CN102066295A - Process for the preparation of fluorinated compounds - Google Patents
Process for the preparation of fluorinated compounds Download PDFInfo
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- CN102066295A CN102066295A CN2009801232906A CN200980123290A CN102066295A CN 102066295 A CN102066295 A CN 102066295A CN 2009801232906 A CN2009801232906 A CN 2009801232906A CN 200980123290 A CN200980123290 A CN 200980123290A CN 102066295 A CN102066295 A CN 102066295A
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- C07—ORGANIC CHEMISTRY
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- C07C21/00—Acyclic unsaturated compounds containing halogen atoms
- C07C21/02—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds
- C07C21/18—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds containing fluorine
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/35—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction
- C07C17/354—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction by hydrogenation
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Abstract
The subject of the invention is a process for the preparation of 2,3,3,3-tetrafluoro-1-propene which comprises the following stages: (i) dehydrofluorination of 1,1,1,2,2,3-hexafluoropropane to 1,2,3,3,3-pentafluoro-1-propene; (ii) hydrogenation of the 1,2,3,3,3-pentafluoro-1-propene obtained in the preceding stage to 1,1,1,2,3-pentafluoropropane; and (iii) dehydrofluorination of the 1,1,1,2,3-pentafluoropropane obtained in the preceding stage to 2,3,3,3-tetrafluoro-1-propene.
Description
Technical field
The present invention relates to be used to prepare fluorine cpd is fluorine cpd 2,3,3, the method for 3-tetrafluoro-1-propylene (1234yf).
Background technology
Hydrogen fluorohydrocarbon (HFC) and particularly HF hydrocarbon (HFO) for example 2,3,3,3-tetrafluoro-1-propylene (HFO1234yf) is because of the well-known compound of its character as following purposes: refrigeration agent and heat exchange agent, fire-fighting medium, propelling agent, whipping agent, swelling agent, dielectric medium gas, polymerization or monomer medium, carrying object (support fluid), abrasive, siccative and energy producing unit fluid.Be different from the CFC and the HCFC that ozonosphere are had potential threat, HFO is not chloride and therefore do not bring problem to ozonosphere.
Several methods that are used to make 1234yf have been known.
WO2007/056194 has described by using potassium hydroxide to make 1,1,1,2,3-pentafluoropropane (HFC245eb) dehydrofluorination and prepare 1234yf, perhaps by make HFC 245eb in gas phase in the presence of the catalyzer particularly on based on the catalyzer of nickel, carbon or the combination of these two dehydrofluorination prepare 1234yf.
WO2008/030440 has described by being prepared as follows 1234yf: make 1,2,3,3,3-five fluoro-1-propylene (1225ye) in the presence of hydrogenation catalyst hydrogenation to produce 245eb, then, use alkaline aqueous solution to make 245eb experience the dehydrofluorination step down at the solvent of non-water and non-alcohol (non-alcholic) and phase-transfer catalyst, perhaps, make 245eb in gas phase in the presence of the catalyzer of the mixture that is selected from aluminum oxide, fluoro aluminum oxide, magnesium oxide, fluorochemical or oxyfluoride, zinc and magnesium and zinc and/or aluminium especially experience dehydrofluorination step.
People's such as Knunyants document (Journal of the USSR Academy of Sciences, Chemistry Department, " Reactions of fluoro-olefins ", report 13, " Catalytichydrogenation of perfluoro-olefins ", 1960) the various chemical reactions about fluorine cpd have clearly been described.Described document description 1,1,1,2,3,3-HFC-236fa (236ea) via by the suspension of KOH dehydrofluorination to produce 1,2,3,3,3-five fluoro-1-propylene (1225ye).Described document description 1,2,3,3,3-five fluoro-1-propylene (1225ye) carry out hydrogenation to produce 1,1,1,2,3-pentafluoropropane (245eb) on the palladium catalyst of alumina load.During this hydrogenation, hydrogenolysis also takes place, produce 1,1,1 of sizable amount, the 2-tetrafluoropropane.Described document description 1,1,1,2,3-pentafluoropropane (245eb) via by the suspension of KOH dehydrofluorination to produce 2,3,3,3-tetrafluoro-1-propylene (HFO 1234yf).These reactions are described independently of one another, might be with their combinations with synthetic various ethene, propylene and the isobutene derivatives that contain the fluorine of variable amount although show.
