CN109534972A - The method that hexafluoropropylene dimmer cracking prepares perfluor five-carbon ketone - Google Patents
The method that hexafluoropropylene dimmer cracking prepares perfluor five-carbon ketone Download PDFInfo
- Publication number
- CN109534972A CN109534972A CN201811458206.3A CN201811458206A CN109534972A CN 109534972 A CN109534972 A CN 109534972A CN 201811458206 A CN201811458206 A CN 201811458206A CN 109534972 A CN109534972 A CN 109534972A
- Authority
- CN
- China
- Prior art keywords
- perfluor
- hexafluoropropylene dimmer
- hexafluoropropylene
- catalyst
- hexafluoropropene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/272—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions
- C07C17/278—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions of only halogenated hydrocarbons
- C07C17/281—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions of only halogenated hydrocarbons of only one compound
-
- 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 chemical fields, and in particular to a kind of method that hexafluoropropylene dimmer cracking prepares perfluor five-carbon ketone.Preparation method enters oxidation furnace and oxygen including 1) hexafluoropropylene dimmer and carries out cracking reaction under the first catalysts conditions；The isolated perfluor acetylfluoride of pyrolysis product；2) the perfluor acetylfluoride prepared using hexafluoropropene and step 1) prepares perfluor five-carbon ketone as raw material under the second catalyst action.The present invention is raw material by hexafluoropropylene trimer, generates perfluor five-carbon ketone, controllability is strong, high conversion efficiency, mild condition, and whole flow process is easy to operate.
Description
Technical field
The invention belongs to fluorine chemical fields, and in particular to a kind of hexafluoropropylene dimmer cracking prepares the side of perfluor five-carbon ketone
Method.
Background technique
In recent years, fluorine-containing ketone compound has in use because of its good inertia, thermal stability and hydrolytic stability
There are short atmosphere duration and low global warming potential, and gets the attention.
The property of fluorine-containing ketone compound is the key that determine its application field, wherein has low boiling point, high volatile, low
Properties such as malicious, non-ignitable, insulating properties is strong, easily vaporization, heat absorption capacity the be strong and fluorine ketone for being easy to storage and transportation is suitable as extinguishing chemical, in USP
In 6478979, Rivers etc. discloses application of the perfluorinated ketone in fire extinguishing.The commodity Novec that Minnesota Mining and Manufacturing Company releases
1230, molecular formula is CF3CF2C (O) CF (CF3) 2, is a kind of environmentally protective extinguishing chemical that can be used for a long time.Perfluor five-carbon ketone
(3M trade name NovecTM 5110) is used as a kind of novel synthesis gas body, and GWP value is less than 1, the potential value (ozone of ozone-depleting
Depleting potential, ODP) it is about 0, atmospheric lifetime is about 16 days, and it is close that dielectric strength, which is about 2 times of SF6 gas,
The insulating gas of the most potential substitution SF6 found over year.ABB AB mixes with air perfluor five-carbon ketone, is used for 22kV
Switchgear has simultaneously passed through the application performance test carried out according to IEC 62271-200-2001
The property that perfluor ketone with oxygen mix, can generate radio frequency plasma can be used to clean chemical vapor deposition
Product room, physical vapor deposition chamber or etching chamber.The standard cleaning gas such as NF3 that the purge gas and semicon industry use,
CF4, C2F6, c-C4F8O and C3F8 are compared, and be can be shortened scavenging period and are reduced PFC discharge.Patent CN 1505694A report
The perfluor ketone for containing 4 to 7 carbon atoms is used to remove unwanted deposit, erosion as active gases in gas-phase reactor
Good effect is achieved when carving dielectric and metal material.Meanwhile the active gases of the perfluor ketone is alternatively arranged as Fluorine source, preparation contains
Fluorine or fluorine doped material.Patent CN1809324A and patent CN101346335A reports halogenated perfluor ketone and respectively containing heteroatomic
Perfluor ketone is in refrigerant, extinguishing chemical, cleaning agent, additive, foaming agent, solvent, aerosol propellants and agrochemical field
Using.Therefore, explore exploitation be easy to industrial amplification production perfluor ketone production technology it is very necessary.
Summary of the invention
The purpose of the present invention is to provide a kind of methods that hexafluoropropylene dimmer cracking prepares perfluor five-carbon ketone.
The present invention to achieve the above object, using following technical scheme:
A kind of method that hexafluoropropylene dimmer cracking prepares perfluor five-carbon ketone, specifically include the following steps: 1) hexafluoro third
Alkene dimer enters oxidation furnace and oxygen and carries out cracking reaction under the first catalysts conditions；The isolated perfluor of pyrolysis product is different
Butyryl fluorine and perfluor acetylfluoride；
2) the perfluor acetylfluoride prepared using hexafluoropropene and step 1) is prepared complete as raw material under the second catalyst action
Fluorine five-carbon ketone；
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
The first catalytic reaction tube column that outlet is recycled to support type ionic fluorides recycles.Take the fluid sample in the first condenser
The purity of sample detection, gained hexafluoropropylene dimmer is greater than 99%.
