CN105198719B - A kind of preparation method of the pentanone of 2 methyl of perfluor 3 - Google Patents
A kind of preparation method of the pentanone of 2 methyl of perfluor 3 Download PDFInfo
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- CN105198719B CN105198719B CN201510558670.XA CN201510558670A CN105198719B CN 105198719 B CN105198719 B CN 105198719B CN 201510558670 A CN201510558670 A CN 201510558670A CN 105198719 B CN105198719 B CN 105198719B
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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
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
- C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
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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
- C07C45/56—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds
- C07C45/57—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom
- C07C45/58—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom in three-membered rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
- C07D301/08—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase
Abstract
The invention discloses a kind of preparation method of the pentanone of 2 methyl of perfluor 3, it is using the amylene of 2 methyl of perfluor 2 as raw material, gas phase reaction is carried out in fixed bed reactors under catalyst existence condition with the oxidizing gas such as a certain amount of oxygen or air, one-step or two-step gas phase reaction directly prepares the pentanone of 2 methyl of perfluor 3, and two steps gas phase reaction therein mainly includes the amylene epoxidation reaction of 2 methyl of perfluor 2 and epoxide gas phase isomerization is reacted.The present invention is by using above-mentioned technology, gas phase reaction is carried out continuously using fixed bed reactors process, its production process is without solvent, greatly reduce cost and problem of environmental pollution, improve process safety, the problems such as recycling of the separation, solvent and the catalyst that it also avoid solvent and product simultaneously, therefore, the present invention has that cost is low, easily controllable, the product isolation of purified for preparing convenient, catalytic reaction process technological parameter is simple etc. the characteristics of be extremely adapted to industrial production.
Description
Technical field
The present invention relates to a kind of preparation method of perfluor -2- methyl-propione, and in particular to it is a kind of by perfluor -2- methyl -
The preparation of the oxidizing gas such as 2- amylenes and oxygen reaction generation perfluor -2- methyl-propione under conditions of catalyst presence
Method.
Background technology
With eliminating for halon fire agent, main extinguishing chemical of new generation mainly has HFC-227ea, FIC-1311, HFC-
125, HFC-236 and perfluor -2- methyl-propione etc..Wherein environmental-protecting performance is it is still further preferred that perfluor -2- methyl-propione（It is smelly
Oxygen layer destruction ODP values are 0, and greenhouse effects GWP value is only 1）And CF3I.But CF3I cost is higher（Iodine compared with
For costliness）, it is big that existing market promotes difficulty.Perfluor -2- methyl-propione has good environmental protection as Halon's succedaneum, gone out
Fiery concentration is small, fire-fighting efficiency is high, toxicity is low, security is good, small influence to equipment and material, noresidue, is easy to store and transports
The series of advantages such as defeated and applied widely, while fire-fighting efficiency is ensured, solves conventional fluorinated hydrocarbon Halon Replacement
Problem of the product in terms of environmental protection.Therefore, as a kind of new clean fire extinguishing agent, the product has higher cost performance, is one
Long-acting Halon Replacement product truly is planted, with vast potential for future development.
United States Patent (USP) US6630075 is disclosed using hexafluoropropene and perfluoro-propionyl fluoride as Material synthesis perfluor -2- methyl -3-
The preparation method of pentanone.In high-pressure reaction vessel, under anhydrous condition, using contracting ether as reaction medium, hexafluoropropene and perfluor third
Acyl fluorides obtains perfluor hexanone crude product in the presence of KF, then removes impurity trimer by the method for simple distillation or rectifying
With a small amount of hexafluoropropene dimers, the yield and selectivity of reaction are higher, but raw material perfluoro-propionyl fluoride prepares more difficulty.
Hexafluoropropene and the institute of Hexafluoropropylene third cesium fluoride make catalyst (Vilenchik, Ya. M et al.,
Synthesis of perfluorinated ethyl ketones. Zh. Khim, 1978, 23(2): 236-237),
Reaction can obtain perfluor -2- methyl-propione with a step at 20~25 DEG C.But perfluor -2- first in this method synthetic product
Base-propione only accounts for 34.6%, and remaining product includes CF3CF2CO(CF2)5CF3And CF (42.6%)3CF2CO(CF2)8CF3（8%）
Deng being polymer compounds, react poor to the selectivity of target product.