In addition, document US-P-5396000 has described by being prepared as follows 1,1,1,2,3-pentafluoropropane: to 1,1,1,2,3,3-HFC-236fa (236ea) is carried out catalytic dehydrofluorination to produce 1,2,3,3,3-five fluoro-1-propylene (1225ye) carry out hydrogenation subsequently to produce required compound.The 236ea dehydrohalogenation is carried out in gas phase to produce 1225ye, in one embodiment, this reaction product is delivered directly to next reactor, in this next reactor, compound 1225ye carries out hydrogenation to produce compound 245eb.
Document US-P-5679875 has described by being prepared as follows 1,1,1,2,3-pentafluoropropane: to 1,1,1,2,3,3-HFC-236fa (236ea) is carried out catalytic dehydrofluorination to produce 1,2,3,3,3-five fluoro-1-propylene (1225ye) carry out hydrogenation subsequently to produce required compound.Described being reflected in the gas phase carried out.
Document WO 2008/040969 has been described hydrogen (halo) the fluoroalkane dehydrohalogenation and prepare (hydrogen) fluoroolefin that contains 3～6 carbon atoms in the presence of the catalyzer that comprises chromium and/or zn cpds that contains 3～6 carbon atoms via making.The document instructs described dehydrofluorination to carry out under the situation that does not have HF (hydrofluoric acid), but the preferred HF that uses is to avoid or to stop the decomposition of organic charging (charge) and/or the coking of catalyzer (fouling by the deposition of coke).
Document WO 2008/008350 has been described by being selected from 1,1,1,2,3,3-HFC-236fa (HFC 236ea) and 1,1,1,2,2, the HFC-236fa of 3-HFC-236fa (HFC 236cb) prepares 1,2,3 in the presence of the fluorine chromium oxide catalyst, 3, the E isomer of 3-five fluoro-1-propylene (1225ye) and the mixture of Z isomer.Embodiment 1 explanation 1,1,1,2,2 of the document, 3-HFC-236fa (HFC 236cb) is to 1,2, and 3,3, the dehydrofluorination of 3-five fluoro-1-propylene (1225ye), and being presented at after 26 hours functionalized, the transformation efficiency of 236cb reduces greatly, and the selectivity of 1225ye is also reduced greatly.In order to set up catalytic activity once more, document instruction makes catalyst regeneration via the processing of using air and HF.
Need such method by the feedstock production 1234yf that obtains easily, this method is with high selectivity and advantageously make required product with high productive rate.
Summary of the invention
Thereby, the invention provides and be used to prepare 2,3,3, the method for 3-tetrafluoro-1-propylene, it comprises the following steps:
(i) make 1,1,1,2,2,3-HFC-236fa dehydrofluorination generates 1,2,3,3,3-five fluoro-1-propylene;
(ii) to obtain in the previous step 1,2,3,3,3-five fluoro-1-propylene carry out hydrogenation to generate 1,1,1,2, the 3-pentafluoropropane;
(iii) make obtain in the previous step 1,1,1,2,3-pentafluoropropane dehydrofluorination generates 2,3,3,3-tetrafluoro-1-propylene.
According to some embodiments:
-during step is (ii), introduce hydrogen with the stoichiometry mol ratio.
-step (i) is carried out in the presence of hydrogen, preferred H
2(product, mol ratio product) is 0.3～30 to the product of/question response, be in particular 0.5～20 and advantageously be 1～10, and step is carried out under the situation that does not have hydrogen (iii).
-step (i) is carried out in the presence of hydrogen, preferred H
2(product, mol ratio product) is 0.3～30 to the product of/question response, is in particular 0.5～20 and advantageously be 1～10, and step is (iii) carried out preferred H in the presence of hydrogen
2The mol ratio of the product of/question response is 0.3～30, is in particular 0.5～20 and advantageously be 1～10.
-the hydrogen of the whole amounts of introducing during step (i).
