperature rectifying tower, the product is perfluoroisobutyronitrile, the purity of the perfluoroisobutyronitrile is 99.3 percent, and the total reaction yield is 80.7 percent.
Example 27
The length of the first tubular fixed bed reactor 5 is 80cm, the pipe diameter is 1 inch, the reaction temperature is 250 ℃, silver oxide with 20 percent of active load capacity is used as a catalyst, the filling proportion of the catalyst in the first tubular fixed bed reactor 5 is 75 percent, and O is added2And hexafluoropropylene dimer in a molar ratio of 1:1 is led into a first tubular fixed bed reactor 5 for reaction, the reaction pressure is 3bar, and the reaction time is 210 s. The gas chromatography detection shows that the product composition contains 65.8 percent of perfluoroisobutyryl fluoride and 34.2 percent of trifluoroacetyl fluoride;
the length of the second tubular fixed bed reactor 10 is 80cm, the pipe diameter is 1 inch, the reaction temperature is 250 ℃, CsF with 10% of activated carbon loading is used as a catalyst, the filling proportion of the catalyst in the second tubular fixed bed reactor 10 is 75%, the obtained trifluoroacetyl fluoride and hexafluoropropylene are introduced into the second tubular fixed bed reactor 10 according to the molar ratio of 1:1, the reaction pressure is 4bar, and the reaction time is 300 s. The product is perfluoro-penta-carbon ketone, and the yield is 89.3%;
the volumes of the first kettle type reactor and the second kettle type reactor are both 3L, and the separated perfluoro isobutyryl fluoride and liquid ammonia in a liquid ammonia tank are put into the second kettle type reactor according to the molar ratio of 1:1.2Starting electric stirring in a one-kettle reactor, setting the stirring speed at 300 r/min, the temperature of a first reaction kettle at 25 ℃ and the reaction pressure at 10bar, keeping the reaction pressure for 1.0h, transferring the obtained product to a second kettle reactor, and adding 2 times of equivalent of activated carbon-loaded Al into the second kettle reactor2O3The catalyst has the loading of 70 percent and the reaction temperature of 25 ℃ for 2.0h, and the gas flowing out of the second kettle-type reactor is further purified by a low-temperature rectifying tower, the purity of the gas is 99.2 percent, and the total reaction yield is 67.9 percent.
Example 28
The length of the first tubular fixed bed reactor 5 is 80cm, the pipe diameter is 1 inch, the reaction temperature is 250 ℃, silver oxide with 20 percent of activated carbon loading is used as a catalyst, the filling proportion of the catalyst in the first tubular fixed bed reactor 5 is 75 percent, and O is added2And hexafluoropropylene trimer in a molar ratio of 1:1 is led into a first tubular fixed bed reactor 5 for reaction, the reaction pressure is 3bar, and the reaction time is 210 s. The gas chromatography detection shows that the product composition contains 61.3 percent of perfluoroisobutyryl fluoride and 38.7 percent of perfluoropenta-carbon ketone.
The volume of the first kettle type reactor and the volume of the second kettle type reactor are 3L, the perfluoro isobutyryl fluoride obtained by separation and liquid ammonia in a liquid ammonia tank are put into the first kettle type reactor according to the molar ratio of 1:1.2, electric stirring is started, the stirring speed is 300 r/min, the reaction temperature of the first kettle type reactor is set to be 25 ℃, the reaction pressure is 10bar, the reaction is kept for 1.0h, the obtained product is transferred to the second kettle type reactor, and then 2 times equivalent of WO loaded by activated carbon is added into the second kettle type reactor3The catalyst has the loading capacity of 80 percent, the reaction temperature of 25 ℃ and the reaction time of 2.0h, the gas flowing out of the second kettle-type reactor is purified by a third low-temperature rectifying tower, the product is perfluoroisobutyronitrile, the purity of the perfluoroisobutyronitrile is 99.1 percent, and the total reaction yield is 84.9 percent.
Example 29
The length of the first tubular fixed bed reactor 5 is 80cm, the pipe diameter is 1 inch, the reaction temperature is 250 ℃, silver oxide with 20 percent of activated carbon loading is used as a catalyst, the filling proportion of the catalyst in the first tubular fixed bed reactor 5 is 75 percent, and O is added2And hexafluoropropylene trimerizationThe molar ratio of the components is 1:1 is led into a first tubular fixed bed reactor 5 for reaction, the reaction pressure is 3bar, and the reaction time is 210 s. The gas chromatography detection shows that the product composition contains 61.3 percent of perfluoroisobutyryl fluoride and 38.7 percent of perfluoropenta-carbon ketone.