United States Patent (USP) US5466877 then has found hexafluoropropylene dimmer（Perfluoro-2-methyl-2-amylene）Made using NaClO
Its epoxide can be made for oxidant.Epoxide under CsF catalysis by rearrangement can prepare perfluor -2- methyl -
Propione.Hexafluoropropylene dimmer can be obtained conveniently by oligomerization of hexafluoropropene.Therefore, using hexafluoropropene as raw material,
Perfluor -2- methyl-propione is prepared respectively through steps such as oligomerisation, epoxidation and isomerization.Not only step is more for this route, route
It is long, and carried out in the tank reactor equipped with a large amount of solvents and catalyst, it is intermittent reaction, the reaction time is long, solvent
Consumption is big.
On this basis, patent CN103787854 proposes a kind of Improving ways.Using perfluoro-2-methyl-2-amylene as original
Material, the aprotic polar solvent of mixture corresponding proportion carries out epoxidation reaction in liquor natrii hypochloritis.Obtain epoxy compound
Epoxide isomerization is carried out using continuous gas phase catalytic reaction after thing and prepares perfluor -2- methyl-propione, so as to avoid
The a large amount of of solvent are used, and isomerization can be carried out continuously point, reduce cost and environmental pollution.
It is existing to prepare perfluor -2- first by steps such as epoxidation and isomerization by raw material of perfluoro-2-methyl-2-amylene
Base-propione technology inevitably needs largely to use the toxic solvents such as acetonitrile and corrosivity and excitant NaClO etc. to aoxidize
Agent, with low production efficiency, cost is high, the shortcomings of environmental pollution.
The content of the invention
For the above-mentioned problems in the prior art, it is an object of the invention to provide one kind with perfluor -2- methyl -2-
Amylene is the raw material method for preparing perfluor -2- methyl-propione, it using the oxidizing gas such as a certain amount of oxygen or air with
Perfluoro-2-methyl-2-amylene steam carries out gas phase reaction under catalyst existence condition, and one-step or two-step prepares perfluor -2- first
Base-propione.
A kind of preparation method of the perfluor -2- methyl-propione, it is characterised in that with a certain amount of oxidizing gas with
Perfluoro-2-methyl-2-amylene steam in the presence of a catalyst, carries out gas phase reaction, using one-step method or two in tubular reactor
Footwork prepares perfluor -2- methyl-propione.
The preparation method of described a kind of perfluor -2- methyl-propione, it is characterised in that described oxidizing gas includes
Oxygen, air or with N2、He、Ar、CO2In one or more of air-fuel mixture enleanments oxygen；Perfluoro-2-methyl-2-amylene and oxygen
The mixed volume of gas is than 0.5~3：1.
The preparation method of described a kind of perfluor -2- methyl-propione, it is characterised in that one-step method is urged using step oxidation
Agent direct catalytic reaction obtains perfluor -2- methyl-propione；Two-step method is first complete using epoxidation catalyst generation intermediate
Fluoro- 2- methyl -2,3- epoxypentane, then intermediate perfluor -2- methyl -2,3- epoxypentanes are entered by promoting the circulation of qi using rearrangement catalyst
Phase isomerization reaction prepares perfluor -2- methyl-propione.
A kind of preparation method of described perfluor -2- methyl-propione, it is characterised in that a described step oxidation catalyst
Including following three kinds：1）Activated carbon is one or more of mixtures in carrier loaded KF, CsF, RbF；2）Ru, Rh, Pd, Pt
Or the noble metal catalyst of Ir load type active carbons；3）Fe with nanotopography2O3、SnO2, BaO or BaF2。
The preparation method of described a kind of perfluor -2- methyl-propione, it is characterised in that a step oxidation catalyst or epoxy
Changing catalyst also has compounding aid to use, wherein the auxiliary agent of a step oxidation catalyst includes KF, La2O3、Sm2O3、CeO2、BaO、
BaF2Or Y2O3, the load capacity of a step oxidation catalysis agent aid is 1 ~ 10%；The auxiliary agent of epoxidation catalyst includes Ag, KF or CsF,
The load capacity of epoxida tion catalyst agent aid is 1 ~ 5%.