-H
2/ 1,2,3,3,3-five fluoro-1-propylene mol ratios are 2.3～30 and advantageously are 3～20.
-H
2/ 1,2,3,3,3-five fluoro-1-propylene mol ratios are about 2.
-step (i) or step (ii) after but isolate before (iii) during step (i) in step also responseless 1,1,1,2,2,3-HFC-236fa and randomly it is recycled to step (ii) and/or in the step (i).
-in step (ii) and do not isolate during step (i) also responseless 1,1,1,2 (iii), 2, the 3-HFC-236fa, during step (iii) by described unreacted 1,1,1,2,2, the 3-HFC-236fa obtains other 1,2,3,3,3-five fluoro-1-propylene, this is other 1,2 years old, 3,3, be separated after the 3-five fluoro-1-propylene and randomly be recycled to step (ii) and/or in the step (i).
-dehydrofluorination step (i) is with (iii) in identical reactor, preferably use identical catalyzer to carry out, comprise also that with wherein said method the product that is used for obtaining from described reactor separates, particularly from described product, isolate and contain 2,3,3, the separating step of the fraction of 3-tetrafluoro-1-propylene.
-will from step (i) contain 1,2,3,3, the logistics of 3-five fluoro-1-propylene do not carry out being delivered directly under the isolating situation carry out hydrogenation therebetween step (ii) in.
-step (i) with (ii) in identical reactor, on different catalyst beds, carry out.
-step (i) and (ii) two directly series connection and do not have to carry out in the reactor of midfeather (separation).
-this step (ii) after, separate, and collect 1,1,1,2,2, the logistics of 3-HFC-236fa is recycled to the initial period (start) of described method and collects 1,1 with optional HF logistics and with it, 1,2, the logistics of 3-pentafluoropropane and optional hydrogen, this logistics be transported to step (iii) in.
-1,1,1,2,2, the 3-HFC-236fa is obtained via addition reaction by tetrafluoroethylene and methylene fluoride.
-1,1,1,2,2, the 3-HFC-236fa is by 2-fluoro-1,1,1,2,3-pentachloropropane or 2, and 2-two fluoro-1,1,1,3-tetrachloro propane obtains by the hydrofluorination in the presence of catalyzer.
-1,1,1,2,2, the 3-HFC-236fa is by 1,1-dichlorohexafluoropr.pane or 1-chloro-1,2,2,3,3, and the 3-HFC-236fa obtains by the hydrogenolysis in the presence of catalyzer.
-1,1,1,2,2, the 3-HFC-236fa is by 1,3-two chloro-1,1,2, and the 2-tetrafluoropropane obtains by the hydrofluorination in the presence of catalyzer.
-1,1,1,2,2, the 3-HFC-236fa is by 2,2,3,3, and 3-five fluorine propyl alcohol obtain by fluoridizing.
Embodiment
The present invention use three one by one by the reaction of continuous or semi-continuous employing, if necessary, after randomly experience has for example been handled separating treatment, it is delivered to next step in reaction product.
In described method, advantageously described reactions steps is carried out in the logistics in the gas phase continuously.Thereby obtain the economic method that is used to prepare compound 1234yf.
The 1225ye hydrogenation step is being that conventional mode is carried out to those skilled in the art.Those skilled in the art's selectively actuatable condition makes that described reaction is quantitative basically.
The catalyzer that can use in these reactions is to become known for those of this purpose.Can mention catalyzer especially based on group VIII metal or rhenium.This catalyzer for example can load on charcoal (charcoal), aluminum oxide, the aluminum fluoride etc., perhaps can not carry out load, for example for drawing Buddhist nun's nickel.As metal, can use platinum or palladium, particularly palladium, it advantageously loads on charcoal or the aluminum oxide.This metal also can with for example silver, copper, gold, tellurium, zinc, chromium, molybdenum or thallium combination of additional metals.These hydrogenation catalysts are known.