The volume of the first kettle type reactor and the second kettle type reactor is 3L, the perfluoro isobutyryl fluoride obtained by separation and liquid ammonia in a liquid ammonia tank are put into the first kettle type reactor according to the molar ratio of 1:1.2, electric stirring is started, the stirring speed is 300 r/min, the reaction temperature of the first kettle type reactor is set to be 25 ℃, the reaction pressure is 10bar, the reaction is kept for 1.0h, the obtained product is transferred to the second kettle type reactor, and then 2 times of equivalent of Al loaded by activated carbon is added into the second kettle type reactor2O3The catalyst has the loading capacity of 80 percent, the reaction temperature of 25 ℃ and the reaction time of 2.0h, the gas flowing out of the second kettle-type reactor is purified by a third low-temperature rectifying tower, the product is perfluoroisobutyronitrile, the purity of the perfluoroisobutyronitrile is 99.1 percent, and the total reaction yield is 84.9 percent.
Example 30
The length of the first tubular fixed bed reactor 5 is 80cm, the pipe diameter is 1 inch, the reaction temperature is 250 ℃, silver oxide with 10 percent of activated carbon loading is used as a catalyst, the filling proportion of the catalyst in the first tubular fixed bed reactor 5 is 75 percent, and O is added2And octafluoro-1-butene in a molar ratio of 1:1 is introduced into a first tubular fixed bed reactor 5 for reaction, the reaction pressure is 3bar, and the reaction time is 300 s. The gas chromatography detection shows that the product composition contains 63.3% of the fluorophosphoric acid and 36.7% of the perfluoropropionyl fluoride. The pure product of the perfluoro propionyl fluoride is obtained after the separation by the first low-temperature rectifying tower.
The length of the second tubular fixed bed reactor 10 is 80cm, the pipe diameter is 1 inch, the reaction temperature is 250 ℃, CsF with 10 percent of activated carbon loading is used as a catalyst, the filling proportion of the catalyst in the reactor is 75 percent, the separated perfluoro propionyl fluoride and hexafluoropropylene are introduced into the second tubular fixed bed reactor 10 according to the molar ratio of 1:1, the reaction pressure is 4bar, and the reaction time is 300 s. The product was perfluorohexa-carbon ketone with a yield of 88.1%.

Claims (10)

1. An economical and efficient perfluoronitrile and perfluoroketone co-production process is characterized by comprising the following steps:
mixing oxygen and asymmetric perfluoroolefin to react to generate two kinds of acyl fluoride gas or generate perfluoroketone gas and acyl fluoride gas;
when two kinds of acyl fluoride gas are generated, separating the two kinds of acyl fluoride gas according to the difference of the boiling points of the two kinds of acyl fluoride gas to obtain a first acyl fluoride gas and a second acyl fluoride gas, wherein the boiling point of the first acyl fluoride gas is higher than that of the second acyl fluoride gas, then contacting and reacting the first acyl fluoride gas with ammonia gas to convert the first acyl fluoride gas into perfluoroamide, and dehydrating the perfluoroamide to convert the perfluoroamide into perfluoronitrile; mixing the second acyl fluoride gas with hexafluoropropylene to react to generate a perfluoroketone compound;
when perfluoroketone gas and acyl fluoride gas are generated, separating the perfluoroketone gas from the acyl fluoride gas, condensing and collecting the perfluoroketone gas, carrying out contact reaction on the acyl fluoride gas and ammonia gas to convert the acyl fluoride gas into perfluoroamide, and dehydrating the perfluoroamide to convert the perfluoroamide into perfluoronitrile.
2. The economical and efficient perfluoronitrile and perfluoroketone co-production process according to claim 1, wherein: the asymmetric perfluoroolefin is hexafluoropropylene dimer, hexafluoropropylene trimer, octafluoro-1-butene or other asymmetric perfluoroolefin.
3. The economical and efficient perfluoronitrile and perfluoroketone co-production process according to claim 1, wherein: the reaction temperature of the oxygen and the asymmetric perfluoroolefin is 150-300 ℃, the molar ratio of the oxygen to the asymmetric perfluoroolefin is 0.5-2: 1, and the contact time of the oxygen and the asymmetric perfluoroolefin is 60-300 s.
4. The economical and efficient perfluoronitrile and perfluoroketone co-production process according to claim 1, wherein: the oxygen and the asymmetric perfluoroolefin are mixed and reacted to be added with a catalyst, and the catalyst used for the oxygen and the asymmetric perfluoroolefin comprises activated carbon or alumina-supported MoO3NiO or Ag2O, oxygenThe loading of the catalyst used for gas and asymmetric perfluoroolefin is 5-50%.
5. The economical and efficient perfluoronitrile and perfluoroketone co-production process according to claim 4, wherein: the preparation method of the catalyst comprises the following steps: weighing ammonium molybdate, nickel nitrate or silver nitrate to prepare 0.2-2mol/L aqueous solution, adding an activated carbon or alumina molecular sieve into the aqueous solution according to the specific gravity of the activated carbon or alumina molecular sieve of the catalyst, stirring for 0.5-3h, removing water by using a rotary evaporator, calcining and drying in a muffle furnace at 150-250 ℃ until the mass of the catalyst is unchanged to obtain the catalyst loaded with the activated carbon or alumina molecular sieve;
when nickel nitrate or silver nitrate is used for preparing the aqueous solution, NaOH solution with the same molar quantity as the nickel nitrate or silver nitrate is also required to be added into the aqueous solution.
