CN109503363A - Hexafluoropropylene dimmer cracking prepares the device of perfluoropentyl ether - Google Patents
Hexafluoropropylene dimmer cracking prepares the device of perfluoropentyl ether Download PDFInfo
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- CN109503363A CN109503363A CN201811458161.XA CN201811458161A CN109503363A CN 109503363 A CN109503363 A CN 109503363A CN 201811458161 A CN201811458161 A CN 201811458161A CN 109503363 A CN109503363 A CN 109503363A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/58—Preparation of carboxylic acid halides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
- C07C45/455—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation with carboxylic acids or their derivatives
Abstract
The invention belongs to Fluorine Equipment fields, and in particular to a kind of hexafluoropropylene dimmer cracking prepares the device of perfluoropentyl ether, including perfluor acetylfluoride generation unit, perfluor five-carbon ketone generation unit and perfluoropentyl ether generation unit；The perfluor acetylfluoride generation unit includes hexafluoropropene air accumulator, the first catalytic reaction tube, the first condenser, pyrolysis furnace, -2 DEG C of cold-traps and -70 DEG C of cold-traps of sequential communication；The perfluor five-carbon ketone generation unit includes the second catalytic reaction tube and the second condenser being linked in sequence；The perfluoropentyl ether generation unit includes reaction kettle, stratification tower, drying tower and the perfluoropentyl ether fluid reservoir being linked in sequence.The present invention devises a kind of device that perfluoropentyl ether is cracked to form using hexafluoropropylene dimmer as raw material, and using hydrofluoroether is cracked to form after hexafluoropropene monomer polymerization under the effect of the catalyst, device design is rationally, simple and safe, it is easy to accomplish.
Description
Technical field
The invention belongs to Fluorine Equipment fields, and in particular to a kind of hexafluoropropylene dimmer cracking prepares perfluoropentyl ether
Device.
Background technique
The technology of preparing of existing Hydrofluoroether compounds mainly includes following several: (1) fluorine gas or metal fluoride are to ether
The fluorination of class compound.(2) electrochemical fluorination of ether compound.(3) fluorine-containing alcohol is in the presence of the hydroxide of alkali metal, with halogen
Hydrofluoroether is obtained for hydrocarbon reaction.(4) addition reaction of fluorine-containing alcohol and Fluorine containing olefine.(5) alkyl of fluorinated acyl fluoride or fluorinated ketone
Change reaction.There is certain deficiency in the above method, generate hydrogen fluoride in method (1) production process, corrosivity is big, sets to reaction
It is standby to require harshness.Method (2) and (3) are since preparation process is at high cost, and product yield is low, in actual production using compared with
It is few.Report that more is that method (4) prepares hydrofluoroether, the hydrofluoroether of production using the addition reaction of fluorine-containing alcohol and Fluorine containing olefine
Product or it is flammable or have penetrating odor, be unsatisfactory for the use demand of the industries such as electronics；And in fluorine-containing alcohol and fluorinated olefins
The double bond by-product production close with target product boiling point is had during reaction preparation hydrofluoroether, therefore increases final production
The purification procedures of product, and all chlorine or bromine toxicity are big in purification process, require operation stringent.Method is usually adopted in (5)
The method of electricity consumption fluorine chemistry prepares fluorinated acyl fluoride, further prepares hydrofluoroether, but electric fluorine chemistry method is in process of production
Not only power consumption is big, low yield, by-product are more, but also needs a large amount of anhydrous hydrogen fluorides in electrolytic process；And electric fluorine chemistry side
Method would generally generate a large amount of isomer rather than certain specific perfluorinated acid fluorides, due to the boiling of these isomers
Point is same or similar, it is virtually impossible to use distillation technology separating-purifying, the hydrofluoroether product thus produced is also mixture, Wu Fatong
It crosses distillation technology and realizes separation.In order to overcome many defects in the prior art, propose few using cracking catalyst hexafluoropropene
The mode of aggressiveness finally synthesizes hydrofluoroether, because it is just particularly important to design a kind of device to generate the product.
Summary of the invention
The purpose of the present invention is to overcome the defects in the prior art, and it is complete to provide a kind of hexafluoropropylene dimmer cracking preparation
The device of fluorine amyl group ether.