A kind of preparation method of described perfluor -2- methyl-propione, it is characterised in that described one-pot oxidation reaction
100 ~ 300 DEG C of temperature, the bar of gross pressure 1 ~ 10, the h of air speed 50-1~500 h-1。
The preparation method of described a kind of perfluor -2- methyl-propione, it is characterised in that two-step method comprises the following steps：
Perfluoro-2-methyl-2-amylene and oxidizing gas are mixed, first reaction generation intermediate is complete in the presence of epoxidation catalyst
Fluoro- 2- methyl -2,3- epoxypentane, reaction condition is 100 ~ 200 DEG C of temperature, the bar of gross pressure 1 ~ 10, the h of air speed 50-1~500
h-1；Then recycle epoxide rearrangement catalyst to carry out gas phase isomerization reaction and prepare target product perfluor -2- methyl -3-
Pentanone, 50 ~ 300 DEG C of temperature, the bar of gross pressure 1 ~ 10, the h of air speed 50-1~300 h-1。
The preparation method of described a kind of perfluor -2- methyl-propione, it is characterised in that the absorbent charcoal carrier includes coconut palm
Shell charcoal, graphite charcoal or mesoporous carbon, activity component load quantity are 1 ~ 15%.
The preparation method of described a kind of perfluor -2- methyl-propione, it is characterised in that the epoxidation catalyst is tool
There are BaO, BaF of nanotopography2、CaO、CaF2, MgO or MgF2；The rearrangement catalyst is Cr2O3, fluorination or it is partially fluorinated
Cr2O3、Al2O3, fluorination or partially fluorinated Al2O3、FeCl3, one or more of mixtures in activated carbon.
A kind of preparation method of described perfluor -2- methyl-propione, it is characterised in that described epoxidation catalyst and
Rearrangement catalyst is filled in the tubular reactor of two series connection respectively, or is filled in same tubular reactor, leading portion filling
Epoxidation catalyst, back segment filling rearrangement catalyst.
The present invention prepares perfluor -2- methyl-propione by raw material of perfluoro-2-methyl-2-amylene, using a certain amount of oxygen
The oxidizing gas such as gas or air carries out gas phase reaction, one with perfluoro-2-methyl-2-amylene steam under catalyst existence condition
Step or two steps prepare perfluor -2- methyl-propione, and its reaction equation is as follows：
（1）One step oxidation perfluoro-2-methyl-2-amylene prepares perfluor -2- methyl-propione
；
（2）Two one step preparation methods of perfluor -2- methyl-propione
I）Perfluoro-2-methyl-2-amylene gas phase catalysis epoxidation generates perfluor -2- methyl -2,3- epoxypentanes
；
II）Perfluor -2- methyl -2,3- epoxypentane gas phase catalysis rearrangements prepare target product perfluor -2- methyl-propione
。
By using above-mentioned technology, compared with prior art, the beneficial effects of the present invention are：
1）Because the present invention is exothermic reaction, the present invention is by using N2、He、Ar、CO2In one or more of gaseous mixtures
Dilution oxygen, on the one hand can suppress over oxidation, prevent burning from making oxygen depletion, reduce its activity, and can reduce carbon distribution
Generation, while dilution gas can eliminate part carbon distribution, improves the service life of catalyst, is conducive to industrializing implementation；
2）Gas phase catalyst in the one-step method or two-step method of the present invention can use catalyst aid, can improve conversion ratio；
3）The present invention is carried out continuously gas-phase catalysis one using perfluoro-2-methyl-2-amylene using tubular reactor process
Step or two steps directly prepare perfluor -2- methyl-propione, and its reactions steps is few, and production process is greatly reduced into without solvent
This and problem of environmental pollution, improve process safety, while it also avoid the separation of solvent and product, solvent and catalyst
The problems such as recycling, reduce post-processing step；By using gas phase catalyst, its cost is low, and it is convenient to prepare, catalytic reaction
Process parameter is easily controllable, and product isolation of purified is simple, is extremely adapted to industrial production.
Embodiment
With reference to specific embodiment, the invention will be further described, but protection scope of the present invention is not limited to this.