Described catalyzer can any suitable form for example exist with the form of fixed bed or fluidized-bed, preferably exists as fixed bed.The mobile direction can be downward or makes progress.Flowing of the heat that the specific distribution that described catalyst bed also can comprise catalyzer is produced by described thermopositive reaction with control.Thereby the porosity, electric density gradient etc. that can look forward to catalyzer are to control the exothermicity of described reaction.For example, the first part that can look forward to described bed comprises less catalyzer, and second section comprises more catalyzer.
Also can look forward to the step that makes catalyst regeneration in known manner.
Also can look forward to and use for example nitrogen of diluent gas.
Described hydrogenation step is heat release.If necessary, can come control reaction temperature by means of the device that is provided with for the purpose of control reaction temperature in the reactor.Between the described reaction period, the tens of degree of variable temperaturesization.For example, inlet temperature can be 20 ℃～150 ℃, and the temperature increase can be 5 ℃～100 ℃.
Duration of contact, (ratio of the volume of catalyzer and total charging (charge) flow) was generally 0.1～100 second, was preferably 1～50 second and advantageously was 2～10 seconds.
The amount of the hydrogen that injects can change in wide scope.H
2/ charge ratio can change in wide scope, is in particular 1 (stoichiometric amount)～30, is in particular 1.5～20 and advantageously be 3～10.High ratio will cause dilution, and cause the better management to exothermic heat of reaction thus.
Dehydrofluorination is also being that conventional mode is carried out to those skilled in the art.
Can carry out dehydrofluorination via basic solution by basic solution, particularly KOH.
Dehydrofluorination is preferably carried out in the presence of Dehydrofluorination catalyst in gas phase.This catalyzer for for example based on metal, the catalyzer of oxide compound, halogenide or the oxyhalogenide derivative of transition metal or such metal particularly.Catalyzer is for example FeCl
3, fluorine chromic oxide, Ni (comprising the Ni lattice), NiCl
2, CrF
3, and composition thereof.Other possible catalyzer be load on catalyzer on the charcoal, based on the catalyzer of antimony, based on the catalyzer of aluminium (AlF for example
3, Al
2O
3, fluorine alumina and fluorizated aluminum oxide), palladium, platinum, rhodium and ruthenium.The list that provides during but the list that reference US-P-5396000 the 1st hurdle the 50th row provides in going to the 2nd hurdle the 2nd or the 16th page of 13-23 of WO2007/056194 are capable.
According to a modification, make spent mixed catalyst.
This catalyzer contains chromium and nickel.About metallic element, Cr: the Ni mol ratio is generally 0.5～5, and for example 0.7～2, be in particular about 1.Described catalyzer can contain 0.5～20% chromium and 0.5～20% nickel, preferred 2%～10% chromium and 2%～10% nickel by weight.
Described metal can metallic forms or is existed with the form of derivative (particularly oxide compound, halogenide or oxyhalogenide), and these derivatives (particularly halogenide and oxyhalogenide) obtain via the activation of catalytic metal.Though the activation of described metal is optional, it is preferred.
Carrier is based on aluminium.Can mention several possible carriers, for example aluminum oxide, activated aluminum oxide or aluminium derivative.These aluminium derivatives are aluminum halide or zirconyl oxyhalides aluminium particularly, and it for example is described among the US-P-4902838 or via the activation method that describes below and obtains.
Described catalyzer can be included in the activated form on the carrier or without the chromium and the nickel of activatory form, described carrier has also experienced the activation of described metal, does not perhaps experience the activation of described metal.
Described catalyzer can (be generally " activated " aluminum oxide by aluminum oxide; This activated aluminum oxide is the aluminum oxide of high porosity, and is different from the aluminum oxide that experiences the metal activation processing) preparation.In first step, aluminum oxide is converted into aluminum fluoride or is converted into aluminum fluoride and the mixture of aluminum oxide by using air and hydrofluoric acid to fluoridize, the transformation efficiency that aluminum oxide is converted into aluminum fluoride depends primarily on the fluorizated temperature of carrying out aluminum oxide (be generally 200 ℃～450 ℃ and be preferably 250 ℃～400 ℃).Use the aqueous solution of chromic salts and nickel salt then or use the solution impregnating carrier of chromic acid, nickel salt and methyl alcohol (being used as chromium reducing agent).Spendable chromic salts and nickel salt comprise muriate, or other salt for example oxalate, formate, acetate, nitrate and vitriol, or dichromic acid nickel, dissolve in the water of the amount that suppressed by vector absorbs but condition is these salt.Described catalyzer also can carry out direct impregnation to aluminum oxide (normally activated) via the solution by means of above-mentioned chromium cpd and nickel compound and prepare.In this case, during the activation step of the metal of described catalyzer, proceed to of the conversion of the aluminum oxide of small part (for example 70% or more) to aluminum fluoride or fluorine alumina.