The present invention to achieve the above object, using following technical scheme:
A kind of hexafluoropropylene dimmer cracking prepares the device of perfluoropentyl ether, including perfluor acetylfluoride generation unit, complete
Fluorine five-carbon ketone generation unit and perfluoropentyl ether generation unit；The perfluor acetylfluoride generation unit includes sequential communication
Hexafluoropropene air accumulator, the first catalytic reaction tube, the first condenser, pyrolysis furnace, -2 DEG C of cold-traps and -70 DEG C of cold-traps；As one
Preferably, activating chamber is arranged between the first condenser and pyrolysis furnace in kind；The perfluor five-carbon ketone generation unit includes being linked in sequence
The second catalytic reaction tube and the second condenser；- 70 DEG C of cold-traps are connected to second catalytic reaction tube；It is described
Perfluoropentyl ether generation unit include be linked in sequence reaction kettle, stratification tower, drying tower and perfluoropentyl ether liquid storage
Tank；Second condenser is connected to the reaction kettle.
The liquid outlet of -2 DEG C of cold-traps is connected to perfluor isobutyl group acyl fluorides fluid reservoir.
The upper end of first condenser is provided with outlet and connect with first catalytic tower to recycle not
The hexafluoropropene of reaction.
First condenser and the second condenser external is respectively arranged with condensation collet；The condensation collet is set
It is equipped with the condensation water inlet and condensation-water drain for condensed water inlet and outlet.
Heating mantle is provided with outside the first catalytic reaction tube of the ground and the second catalytic reaction tube.
The activating chamber and the pyrolysis furnace are connect with heater respectively.
The method that the device production perfluoropentyl ether of perfluoropentyl ether is prepared using the hexafluoropropylene dimmer cracking,
Specifically include the following steps: 1) preparation of perfluor five-carbon ketone: 1.1) hexafluoropropylene dimmer enters oxidation furnace and oxygen first
Cracking reaction is carried out under catalysts conditions；The isolated perfluor isobutyl acyl fluorides of pyrolysis product and perfluor acetylfluoride；
1.2) the perfluor acetylfluoride prepared using hexafluoropropene and step 1.1) is made under the second catalyst action as raw material
Standby perfluor five-carbon ketone；
2) five-carbon ketone and alkylating reagent obtained using step 1) is raw material, under alkali metal fluoride effect, selection
Addition tertiary amine or the phase transfer catalyst reaction in inert dipolar aprotic organic compound solvent of property prepare perfluor penta
Base ether；
The hexafluoropropylene dimmer is obtained under the catalysis of support type ionic fluorides through gas phase reaction by hexafluoropropene；
Reaction temperature is 150-220 DEG C, time of contact 0.1-30s；The load capacity of support type ionic fluorides is 10%-20%；It carries
Body is activated carbon, aluminum oxide, silica or magnesia；Ionic fluorides are AgF, NaF, KF, RbF or CsF.System
When standby, the upper end product exit of the first catalytic reaction tube of the support type ionic fluorides and first with condensation water leg
The air inlet of one end of condenser is connected, and the first condenser other end is gas vent, and unreacted hexafluoropropene passes through gas
Outlet is recycled to the first catalytic reaction tube column of support type ionic fluorides.The fluid sample sample in the first condenser is taken to detect,
The purity of gained hexafluoropropylene dimmer is greater than 99%.
Step 1.1) specifically include the following steps:
A) using oxygen and hexafluoropropylene dimmer as raw material, under the first catalyst action with perfluor second is prepared in reactor
Acyl fluorides, catalytic time are 0.1s to 200s, and temperature is 150-600 DEG C；Pressure is 0-1MP；Wherein, it described first urges
Agent is loaded catalyst, active constituent Ag2O, Al2O3, CuO, AgF, NaF, KF, RbF or CsF；Oxygen and hexafluoro
The molar ratio of propylene dimerization body is 1:10-10:1；- 2 DEG C of cold-traps to product be collected available perfluor isobutyl acyl fluorides and
A small amount of hexafluoropropylene dimmer.Rectifying is carried out to it, obtained a small amount of hexafluoropropylene dimmer is passed through pyrolysis furnace progress again
Cracking.It collects to obtain perfluor acetylfluoride in -70 DEG C of cold-trap cold-traps.
Hexafluoropropylene dimmer enters reactor with liquid form in the device, since fluid molecule is compared to gas molecule
With shorter intermolecular distance, therefore more gaseous state hexafluoropropylene dimmers point are had in the slow gasification of liquid charging stock
Son comes into full contact with oxygen, so as to shorten the pyrolysis time of hexafluoropropylene dimmer, significantly improves raw material entirety lysis efficiency.