6. The economical and efficient perfluoronitrile and perfluoroketone co-production process according to claim 1, wherein: the reaction temperature of the second acyl fluoride gas and hexafluoropropylene is 100-250 ℃, and the contact reaction time of the second acyl fluoride gas and hexafluoropropylene is 10-600 s.
7. The economical and efficient perfluoronitrile and perfluoroketone co-production process according to claim 1, wherein: and adding a catalyst in the mixed reaction of the second acyl fluoride gas and hexafluoropropylene, wherein the catalyst used in the reaction of the second acyl fluoride gas and hexafluoropropylene is an alkali metal fluoride salt loaded by active carbon, or a composite catalyst of dimethylethanolamine, 2-morpholinoethanol and DABCO grafted on the surface of alumina.
8. The economical and efficient perfluoronitrile and perfluoroketone co-production process according to claim 7, wherein: the preparation method of the alkali metal fluoride salt loaded by the activated carbon comprises the following steps: respectively preparing NaF, KF or CsF aqueous solution with the concentration of 0.2-2mol/L, adding activated carbon according to the activated carbon loading amount in the catalyst, stirring for 2h, removing water through a rotary evaporator, and placing in a muffle furnace to burn for 4h at 200 ℃;
the preparation method of the alumina composite catalyst comprises the following steps: surface treatment of alumina support with thionyl chloride or acid chloride followed by Me addition2NCH2CH2OH、O(CH2CH2)2NCH2CH2OH or N (CH)2CH2)3Carrying out contact reaction on N and an alumina loading agent, removing the solvent after the reaction is finished, washing for 6 times, and drying to obtain a catalyst used for the reaction of the second acyl fluoride gas and hexafluoropropylene; the second acyl fluoride gas is reacted with hexafluoropropylene using a catalyst having a loading of 5-25%.
9. The economical and efficient perfluoronitrile and perfluoroketone co-production process according to claim 1, wherein: the reaction temperature of the first acyl fluoride gas and the reaction temperature of the ammonia gas are both 0-50 ℃, the reaction temperature of perfluoroamide dehydration is 0-50 ℃, and when the perfluoroamide is dehydrated by adopting a catalyst, the catalyst used by the perfluoroamide is WO loaded by active carbon3、Al2O3The loading amount of the catalyst used for the perfluoroamide is 10-80%; when the perfluoroamide is dehydrated by adopting a dehydrating agent, the dehydrating agent used by the perfluoroamide is trifluoroacetic anhydride, phosphorus oxychloride, thionyl chloride or phosphorus pentoxide.
10. An economic and efficient perfluoronitrile and perfluoroketone co-production device is characterized in that: the device comprises an oxygen bottle (1), wherein an outlet of the oxygen bottle (1) is connected with a first inlet of a first gas mixer (4), a second inlet of the first gas mixer (4) is connected with an outlet of a gasifier (3), an inlet of the gasifier (3) is connected with an outlet of a liquid storage tank (2), asymmetric perfluoroolefin is filled in the liquid storage tank (2), an outlet of the first gas mixer (4) is connected with an inlet of a first tubular fixed bed reactor (5), and an outlet of the first tubular fixed bed reactor (5) is connected with a first cryogenic rectification tower (6);
the overhead condenser (7) of the first cryogenic rectification tower (6) is connected with the first inlet of a second gas mixer (8), the second inlet of the second gas mixer (8) is connected with the outlet of a hexafluoropropylene gas tank (9), the outlet of the second gas mixer (8) is connected with the inlet of a second tubular fixed bed reactor (10), the outlet of the second tubular fixed bed reactor (10) is connected with a second cryogenic rectification tower (11), and the overhead condenser (7) of the second cryogenic rectification tower (11) is connected with the inlet of a perfluoroketone collection tank (12);
the tower kettle of the first cryogenic rectification tower (6) is connected with a first inlet of the first kettle type reactor (13), a second inlet of the first kettle type reactor (13) is connected with an outlet of the liquid ammonia tank (14), an outlet of the first kettle type reactor (13) is connected with an inlet of the second kettle type reactor (15), an outlet of the second kettle type reactor (15) is connected with a third cryogenic rectification tower (16), and a tower top condenser (7) of the third cryogenic rectification tower (16) is connected with a perfluoronitrile collecting tank (17).
CN202010245249.4A 2020-03-31 2020-03-31 Economical and efficient perfluoronitrile and perfluoroketone co-production process and device Pending CN111233653A (en)

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