Step 1) specifically include the following steps:
Using oxygen and hexafluoropropylene dimmer as raw material, under the first catalyst action with perfluor acetyl is prepared in reactor
Fluorine, catalytic time are 0.1s to 200s, and temperature is 150-600 DEG C；Pressure is 0-1MP；Wherein, first catalysis
Agent is loaded catalyst, active constituent Ag2O, Al2O3, CuO, AgF, NaF, KF, RbF or CsF；Oxygen and hexafluoro third
The molar ratio of alkene dimer is 1:10-10:1；Available perfluor isobutyl acyl fluorides is collected to product in -2 DEG C of cold-traps and is lacked
Measure hexafluoropropylene dimmer.Rectifying is carried out to it, obtained a small amount of hexafluoropropylene dimmer is passed through pyrolysis furnace again and is split
Solution.It collects to obtain perfluor acetylfluoride in -70 DEG C of cold-trap cold-traps.
Hexafluoropropylene dimmer enters reactor with liquid form in step reaction, since fluid molecule is compared to gas point
Son has shorter intermolecular distance, therefore more gaseous state hexafluoropropylene dimmers are had in the slow gasification of liquid charging stock
Molecule comes into full contact with oxygen, so as to shorten the pyrolysis time of hexafluoropropylene dimmer, significantly improves raw material and integrally cracks effect
Rate.And the presence of the hexafluoropropylene dimmer more contacted with oxygen can prevent the perfluor isobutyl acyl fluorides being cracked to form and perfluor second
The further cracking of acyl fluorides, to guarantee that gained perfluor acetylfluoride has higher degree.
Preferably, it further include pre-activate step in step 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 group) boron
Hydrochlorate and alkyl fluoride aluminium salt according to mass ratio 1:1-1:5 mixture；Wherein n=1-6；The carrier of pre-activate carrier be 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.
2) perfluor five-carbon ketone is prepared as raw material using perfluor acetylfluoride prepared by hexafluoropropene and step 1)；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%.
Method of the invention can in an intermittent fashion or continuously mode carries out.
Compared with prior art, the beneficial effects of the present invention are:
The present invention is raw material by hexafluoropropylene dimmer, generates perfluor five-carbon ketone；In hexafluoropropylene dimmer cracking
In the process, be capable of selectivity controllably obtains target pyrolysis product perfluor acetylfluoride and perfluor isobutyl group acyl fluorides, high conversion efficiency,
Mild condition, whole flow process is easy to operate, in addition, cracking needed for hexafluoropropylene dimmer using hexafluoropropene gas as raw material,
By controlling reaction condition, available hexafluoropropylene dimmer, yield is high, and by-product is few.
Specific embodiment
In order to make those skilled in the art more fully understand technical solution of the present invention, implement below with reference to best
The present invention is described in further detail for example.
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%.
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 (6)
1. a kind of method that hexafluoropropylene dimmer cracking prepares perfluor five-carbon ketone, which is characterized in that include the following steps:
1) hexafluoropropylene dimmer enters oxidation furnace and oxygen and carries out cracking reaction under the first catalysts conditions；Pyrolysis product point
From obtaining perfluor acetylfluoride；
2) the perfluor acetylfluoride prepared using hexafluoropropene and step 1) prepares perfluor five as raw material under the second catalyst action
Carbon ketone；
2. the method that hexafluoropropylene dimmer cracking according to claim 1 prepares perfluor five-carbon ketone, which is characterized in that institute
The hexafluoropropylene dimmer stated 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 ionic fluorides is 10%-20%；Carrier is activated carbon, three oxidations
Two aluminium, silica or magnesia；Ionic fluorides are AgF, NaF, KF, RbF or CsF.
3. the method that hexafluoropropylene dimmer cracking according to claim 1 prepares perfluor five-carbon ketone, which is characterized in that step
It is rapid 1) specifically include the following steps: using oxygen and hexafluoropropylene dimmer as raw material, in reactor under the first catalyst action
In prepare perfluor acetylfluoride, the catalytic time is 0.1s to 200s, and temperature is 150-600 DEG C；Pressure is 0-1MP；Wherein,
First catalyst be loaded catalyst, active constituent Ag2O, Al2O3, CuO, AgF, NaF, KF, RbF or
CsF；The molar ratio of oxygen and hexafluoropropylene dimmer is 1:10-10:1.
4. the method that hexafluoropropylene dimmer cracking according to claim 3 prepares perfluor five-carbon ketone, which is characterized in that step
It is rapid 1) in further include hexafluoropropylene dimmer pre-activate step；It specifically includes and hexafluoropropylene dimmer is passed through 180-220 DEG C
1-2h is activated in reactor filled with pre-activate carrier；The active constituent of the pre-activate carrier is four (pentafluorophenyl group) boric acid
Salt and alkyl fluoride aluminium salt according to mass ratio 1:1-1:5 mixture；N=1-6；The carrier of pre-activate carrier is S iO2, Al
2O3 or B2O3；Load capacity is 10%-20%.