And the presence of the hexafluoropropylene dimmer more contacted with oxygen can prevent the perfluor isobutyl acyl fluorides being cracked to form and perfluor acetyl
The further cracking of fluorine, to guarantee that gained perfluor isobutyl acyl fluorides has higher degree.
Preferably, it further include pre-activate step in step 1.1)；It specifically includes and hexafluoropropylene dimmer is passed through 180-220
DEG C the reactor filled with pre-activate carrier in activate 1-2h；The active constituent of the pre-activate carrier is four (pentafluorophenyl groups)
Borate and alkyl fluoride aluminium salt according to mass ratio 1:1-1:5 mixture；Wherein n=1-6；The carrier of pre-activate carrier is
SiO2, Al2O3 or B2O3；Load capacity is 10%-20%.
The alkyl fluoride aluminium salt is Al ((CR1R2R3) n) 3 monomers or mixture；Wherein R1, R2 and R3 be H or
Person F and at least one be F, n=1-6.
(pentafluorophenyl group) borate and alkyl fluoride aluminium salt mixed catalyst have good activation to C=C four in the reaction
Effect is activated the activation energy that can further decrease C=C cracking to hexafluoropropylene dimmer using the mixed catalyst, mentioned
The accuracy of high C=C fracture.And the pyrolysis product of perfluoroolefine is usually present carbonyl fluoride or all phosphinylidynes in the prior art
Fluorine, thus pre-activate step implementation can guarantee hexafluoropropylene dimmer rule be cracked into perfluor isobutyl acyl fluorides and perfluor second
Acyl effectively avoids the generation of perfluor carbonyl fluoride by-product.
B) perfluor five-carbon ketone is prepared as raw material using perfluor acetylfluoride prepared by hexafluoropropene and step a)；In the second catalysis
The second catalyst that load capacity is 1%-60% is added in reaction tube, by perfluor acetylfluoride and hexafluoropropene gas reaction raw materials with
The second catalytic reaction tube for being filled with the second catalyst is connected；Check device air-tightness, control reaction temperature are 50 DEG C -300 DEG C, pressure
Power is normal pressure, and the Ventilation Rate of raw material is 5g/h-100g/h, by the Ventilation Rate of control perfluor acetylfluoride and hexafluoropropene come
The reaction rate is controlled, after perfluor acetylfluoride and hexafluoropropene 1-2h are passed through in system, opens outlet valve, it is cold by second
Condenser carries out condensation collection to product at this time and obtains perfluor five-carbon ketone.Second catalyst is the loaded catalyst of active constituent；
Second catalyst active component includes one or more of LiF, NaF, KF, RbF or CsF.The system of second catalyst
Preparation Method uses following step: the aqueous solution that alkali metal fluoride is configured to concentration as 0.01~10mol/L is weighed, to above-mentioned molten
Activated carbon is added in liquid, is sufficiently stirred, mixing time is 5~60h；Stop stirring, mixed liquor is put in Muffle furnace, evaporation is wherein
Moisture, evaporating temperature is 50~200 DEG C, sufficiently dry to constant weight under conditions of vacuum and room temperature, and black powder can be obtained
The second catalyst of shape；Weighing guarantees that the load capacity of alkali metal fluoride in the loaded catalyst is 1-60%.
The actual conditions of step 2) are as follows: the molal weight ratio of the substance of alkylating reagent and five-carbon ketone are as follows: 1:5-5:1；
The reaction pressure of reaction kettle is 1atm-20atm；Reaction temperature is 20-220 DEG C, and heat preservation is reacted for 5-60 hours, in reaction kettle
When pressure is constant, reaction terminates.Alkali metal fluoride in step 2) is NaF, KF, RbF or CsF；The inert idol
Extremely non-proton organic compound be diethylene glycol dimethyl ether, tetraethyleneglycol dimethyl ether, dimethylformamide, dimethyl sulfoxide or
Acetonitrile；The alkylating reagent is dialkyl sulfate, iodo-alkyl, alkyl tosylate, chloroformic acid ester；It is described
Phase transfer catalyst includes quaternary ammonium salt, quaternary phosphonium salt, crown ether, cryptand and their mixture.Reaction kettle and rectifying column phase
Even, after reaction by the available hydrofluoroether product of rectification and purification, final products purity is greater than 99.9%.Wherein, dipole
The suspension/solution of non-proton organic compound and ionic fluorides can be recycled and reused, and be used multiple times.