The activated aluminum oxide that can be used for preparing described catalyzer is known commercially available prod.They are usually by the calcining preparation of hydrated alumina (aluminium hydroxide) under 300 ℃～800 ℃ temperature.
Preferably, but not necessarily, catalyzer is nursed one's health (condition) or activation, be about to it and be converted into composition active and stable (under reaction conditions) via preparation " activation " operation.This processing can " original position " (in dehydrofluorination device) or is carried out in suitable being designed to tolerates the device of activation condition.
This activation step generally includes the following step:
-drying step.This drying step carries out under high temperature (250 ℃～450 ℃, and preferred 300 ℃～350 ℃) under nitrogen or airflow usually.In the fs, before this drying step, can randomly have in the presence of air or nitrogen under low temperature (100 ℃～150 ℃, and preferred 110 ℃～120 ℃) and carry out the exsiccant first step.The time length of this drying step can be 10～50 hours.
-fluorination step.This fluorination step uses the mixture of hydrofluoric acid and nitrogen carrying out when control HF content makes temperature be no more than 350 ℃ under the low temperature (180 ℃～350 ℃).The time length of this fluorination step can be 10～50 hours.
-optional refining (finishing) step, it flows down under the temperature that can be up to 450 ℃ at pure hydrofluoric acid stream or with the hydrofluoric acid of nitrogen dilution and carries out.The time length of this purification step can be 2～15 hours.
In this operating period, catalyged precursor (for example halogenide of nickel and chromium, chromic acid nickel or dichromic acid nickel, chromic oxide) is converted into corresponding fluorochemical and/or oxyfluoride, and this causes discharging water outlet and/or spirit of salt.The chemical analysis of the element after this activation (chromium, nickel, fluorine, aluminium, oxygen) can be confirmed the inorganic composition of catalyzer.
Such catalyzer is described among the EP-A-486333, and particularly page 3 the 11st～48 is gone, among embodiment 1A, 2A and the 4A, with reference to these paragraphs.
Can be 150 ℃～600 ℃, be preferably 300 ℃～500 ℃ and advantageously be to carry out the dehydrofluorination step under 300 ℃～450 ℃ particularly 300 ℃～400 ℃ the temperature.
Under the situation of the reaction that produces 1234yf, be generally 0.1～100 second the duration of contact ratio of total feed rate (volume of catalyzer with), is preferably 1～50 second and advantageously is 2～20 seconds; Under the situation of the reaction that produces 1225ye, be 5～40 seconds duration of contact.
In described reaction, can use diluent gas (nitrogen, helium or argon gas).Pressure in the various reactions can be normal atmosphere, perhaps is below or above this normal atmosphere.When appropriate, the pressure of reaction can have nothing in common with each other.
Described being reflected in one or more reactors that are exclusively used in the reaction that relates to halogen carried out.Such reactor is well known by persons skilled in the art, and can comprise based on for example
Or the lining of fluoropolymer.If necessary, reactor also can comprise heat exchanger.
Use under the situation of hydrogen H in dehydrofluorination step (i) and/or step in (iii) therein
2/ dehydrofluorination charge ratio can change in wide scope, is in particular 0.3～30, especially is 0.5～20 and advantageously is 1～10.
The feasible transformation efficiency and/or the selectivity higher stability in time that can obtain required product of this existence of hydrogen.Similarly, preferably reduce the formation of heavy fraction.In the presence of hydrogen, very high to the selectivity of required product 1225ye or 1234yf, the passing that this selectivity is preferably in time is stable.