Embodiment 1
The step catalysis oxidation perfluoro-2-methyl-2-amylene of activated carbon supported KF, RbF mono- prepares perfluor -2- methyl-propione
（i）The pretreatment of absorbent charcoal carrier
Prepare 4.6 mol/L HNO3The mL of solution 50, then weighs 10g cocoanut active charcoals and is put into round-bottomed flask, pour into and match somebody with somebody
The nitric acid made, the reflow treatment 5h in 90 DEG C of water-baths, then at the same temperature with water washing is distilled 8 hours, by 10 g coconut palms
Shell activated carbon is placed in vacuum drying oven, 110 DEG C of 6 h of drying, is taken out；
（ii）Catalyst is prepared with equi-volume impregnating
By preparing activated carbon is added drop-wise to containing 1g potassium fluorides and the mL of 0.5g rubidium fluoride RbFs mixed liquor 12 under stirring
On, 24h, 110 DEG C of dry 8h are stood, then 550 DEG C of roasting 3h in nitrogen atmosphere, obtain catalyst RbF-KF/AC；
（iii）Catalytic reaction
The reaction tube that catalytic reaction is used is nichrome reaction tube（The mm of internal diameter 8）, constant temperature section length is 100mm, instead
Ying Qian, by 4mL steps（ii）Obtained catalyst puts into the flat-temperature zone of reaction tube, in order to prevent material from condensing, and all reactions connect
Adapter line uses stainless steel tube, and with Heat preservation chuck constant temperature at 70 DEG C or so, perfluoro-2-methyl-2-amylene is using micro
Measuring pump control flow is thermally formed steam into coil evaporator and (enters the perfluoro-2-methyl-2-amylene raw material of reactor
Gas flow is 20mL/min), reactor feed gas O2With diluent gas N2Feed and be respectively using mass flowmenter control flow
20mL/min and 80mL/min, enters reactor together with perfluoro-2-methyl-2-amylene steam, and reaction temperature is stable 200
DEG C, reaction pressure is that gas is received and quantitative analysis using condensing mode after 0.1MPa, reaction, is as a result shown, perfluor -2- first
Base -2- pentene conversions are 65.6%, and perfluor -2- methyl-propione is selectively 68.5%.
Embodiment 2
The step catalysis oxidation perfluoro-2-methyl-2-amylene of activated carbon supported KF, RbF mono- prepares perfluor -2- methyl-propione
Implementation steps be the same as Example 1, changes step（iii）In catalytic reaction temperature be 250 DEG C, reaction pressure is 0.7
Gas is received and quantitative analysis using condensing mode after MPa, reaction, is as a result shown, perfluoro-2-methyl-2-amylene conversion ratio is
76.7%, perfluor -2- methyl-propione are selectively 59.1%.
Embodiment 3
La2O3RbF-KF/AC catalyst preparation perfluor -2- methyl-propione of promotion
（i）Catalyst preparation
RbF-KF/AC catalyst is prepared by embodiment 1 first, 1.06g lanthanum nitrate is weighed, is dissolved in 12mL distilled water
In, it will be added drop-wise under lanthanum nitrate hexahydrate stirring in Rb-KF/AC catalyst, in 110 DEG C of dry 8h, then in nitrogen atmosphere
In 550 DEG C roasting 3h, obtain La2O3- RbF-KF/AC catalyst；
（ii）Catalytic reaction
The step of catalytic reaction process be the same as Example 1（iii）, as a result show, perfluoro-2-methyl-2-amylene conversion ratio is
78.5%, perfluor -2- methyl-propione are selectively 81.1%.
Embodiment 4
La2O3RbF-KF/AC catalyst preparation perfluor -2- methyl-propione of promotion
Implementation process be the same as Example 3, difference part is the flow of oxygen being changed to 40 mL/min, as a result shown, entirely
Fluoro- 2- methyl -2- pentene conversions are 88.9%, and perfluor -2- methyl-propione is selectively 78.3%.
Embodiment 5
The step catalysis oxidation perfluoro-2-methyl-2-amylene of high-ratio surface mineral carbon load Ru and KF mono- prepare perfluor -2- methyl -
Propione
（i）It is prepared by high-ratio surface mineral carbon load KF-Ru catalyst precursors
It is 400 m to take 9.0 g specific surface areas2/ g high-ratio surface graphite（Average grain diameter is 2.0 μm）, in air dry oven
12 h of interior 110 DEG C of dryings, by its Ru with 0.760 g3(CO)12It is put into ball grinder, the min of 300 r/min ball milling mixings 60,
On the basis of weight of carbon carriers, the wt% of control carrier amount containing Ru 4.0.933g KNO3Plus 5 mL water be made into mixed aqueous solution, 9.0
G high-ratio surfaces graphite is added to be impregnated in mixed aqueous solution.On the basis of weight of carbon carriers, carrier 4wt% containing K concentration is controlled,
Dipping 12h obtains being crushed to 14 again after powder, 30 MPa compression moldings after 110 DEG C of drys 12 h removing moisture ~
18 mesh（1.0~1.4mm）Produce catalyst precursor.