Compared with prior art, the beneficial effects of the present invention are:
The present invention devises a kind of device that perfluoropentyl ether is cracked to form using hexafluoropropylene dimmer as raw material, utilizes six
Acyl fluorides is cracked to form after fluoropropene monomer polymerization under the effect of the catalyst and obtains hydrofluoroether later, device design is reasonable, simply
Safety, it is easy to accomplish.Hexafluoropropylene dimmer needed for present invention production is reacted using hexafluoropropene gas as raw material by control
Condition is vaporized to obtain required product, and without generation or generation carbonyl fluoride as few as possible, yield is high, and controllability is strong.
Detailed description of the invention
Fig. 1 is overall structure of the present invention.
Specific embodiment
In order to make those skilled in the art more fully understand technical solution of the present invention, with reference to the accompanying drawing and most
The present invention is described in further detail for good embodiment.
Fig. 1 shows the device that a kind of hexafluoropropylene dimmer cracking prepares perfluoropentyl ether, including perfluor acetylfluoride generates
Unit, perfluor five-carbon ketone generation unit and perfluoropentyl ether generation unit；The perfluor acetylfluoride generation unit includes suitable
Hexafluoropropene air accumulator 1, first catalysis reaction 2 pipes, 5, -2 DEG C of the first condenser 3, pyrolysis furnace cold-traps 6 and -70 of sequence connection
DEG C cold-trap 7；As a preference, activating chamber 4 is arranged between the first condenser and pyrolysis furnace；The perfluor five-carbon ketone generates single
Member includes the second catalytic reaction tube 8 and the second condenser 9 being linked in sequence；- 70 DEG C of cold-traps 7 are urged with described second
Change reaction tube 8 to be connected to；The perfluoropentyl ether generation unit includes the reaction kettle 10 being linked in sequence, stratification tower 11, does
Dry tower 12 and perfluoropentyl ether fluid reservoir 13；Second condenser 9 is connected to the reaction kettle 10.Described -2 DEG C
The liquid outlet of cold-trap is connected to perfluor isobutyl group acyl fluorides fluid reservoir 14.The upper end of first condenser is provided with outlet
It connect with first catalytic tower to recycle unreacted hexafluoropropene.First condenser and second cold
Condensation collet is respectively arranged with outside condenser；The condensation collet is provided with the condensation water inlet for condensed water inlet and outlet
And condensation-water drain.Heating mantle is provided with outside the first catalytic reaction tube of the ground and the second catalytic reaction tube.Described
Activating chamber and the pyrolysis furnace are connect with heater respectively.
Embodiment 1: the preparation of hexafluoropropylene dimmer raw material: by hexafluoropropene gas by being catalyzed equipped with NaF/Al2O3
The catalytic reaction tube of agent, the load capacity of catalyst are 10%, time of contact 0.1s；The temperature of catalytic reaction tube is 150 DEG C, instead
Mixed gas after answering enters the condenser with cooling jacket by port entrance, and condensate temperature is 10 DEG C, and unreacted six
Fluoropropene is recycled to catalytic reaction tube through gas vent.The purity of liquid hexafluoropropylene dimmer in detection condenser receiver
It is 99.3%.The yield of hexafluoropropylene dimmer is shown in Table 1.
Embodiment 2: the preparation of hexafluoropropylene dimmer raw material: by hexafluoropropene gas by being equipped with AgF/C catalyst
Catalytic reaction tube, the load capacity of catalyst are 15%, and the temperature of catalyst filling column is 180 DEG C, time of contact 10s, reaction
Mixed gas afterwards enters the condenser with cooling jacket by air inlet, and condensate temperature is 10 DEG C；Unreacted hexafluoro third
Alkene is recycled to catalytic reaction tube column through outlet.The purity of liquid hexafluoropropylene dimmer is 99.2% in detection condenser.Set
1 is shown in Table with the yield of rear hexafluoropropylene dimmer.
Embodiment 3: hexafluoropropene gas the preparation of hexafluoropropylene dimmer raw material: is passed through into urging equipped with KF/C catalyst
Change reaction tube, the load capacity of catalyst is 20%, and the temperature of catalyst filling column is 220 DEG C, time of contact 30s；After reaction
Mixed gas by air inlet enter with cooling jacket condenser, condensate temperature be 10 DEG C, unreacted hexafluoropropene
Catalytic reaction tube is recycled to through outlet.The purity of liquid hexafluoropropylene dimmer is 99.3% in detection condenser.After applying
The yield of hexafluoropropylene dimmer is shown in Table 1.