Normally continuously feeding of reactant, perhaps charging by stages when appropriate.The point (point) of possible separation and/or recirculation operation is variable, its described method begin the place or in the mid-way (level) locates.
According to an embodiment, during dehydrofluorination step (i), there is hydrogen.This hydrogen can remain to hydrogenation step and (ii) and randomly remain at most corresponding to the final step of second dehydrofluorination (iii); This step (iii) also can be carried out under the situation that does not have hydrogen.
Hydrogen also can be introduced by stages, introducing extra hydrogen before (iii) before the hydrogenation step and/or in the dehydrofluorination step, carries out in the presence of hydrogen if expect this step.Thereby, be right after afterwards in step (i), can add hydrogen so that H
2: 1225ye is than equal 1 and advantageously greater than 1 (so that last dehydrofluorination step is (iii) carried out) at least in the presence of hydrogen.If desired, also can before each step, hydrogen be joined in the reaction medium.Dehydrofluorination step (i) can be carried out in the presence of hydrogen, and last step (iii) can not carried out in the presence of hydrogen.
The Hydrogen Separation that advantageously will not have to consume in one or more steps is come out and is recycled in the described method, advantageously is recycled to the initial period of described method.
Hydrogenation reaction preferably is quantitative basically.Each dehydrofluorination is not necessarily always quantitative; Especially, the reaction (i) that is used to form 1225ye is not necessarily quantitative, and unreacted 236cb can be remaining.
Can step (i) afterwards or step (ii) after (but step (iii) before) should separate by unreacted compound 236cb.Advantageously, the described step that is separated in is (ii) carried out afterwards, and the boiling point of 236cb and 245eb is respectively-1.4 ℃ and 22.7 ℃, thereby has the difference above 24 ℃.Described separation can be carried out in these two times, because hydrogenation reaction does not (ii) influence 236cb basically.This isolated 236cb can be recycled in the described method.It can be recycled in the step (i), during step (i), it reacts.Yet can this unreacted compound 236cb not separated and it can be retained in the described method, especially remain into as many as step (iii).During this dehydrofluorination step is (iii), then form by this unreacted 236cb other 1,2,3,3,3-five fluoro-1-propylene (1225ye).In addition, the diluting effect of 236cb makes the exothermicity of may command hydrogenation step.Two kinds of compound 1225ye can be separated with 1234yf then and with 1225ye recirculation.Really, the boiling point of these two kinds of fluoroolefin is similarly, but still can realize the separation of these two kinds of compounds.Can be recycled to step (i) and/or step (ii) in.During quantitative step hydrogenation reaction (ii) basically, this 1225ye transforms quantitatively.
Thereby, can be according to the product stream (product flows) in possible separation needs control the method according to this invention.Can be after each dehydrofluorination, between these two reactions or only isolate formed HF in the latter stage of described method.Can isolate HF by washing or by steaming level.Can also can be separated after the step that they form during it or after step subsequently or with the azeotrope that HF forms in the latter stage of described method.Thereby, according to various needs these separating steps are set in described method.Also can look forward to the only recirculation of some isolated compound (for example unreacted 236cb), and other isolating component is transported to other process.
Advantageously, do not isolate 1,2,3,3,3-five fluoro-1-propylene (1225ye), this has been avoided the processing of this toxic products.Logistics from step (i) can be delivered directly in the step of back.
For example, described method can be such method, wherein, step (i) with (ii) in identical reactor, on different catalyst beds, carry out.Advantageously, in this case, step (ii) after, carry out the separation of HF and optional removing, collect 1,1,1,2,2, the logistics of 3-HFC-236fa also is recycled to it in starting stage of described method, and collect 1,1,1,2, the logistics of 3-pentafluoropropane and optional (but preferred) hydrogen and be transported to step (iii) in.Do not isolate 1,2,3,3,3-five fluoro-1-propylene (1225ye), because it is converted into 245eb in reactor, this has been avoided the processing of this toxic products 1225ye.Also can look forward to two direct placed in-line reactors, the logistics of leaving first reactor is delivered directly in next reactor and does not separate.