（ii）Activation of catalyst
4mL catalyst is put into the flat-temperature zone of reaction tube, 80mL/min N is passed through2, and reactor is warming up to 350℃,
And constant temperature 2h.200 DEG C are cooled to, while being passed through 80mL/min N2With 20mL/min perfluoro-2-methyl-2-amylenes, to catalysis
Agent carries out activation 4h, is being cooled to 150 DEG C.
（iii）Catalytic reaction
The step of catalytic reaction process be the same as Example 1（iii）.Difference part is catalytic reaction temperature being set as 150
DEG C, after induction period short time, reaction tends towards stability.As a result show, perfluoro-2-methyl-2-amylene conversion ratio is 68.5%,
Perfluor -2- methyl-propione is selectively 89.1%.
Embodiment 6
Nanometer BaO catalyst preparation perfluor -2- methyl-propione that KF promotes
（i）Catalyst preparation
Catalyst is prepared using solution combustion method.Weigh 20 g Ba (NO3)2, 0.65 g KF and 15.43 g C2H5NO2
（Glycine）It is dissolved in 300 ml distilled water and is sufficiently mixed stirring.Solution is heated to 70 DEG C, glue is evaporated to, is transferred to micro-wave oven
Middle heating burning, naturally cools to room temperature, 2 h of the lower 400 DEG C of roastings of air atmosphere.Above-mentioned foaming solid is scattered in second again
In alcohol, ultrasonically treated 50 min, 50 ~ 60 DEG C of evaporation solvents obtain scattered nanoscale KF-BaO powder.30 MPa compression moldings
It is crushed to 14 ~ 18 mesh again afterwards（1.0~1.4mm）Produce catalyst precursor.
（ii）Catalytic reaction
The step of catalytic reaction process be the same as Example 1（iii）.Difference part is catalytic reaction temperature being set as 220
DEG C, after induction period short time, reaction tends towards stability.As a result show, perfluoro-2-methyl-2-amylene conversion ratio is 67.5%,
Perfluor -2- methyl-propione is selectively 79.1%.
Embodiment 7
Nanometer BaO-Ag catalysis perfluoro-2-methyl-2-amylenes prepare intermediate perfluor -2- methyl -2,3- epoxypentanes
（i）Catalyst preparation
Catalyst is prepared using solution combustion method.Weigh 20 g Ba (NO3)2, 1.02 g AgNO3With 12.43 g
C2H5NO2（Glycine）It is dissolved in 200 ml distilled water and is sufficiently mixed stirring.Solution is heated to 70 DEG C, glue is evaporated to, is transferred to
Burning is heated in micro-wave oven, room temperature, 2 h of the lower 400 DEG C of roastings of air atmosphere is naturally cooled to.Again by above-mentioned foaming solid point
Dissipate in ethanol, ultrasonically treated 50 min, 50 ~ 60 DEG C of evaporation solvents obtain scattered nanoscale Ag2O-BaO powder.30 MPa
14 ~ 18 mesh are crushed to after compression molding again（1.0~1.4mm）Produce catalyst precursor.
（ii）Activation of catalyst
4mL catalyst is put into the flat-temperature zone of reaction tube, 80mL/min N is passed through2, and reactor is warming up to 350 DEG C,
And constant temperature 2h.200 DEG C are cooled to, while being passed through 80mL/min N2With 20mL/min hydrogen, activation 2h is carried out to catalyst,
It is cooled to 150 DEG C.
（iii）Catalytic reaction
The step of catalytic reaction process be the same as Example 1（iii）.Difference part is catalytic reaction temperature being set as 150
℃.As a result show, perfluoro-2-methyl-2-amylene conversion ratio is 67.5%, intermediate perfluor -2- methyl -2,3- epoxypentanes
Selectivity is 89.0%.