Comparative example 1: the preparation of hexafluoropropylene trimer raw material: by hexafluoropropene gas by being catalyzed equipped with NaF/Al2O3
The catalytic reaction tube of agent, the load capacity of catalyst are 10%, and the temperature of catalyst reaction tube is 260 DEG C, and time of contact is
0.1s；Mixed gas after reaction enters the condenser with cooling jacket by air inlet, and condensate temperature is 10 DEG C, unreacted
Hexafluoropropene through outlet be recycled to catalyst reaction tube.The purity of liquid hexafluoropropylene trimer in detection condenser
It is 99.3%.The yield of hexafluoropropylene trimer is shown in Table 1.
Comparative example 2: the preparation of hexafluoropropylene trimer raw material: by hexafluoropropene gas by being equipped with AgF/C catalyst
Catalytic reaction tube, the load capacity of catalyst are 15%, and the temperature of catalyst reaction tube is 300 DEG C, time of contact 10s,
Mixed gas after reaction enters the condenser with cooling jacket by air inlet, and condensate temperature is 10 DEG C；Unreacted six
Fluoropropene is recycled to catalyst reaction tube through outlet.The purity of liquid hexafluoropropylene trimer is in detection condenser
99.3%.The yield for applying rear hexafluoropropylene trimer is shown in Table 1.
Comparative example 3: hexafluoropropene gas the preparation of hexafluoropropylene trimer raw material: is passed through into urging equipped with KF/C catalyst
Change reaction tube, the load capacity of catalyst is 20%, and the temperature of catalyst reaction tube is 320 DEG C, time of contact 30s；Instead
Mixed gas after answering enters the condenser with cooling jacket by air inlet, and condensate temperature is 10 DEG C, unreacted hexafluoro
Propylene is recycled to catalyst reaction tube through outlet.The purity of liquid hexafluoropropylene trimer is in detection condenser
99.3%.The yield for applying rear hexafluoropropylene trimer is shown in Table 1.
Table 1
Embodiment 4: it hexafluoropropylene dimmer cracking: 1) pre-activate: specifically includes and hexafluoropropylene dimmer is passed through 200 DEG C
The reactor filled with pre-activate carrier in activate 1.5h；The active constituent of the pre-activate carrier is four (pentafluorophenyl group) boron
Hydrochlorate and Al ((CF3) 3) 3 according to mass ratio 1:3 mixture；The carrier of pre-activate carrier is SiO2；Load capacity is 15%.2)
Load capacity is filled in pyrolysis furnace and is 15% Ag2O/Al2O3 catalyst, and pyrolysis furnace is heated to 400 DEG C.By oxygen and activation
Hexafluoropropylene dimmer afterwards is passed through in pyrolysis furnace according to molar ratio 1:1.Reaction pressure is that 5bar. product is perfluor butyryl fluorine
50.09%, perfluor acetylfluoride 26.92%.
Embodiment 5: it hexafluoropropylene dimmer cracking: 1) pre-activate: specifically includes and hexafluoropropylene dimmer is passed through 200 DEG C
The reactor filled with pre-activate carrier in activate 1.5h；The active constituent of the pre-activate carrier is four (pentafluorophenyl group) boron
Hydrochlorate and Al ((CF3) 3) 3 according to mass ratio 1:3 mixture；The carrier of pre-activate carrier is SiO2；Load capacity is 15%.It splits
Load capacity is filled in solution furnace and is 15% KF/Al2O3 catalyst, and pyrolysis furnace is heated to 400 DEG C.After oxygen and activation
Hexafluoropropylene dimmer is passed through in pyrolysis furnace according to molar ratio 1:1, reaction pressure 5bar.Product is perfluor butyryl fluorine
62.46%, perfluor acetylfluoride 33.54%.
Embodiment 6: it hexafluoropropylene dimmer cracking: 1) pre-activate: specifically includes and hexafluoropropylene dimmer is passed through 180 DEG C
The reactor filled with pre-activate carrier in activate 2h；The active constituent of the pre-activate carrier is four (pentafluorophenyl group) boric acid
Salt and Al ((CFH2) 6) 3 according to mass ratio 1:1 mixture；The carrier of pre-activate carrier is Al2O3；Load capacity is 10%.It splits
Load capacity is filled in solution furnace and is 20% CuO/C catalyst, and pyrolysis furnace is heated to 600 DEG C.By six after oxygen and activation
Fluoropropene dimer is passed through in pyrolysis furnace according to molar ratio 10:1, and reaction pressure is normal pressure.Product is perfluor butyryl fluorine
57.90%, perfluor acetylfluoride 31.09%.