5. the method that hexafluoropropylene dimmer cracking according to claim 4 prepares perfluor five-carbon ketone, which is characterized in that institute
The alkyl fluoride aluminium salt stated is Al ((CR1R2R3) n) 3 monomers or mixture；Wherein R1, R2 and R3 be H or F and at least its
One of be F, n=1-6.
6. the method that hexafluoropropylene dimmer cracking according to claim 1 prepares perfluor five-carbon ketone, which is characterized in that step
It is rapid 2) specifically include the following steps: preparing five carbon of perfluor as raw material using perfluor acetylfluoride prepared by hexafluoropropene and step 1)
Ketone；The second catalyst that load capacity is 1%-60% is added in reaction column, perfluor acetylfluoride is reacted with hexafluoropropene gas
Raw material is connected with the reaction column for being filled with the second catalyst；Check device air-tightness, control reaction temperature are 50 DEG C -300 DEG C, pressure
For normal pressure, the Ventilation Rate of raw material is 5g/h-100g/h, is controlled by the Ventilation Rate of control perfluor acetylfluoride and hexafluoropropene
Make the reaction rate, after perfluor acetylfluoride and hexafluoropropene 1-2h are passed through in system, open outlet valve, at this time to product into
Row condensation is collected.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811458206.3A CN109534972A (en) | 2018-11-30 | 2018-11-30 | The method that hexafluoropropylene dimmer cracking prepares perfluor five-carbon ketone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811458206.3A CN109534972A (en) | 2018-11-30 | 2018-11-30 | The method that hexafluoropropylene dimmer cracking prepares perfluor five-carbon ketone |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109534972A true CN109534972A (en) | 2019-03-29 |
Family
ID=65851958
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811458206.3A Pending CN109534972A (en) | 2018-11-30 | 2018-11-30 | The method that hexafluoropropylene dimmer cracking prepares perfluor five-carbon ketone |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109534972A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111233653A (en) * | 2020-03-31 | 2020-06-05 | 国网陕西省电力公司电力科学研究院 | Economical and efficient perfluoronitrile and perfluoroketone co-production process and device |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106946669A (en) * | 2017-03-21 | 2017-07-14 | 国家电网公司 | A kind of environmentally friendly insulating gas joint production process and industrial production device |
-
2018
- 2018-11-30 CN CN201811458206.3A patent/CN109534972A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106946669A (en) * | 2017-03-21 | 2017-07-14 | 国家电网公司 | A kind of environmentally friendly insulating gas joint production process and industrial production device |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111233653A (en) * | 2020-03-31 | 2020-06-05 | 国网陕西省电力公司电力科学研究院 | Economical and efficient perfluoronitrile and perfluoroketone co-production process and device |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| AU2012339415B2 (en) | Method for preparing fluorine-containing vinyl ether | |
| KR20030092096A (en) | Use of Perfluoroketones as Vapor Reactor Cleaning, Etching, and Doping Gases | |
| CN104610035A (en) | Method for preparing high-purity 4,4'-difluorobenzophenone | |
| CN104844411B (en) | A kind of method for synthesizing the butadiene of hexafluoro 1,3 | |
| CN111825568A (en) | Synthesis method of perfluoroisobutyronitrile | |
| TW201121938A (en) | Manufacture of difluoroethylene carbonate, trifluoroethylene carbonate and tetrafluoroethylene carbonate | |
| CN111848444A (en) | Synthesis method of perfluoroisobutyronitrile | |
| CN109534972A (en) | The method that hexafluoropropylene dimmer cracking prepares perfluor five-carbon ketone | |
| CN109534963A (en) | The method that hexafluoropropylene trimer cracking prepares perfluor five-carbon ketone | |
| CN105541606A (en) | Synthetic method of perfluoropropanoyl fluoride and preparation method of catalyst applied to reaction | |
| CN106495982A (en) | A kind of method that catalysis prepares 1,3 butadiene of hexafluoro | |
| US20100331582A1 (en) | Process and Catalyst for Converting Alkanes | |
| CN109503341A (en) | The method for preparing seven carbon ketone of perfluor five-carbon ketone and perfluor simultaneously | |
| JP5301984B2 (en) | 1,4-bis (bromodifluoromethyl) tetrafluorobenzene and process for producing the same | |
| CN111777503A (en) | Synthetic method of heptafluoroisobutyronitrile | |
| CN116514642A (en) | Preparation method and application of perfluoro-hexanone | |
| CN109761795A (en) | The method that hexafluoropropylene trimer prepares perfluor isobutyl acyl fluorides | |
| RU2494086C2 (en) | Method of producing perfluoroethyl isopropyl ketone | |
| CN106542981B (en) | Preparation method of perfluoro nonacarbon ketone | |
| CN111187145B (en) | Preparation method of hexafluorobutadiene | |
| CN106554262B (en) | Perfluorononacarbon ketone and application thereof | |
| CN106748741A (en) | Perfluor acetylfluoride and preparation method thereof | |
| CN109503365A (en) | The method for preparing perfluor acetylfluoride and perfluor butyryl fluorine simultaneously | |
| RU2526249C2 (en) | Method of obtaining 1,1-difluorochloroethanes | |
| CN101703947B (en) | Complexation-system ionic liquid catalyst-HF solution, preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190329 |