Embodiment 8
Nanometer Cr2O3It is perfluor -2- methyl -3- penta to be catalyzed perfluor -2- methyl -2,3- epoxypentane and reset gas phase isomerization
Ketone
（i）Catalyst preparation
The chromic nitrate for weighing 30 g is dissolved in 100 ml water, and the ammonium oxalate for weighing 28.0 g adds above-mentioned solution.In stirring
Above-mentioned mixed solution is heated into 60 DEG C under state promotes ammonium oxalate to be completely dissolved.Then solution is cooled to 20 DEG C, by this solution
The rapid in the mixed solvent being made up of 375mL methanol and 375mL acetone for pouring into 750mL.It is heavy to be filtered out after standing aging 60min
Starch and with drying 24 h at alcohol flushing three times, 60 DEG C.Obtained above-mentioned solid sample is in Muffle furnace, 350 DEG C of air atmosphere
It is calcined 2h.Finally, 14 ~ 18 mesh are crushed to again after 30 MPa compression moldings（1.0~1.4mm）Produce catalyst.
（ii）Activation of catalyst
Catalyst loads after reaction tube, passes first into 50 mL/min CHClF22h is fluorinated at 250 DEG C.
（iii）Catalytic reaction
The step of catalytic reaction process be the same as Example 1（iii）.Difference part is catalytic reaction temperature being set as 150
DEG C, charging is changed to perfluor -2- methyl -2,3- epoxypentanes, closes oxygen path.As a result show, intermediate perfluor -2- methyl -
2,3- epoxypentane conversion ratios are 57.5%, and the selectivity of perfluor -2- methyl-propione is 88.7%.
Embodiment 9
Epoxidation catalyst and rearrangement catalyst are filled in same tubular reactor
Catalyst prepared by embodiment 7 and embodiment 8 is filled in the isothermal region upper half in same tubular reactor respectively
A small amount of graphite fibre is filled between part and isothermal region the latter half, two catalyst to separate.Reaction temperature sets 150 DEG C, remaining
The step of process be the same as Example 1（iii）.As a result show, perfluoro-2-methyl-2-amylene conversion ratio is 68.9%, perfluor -2- first
The selectivity of base-propione is 78.7%.
Embodiment 10
Epoxidation catalyst and rearrangement catalyst are filled in same tubular reactor
Implementation steps be the same as Example 9, difference part is reaction temperature rising to 200 DEG C, as a result shown, perfluor -2- first
Base -2- pentene conversions are 85.4%, and the selectivity of perfluor -2- methyl-propione is 74.3%.
Claims (6)
1. a kind of preparation method of perfluor -2- methyl-propione, it is characterised in that with a certain amount of oxidizing gas and perfluor -
2- methyl -2- amylenes steam in the presence of a catalyst, carries out gas phase reaction, using one-step method or two-step method system in tubular reactor
Standby perfluor -2- methyl-propione, one-step method obtains perfluor -2- methyl -3- penta using a step oxidation catalyst direct catalytic reaction
Ketone；Two-step method first generates intermediate perfluor -2- methyl -2,3- epoxypentanes using epoxidation catalyst, then is catalyzed using resetting
The progress gas phase isomerization reaction of intermediate perfluor -2- methyl -2,3- epoxypentane is prepared perfluor -2- methyl-propione, institute by agent
The step oxidation catalyst stated includes following three kinds：1）Activated carbon is carrier loaded KF and one or both of CsF or RbF
Mixture；Two-step method comprises the following steps：Perfluoro-2-methyl-2-amylene and oxidizing gas are mixed, first in epoxida tion catalyst
Reaction generation intermediate perfluor -2- methyl -2,3- epoxypentanes in the presence of agent, reaction condition is 100 ~ 200 DEG C of temperature, stagnation pressure
The bar of power 1 ~ 10, the h of air speed 50-1~500 h-1；Then epoxide rearrangement catalyst is recycled to carry out gas phase isomerization reaction
Prepare target product perfluor -2- methyl-propione, 50 ~ 300 DEG C of temperature, the bar of gross pressure 1 ~ 10, the h of air speed 50-1~300 h-1,
The epoxidation catalyst is BaO, BaF with nanotopography2、CaO、CaF2, MgO or MgF2；The rearrangement catalyst is
Cr2O3, fluorination or partially fluorinated Cr2O3。
2. a kind of preparation method of perfluor -2- methyl-propione as claimed in claim 1, it is characterised in that described oxidation
Property gas include oxygen, air or with N2、He、Ar、CO2In one or more of air-fuel mixture enleanments oxygen；Perfluor -2- methyl -
The mixed volume ratio 0.5~3 of 2- amylenes and oxygen：1.