Embodiment 7: it hexafluoropropylene dimmer cracking: 1) pre-activate: specifically includes and hexafluoropropylene dimmer is passed through 220 DEG C
The reactor filled with pre-activate carrier in activate 1h；The active constituent of the pre-activate carrier is four (pentafluorophenyl group) boric acid
Salt and Al (CF2H) 3 according to mass ratio 1:5 mixture；The carrier of pre-activate carrier is B2O3；Load capacity is 20%.Pyrolysis furnace
In fill the CsF/C catalyst that load capacity is 10%, and pyrolysis furnace is heated to 150 DEG C.By the hexafluoro third after oxygen and activation
Alkene dimer is passed through in pyrolysis furnace according to molar ratio 1:10, reaction pressure 10bar.Product is perfluor butyryl fluorine 63.76%, entirely
Fluoracyl fluoride 34.24%.
Embodiment 8: hexafluoropropylene dimmer cracking: the Ag2O/Al2O3 that load capacity is 15% is filled in pyrolysis furnace and is catalyzed
Agent, and pyrolysis furnace is heated to 400 DEG C.Oxygen and hexafluoropropylene dimmer are passed through in pyrolysis furnace according to molar ratio 1:1.Reaction
Pressure is that 5bar. product is perfluor butyryl fluorine 35.13%, perfluor acetylfluoride 18.86%.Carbonyl fluoride 12.52%.
Embodiment 9: hexafluoropropylene dimmer cracking: filling the KF/Al2O3 catalyst that load capacity is 15% in pyrolysis furnace,
And pyrolysis furnace is heated to 400 DEG C.Oxygen and hexafluoropropylene dimmer are passed through in pyrolysis furnace according to molar ratio 1:1, reaction pressure
Power is 5bar.Product is perfluor butyryl fluorine 50.74%, perfluor acetylfluoride 27.25%.Carbonyl fluoride 6.32%.
Embodiment 10: hexafluoropropylene dimmer cracking: filling the CuO/C catalyst that load capacity is 20% in pyrolysis furnace, and
Pyrolysis furnace is heated to 600 DEG C.Oxygen and hexafluoropropylene dimmer are passed through in pyrolysis furnace according to molar ratio 10:1, reaction pressure
For normal pressure.Product is perfluor butyryl fluorine 44.24%, perfluor acetylfluoride 23.76%.Carbonyl fluoride 12.35%.
Embodiment 11: hexafluoropropylene dimmer cracking: filling the CsF/C catalyst that load capacity is 10% in pyrolysis furnace, and
Pyrolysis furnace is heated to 150 DEG C.Hexafluoropropylene dimmer after oxygen and activation is passed through in pyrolysis furnace according to molar ratio 1:10,
Reaction pressure is 10bar.Product is perfluor butyryl fluorine 52.69%, perfluor acetylfluoride 28.3%, carbonyl fluoride 5.64%.
Embodiment 12: perfluor five-carbon ketone is prepared by raw material of perfluor acetylfluoride: load being added in the second catalytic reaction tube
The CsF/C that amount is 1%, by perfluor acetylfluoride and hexafluoropropene gas reaction raw materials and the second catalytic reaction tube for being filled with catalyst
It is connected；Check device air-tightness, control reaction temperature are 50 DEG C, and pressure is normal pressure, and the Ventilation Rate of raw material is 5g/h, pass through control
The Ventilation Rate of perfluor acetylfluoride and hexafluoropropene processed controls the reaction rate, and perfluor acetylfluoride and hexafluoro are passed through in system
After propylene 1-2h, outlet valve is opened, condensation collection is carried out to product at this time.Obtained perfluor five-carbon ketone yield is 35%.
Embodiment 13: perfluor five-carbon ketone is prepared by raw material of perfluor acetylfluoride: load being added in the second catalytic reaction tube
The NaF/C that amount is 20% reacts perfluor acetylfluoride with hexafluoropropene gas reaction raw materials with the second catalysis for being filled with catalyst
Pipe is connected；Check device air-tightness, control reaction temperature are 200 DEG C, and pressure is normal pressure, and the Ventilation Rate of raw material is 50g/h, are led to
The Ventilation Rate for crossing control perfluor acetylfluoride and hexafluoropropene controls the reaction rate, be passed through in system perfluor acetylfluoride with
After hexafluoropropene 1-2h, outlet valve is opened, condensation collection is carried out to product at this time.Obtained perfluor five-carbon ketone yield is
82%.
Embodiment 14: perfluor five-carbon ketone is prepared by raw material of perfluor acetylfluoride: load being added in the second catalytic reaction tube
The NaF/C that amount is 60% reacts perfluor acetylfluoride with hexafluoropropene gas reaction raw materials with the second catalysis for being filled with catalyst
Pipe is connected；Check device air-tightness, control reaction temperature are 300 DEG C, and pressure is normal pressure, and the Ventilation Rate of raw material is 100g/h,
The reaction rate is controlled by the Ventilation Rate of control perfluor acetylfluoride and hexafluoropropene, perfluor acetylfluoride is passed through in system
After hexafluoropropene 1-2h, outlet valve is opened, condensation collection is carried out to product at this time.Obtained perfluor five-carbon ketone yield is
85%.
Embodiment 15: perfluoropentyl ether is prepared by raw material of perfluor five-carbon ketone: by perfluor five-carbon ketone, 71g iodine first obtained by 28g
Alkane, 55g diethylene glycol dimethyl ether, 5.8g anhydrous potassium fluoride, 2g methyl tricapryl ammonium chloride, put into can in pressure-bearing reaction kettle,
Electric stirring is opened, speed of agitator is 300 revs/min, sets temperature of reaction kettle as 100 DEG C, the reaction pressure of reaction kettle is
1atm；It is kept for 28 hours, the KOH aqueous solution of 15g mass fraction 30% is added into reaction kettle.The further water of gained mixed liquor
It washes, liquid separation, recycles and use after the dry water removal of upper layer organic solvent, lower layer's fluorine mutually obtains perfluor penta after drying, rectifying column rectifying
Base methyl ether.It is greater than 99.9% through gas chromatographic detection product purity.Conversion rate of products 92.8%, product selectivity 99%.
Embodiment 16: perfluoropentyl ether is prepared by raw material of perfluor five-carbon ketone: by perfluor five-carbon ketone, 15.6g obtained by 108g
Iodoethane, 30g diethylene glycol dimethyl ether, 5.8g anhydrous potassium fluoride, 1g methyl tricapryl ammonium chloride, putting into can pressure-bearing reaction kettle
Interior, the reaction pressure of reaction kettle is 10atm；Open electric stirring, speed of agitator be 300 revs/min, set temperature of reaction kettle as
220 DEG C, temperature is kept for 8 hours after rising to 220 DEG C, the KOH aqueous solution of addition 60g mass fraction 30% into reaction kettle, and
220 DEG C are continued to cool down to room temperature after being kept for 1 hour.Gained mixed liquor further washes, liquid separation, and organic solvent drying in upper layer removes
It recycles and uses after water, lower layer's fluorine mutually obtains perfluoropentyl ether after drying, rectifying column rectifying.It is pure through gas chromatographic detection product
Degree is greater than 99.9%.Conversion rate of products 18.95%.
Embodiment 17: by perfluor five-carbon ketone, 12.6g dimethyl suflfate, 25g diethylene glycol dimethyl ether, 5.8g obtained by 21.6g
Anhydrous potassium fluoride, 1g methyl tricapryl ammonium chloride, putting into can be in pressure-bearing reaction kettle, and the reaction pressure of reaction kettle is 20atm；It opens
Electric stirring is opened, speed of agitator is 300 revs/min, sets temperature of reaction kettle as 120 DEG C, holding 9 is small after temperature rises to 120 DEG C
When, the KOH aqueous solution of 20g mass fraction 30% is added into reaction kettle, and continue to cool down to after being kept for 1 hour at 120 DEG C
Room temperature.Gained mixed liquor further washes, liquid separation, recycles and uses after the dry water removal of upper layer organic solvent, lower layer's fluorine mutually through drying,
Perfluoropentyl methyl ether is obtained after rectifying column rectifying.It is greater than 99.9% through gas chromatographic detection product purity.Conversion rate of products
82.8%.