3. a kind of preparation method of perfluor -2- methyl-propione as claimed in claim 1, it is characterised in that step oxidation is urged
Agent or epoxidation catalyst also have compounding aid to use, wherein the auxiliary agent of a step oxidation catalyst includes La2O3、Sm2O3、
CeO2、BaO、BaF2Or Y2O3, the load capacity of a step oxidation catalysis agent aid is 1 ~ 10%；The auxiliary agent of epoxidation catalyst includes
Ag, the load capacity of epoxida tion catalyst agent aid is 1 ~ 5%.
4. a kind of preparation method of perfluor -2- methyl-propione as claimed in claim 1, it is characterised in that a described step
100 ~ 300 DEG C of method oxidizing reaction temperature, the bar of gross pressure 1 ~ 10, the h of air speed 50-1~500 h-1。
5. a kind of preparation method of perfluor -2- methyl-propione as claimed in claim 1, it is characterised in that the activated carbon
Carrier includes coconut husk charcoal, graphite charcoal or mesoporous carbon, and activity component load quantity is 1 ~ 15%.
6. a kind of preparation method of perfluor -2- methyl-propione as claimed in claim 1, it is characterised in that described epoxy
Change catalyst and rearrangement catalyst is filled in the tubular reactor of two series connection respectively, or be filled in same tubular reactor
It is interior, leading portion filling epoxidation catalyst, back segment filling rearrangement catalyst.
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| CN107235834B (en) * | 2017-06-28 | 2020-09-08 | 江苏科技大学 | Preparation method of perfluoroethyl isopropyl ketone |
| CN110013638B (en) * | 2019-04-22 | 2021-10-12 | 北京航天神禾防务技术有限公司 | Fire extinguishing system based on perfluorohexanone fire-fighting agent |
| CN111484398A (en) * | 2019-04-22 | 2020-08-04 | 北京航天神禾防务技术有限公司 | Method for preparing perfluorohexanone |
| CN111004100A (en) * | 2019-12-26 | 2020-04-14 | 西安元创化工科技股份有限公司 | Method for synthesizing perfluorohexanone |
| CN112142578B (en) * | 2020-10-26 | 2021-04-30 | 安徽航天立安安全科技有限公司 | Preparation method of perfluorohexanone |
| CN112500285B (en) * | 2020-11-24 | 2022-10-11 | 天津长芦新材料研究院有限公司 | Continuous preparation method of trifluoroacetyl fluoride |
| CN114591158B (en) * | 2020-12-04 | 2024-01-30 | 福建省漳平市九鼎氟化工有限公司 | Method and device for preparing pentafluoropropionyl fluoride and hexafluoroacetone from perfluoro-2-methyl-2-pentene |
| CN113634263B (en) * | 2021-06-16 | 2023-04-25 | 浙江诺亚氟化工有限公司 | Perfluoro olefin epoxidation catalyst and application thereof |
| CN115490651A (en) * | 2022-10-17 | 2022-12-20 | 内蒙古永和氟化工有限公司 | Preparation method of epoxy perfluoropentane |
| CN116969825B (en) * | 2023-09-25 | 2023-12-15 | 山东华夏神舟新材料有限公司 | Purifying method of perfluoro-hexanone |
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| CN102140057A (en) * | 2010-01-28 | 2011-08-03 | 中国中化股份有限公司 | Method for preparing hexafluoroacetone |
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| CN102992986B (en) * | 2012-09-29 | 2016-02-03 | 中国人民武装警察部队学院 | The preparation method of perfluorethyl isopropyl ketone |
| CN103787854B (en) * | 2014-01-24 | 2015-06-24 | 奥瑞安有限公司 | Preparation process of perfluoro-2-methyl-3-pentanone |
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| CN101036882A (en) * | 2007-04-13 | 2007-09-19 | 上海泰卓科技有限公司 | Catalyzer of the Epoxide including fluorin isomerization and the preparing method and application |
| CN102140057A (en) * | 2010-01-28 | 2011-08-03 | 中国中化股份有限公司 | Method for preparing hexafluoroacetone |
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