Embodiment 18: by perfluor five-carbon ketone, 12.6g dimethyl suflfate, 25g diethylene glycol dimethyl ether, 5.8g obtained by 21.6g
Anhydrous potassium fluoride, 1g methyl tricapryl ammonium chloride, putting into can be in pressure-bearing reaction kettle, and the reaction pressure of reaction kettle is 10atm, is opened
Electric stirring is opened, speed of agitator is 300 revs/min, sets temperature of reaction kettle as 20 DEG C, and temperature is kept for 9 hours after rising to 20 DEG C,
The KOH aqueous solution of 20g mass fraction 30% is added into reaction kettle, and continues to cool down to room temperature after being kept for 1 hour at 20 DEG C.
Gained mixed liquor further washes, liquid separation, recycles and uses after the dry water removal of upper layer organic solvent, lower layer's fluorine is mutually through drying, rectifying
Perfluoropentyl methyl ether is obtained after tower rectifying.It is greater than 99.9% through gas chromatographic detection product purity.Conversion rate of products 78.8%.
The above is only a preferred embodiment of the present invention, for those of ordinary skill in the art, according to the present invention
Thought, there will be changes in the specific implementation manner and application range, and the content of the present specification should not be construed as to the present invention
Limitation.
Claims (7)
1. the device that a kind of hexafluoropropylene dimmer cracking prepares perfluoropentyl ether, which is characterized in that raw including perfluor acetylfluoride
At unit, perfluor five-carbon ketone generation unit and perfluoropentyl ether generation unit；The perfluor acetylfluoride generation unit includes
The hexafluoropropene air accumulator of sequential communication, the first catalytic reaction tube, the first condenser, pyrolysis furnace, -2 DEG C of cold-traps and -70 DEG C are cold
Trap；The perfluor five-carbon ketone generation unit includes the second catalytic reaction tube and the second condenser being linked in sequence；Described-
70 DEG C of cold-traps are connected to second catalytic reaction tube；The perfluoropentyl ether generation unit includes the reaction being linked in sequence
Kettle, stratification tower, drying tower and perfluoropentyl ether fluid reservoir；Second condenser is connected to the reaction kettle.
2. the device that hexafluoropropylene dimmer cracking according to claim 1 prepares perfluoropentyl ether, which is characterized in that institute
The liquid outlet for -2 DEG C of cold-traps stated is connected to perfluor isobutyl group acyl fluorides fluid reservoir, and -2 DEG C of cold-traps are for collecting perfluor
Acetylfluoride.
3. the device that hexafluoropropylene dimmer cracking according to claim 1 prepares perfluoropentyl ether, which is characterized in that institute
The upper end for the first condenser stated is provided with outlet and connect with first catalytic tower to recycle unreacted hexafluoro
Propylene.
4. the device that hexafluoropropylene dimmer cracking according to claim 1 prepares perfluoropentyl ether, which is characterized in that institute
The first condenser and the second condenser external stated are respectively arranged with condensation collet；The condensation collet is provided with for condensation
The condensation water inlet and condensation-water drain of water inlet and outlet.
5. the device that hexafluoropropylene dimmer cracking according to claim 1 prepares perfluoropentyl ether, which is characterized in that institute
It states and is provided with heating mantle outside the first catalytic reaction tube of ground and the second catalytic reaction tube.
6. the device that hexafluoropropylene dimmer cracking according to claim 1 prepares perfluoropentyl ether, which is characterized in that institute
Activating chamber is provided between the first condenser and the pyrolysis furnace stated.
7. the device that hexafluoropropylene dimmer cracking according to claim 6 prepares perfluoropentyl ether, which is characterized in that institute
The activating chamber and the pyrolysis furnace stated connect with heater respectively.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1177374A (en) * | 1995-01-20 | 1998-03-25 | 美国3M公司 | Cleaning process and composition |
| CN105541606A (en) * | 2015-12-29 | 2016-05-04 | 天津市长芦化工新材料有限公司 | Synthetic method of perfluoropropanoyl fluoride and preparation method of catalyst applied to reaction |
| CN108440261A (en) * | 2018-04-20 | 2018-08-24 | 北京宇极科技发展有限公司 | The preparation method of perfluor ketone |
-
2018
- 2018-11-30 CN CN201811458161.XA patent/CN109503363A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1177374A (en) * | 1995-01-20 | 1998-03-25 | 美国3M公司 | Cleaning process and composition |
| CN105541606A (en) * | 2015-12-29 | 2016-05-04 | 天津市长芦化工新材料有限公司 | Synthetic method of perfluoropropanoyl fluoride and preparation method of catalyst applied to reaction |
| CN108440261A (en) * | 2018-04-20 | 2018-08-24 | 北京宇极科技发展有限公司 | The preparation method of perfluor ketone |
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