Under the situation of above single reactor as object, this reactor can contain two kinds of different catalytic species, and it has different functions.On first catalytic bed, carry out the dehydrofluorination of 236cb, make hydrogen, formed 1225ye and HF second catalytic bed then by under suitable temperature, (for example, carrying out electrically heated).Reaction product then is 245eb, HF, excessive hydrogen and possible unreacted 236cb.Under the situation of above single reactor or two direct placed in-line reactors, then obtain containing the outlet logistics of 245eb, possible excessive hydrogen, HF and possible azeotrope and the possible unreacted 236cb that before hydrogenation step, exists.Isolate hydrogen and it is recycled in the top of reactor (perhaps being recycled in the another location in the described method), and 236cb is separated with 245eb.Also 236cb can be recycled in the reactor inlet.Also separablely go out (by washing randomly part isolate) HF and optional azeotrope.
In described method, also can look forward to dehydrofluorination step (i) and (iii) in same reactor, carry out, preferably use same catalyst to carry out.
Logistics from this dehydrofluorination device contains 1234yf, but also the 1225ye that contains unreacted 236cb and/or 245eb and obtain by the dehydrofluorination of 236cb.This logistics is separated and collects 1234yf, 1225ye, 236cb and 245eb.As mentioned above, separable described two kinds of fluoroolefin.236cb and/or 245eb can be recycled in the top of dehydrofluorination device, and the 1225ye logistics be recycled in the top of hydrogenator.Also can after collecting 1234yf, described logistics be recycled in the top of hydrogenator.On first catalytic bed, carry out the dehydrofluorination of 236cb, and make hydrogen, formed 1225ye and HF are fed in second catalytic bed that (for example, can carry out electrically heated) under the suitable temperature.Reaction product then is 245eb, HF, excessive hydrogen and optional unreacted 236cb.Under the situation of above single reactor or two direct placed in-line reactors, then obtain containing the logistics of 245eb, optional excessive hydrogen, HF and possible azeotrope and the optional unreacted 236cb that before hydrogenation step, exists in the exit.Isolate hydrogen and it is recycled in the top of reactor (perhaps being recycled in the another location in the described method), and 236cb is separated with 245eb.Also 236cb can be recycled in the reactor inlet.Also separablely go out (by washing randomly part isolate) HF and optional azeotrope.
In described method, also can arrange dehydrofluorination step (i) and (iii) in identical reactor, carry out, preferably use identical catalyzer to carry out.
Logistics from this dehydrofluorination device contains 1234yf, but also the 1225ye that contains unreacted 236cb and/or 245eb and obtain by the dehydrofluorination of 236cb.This logistics is separated and collects 1234yf and 1225ye, 236cb and 245eb.As mentioned above, separable described two kinds of fluoroolefin.236cb and/or 245eb can be recycled in the top of dehydrofluorination device, and the 1225ye logistics be recycled in the top of hydrogenator.Also can after collecting 1234yf, described logistics be recycled in the top of hydrogenator.
According to an embodiment, obtain 236cb by addition reaction by tetrafluoroethylene and methylene fluoride.Available radical initiator causes this reaction or uses catalyzer to cause this reaction in the presence of optional promotor, and described catalyzer is preferably selected from louis catalyst and comprises the redox system of mantoquita, molysite or chromic salts.
According to another embodiment, 236cb is by 2-fluoro-1,1,1,2,3-pentachloropropane (231bb) or 2, and 2-two fluoro-1,1,1,3-tetrachloro propane (232cb) obtains by the hydrofluorination in the presence of catalyzer.Described hydrofluorination reaction can at least one step, preferably carries out with two steps and advantageously, first step carries out in liquid phase and second step is carried out in gas phase.
According to another embodiment, 236cb is by 1,1-dichlorohexafluoropr.pane (216cb) or 1-chloro-1,2,2,3,3, and 3-HFC-236fa (226ca) obtains by the hydrogenolysis in the presence of catalyzer.Described catalyzer preferably includes palladium or platinum.Described catalyzer advantageously loads on the charcoal.
According to another embodiment, 236cb is by 1,3-two chloro-1,1,2, and 2-tetrafluoropropane (234cc) obtains by the hydrofluorination in the presence of catalyzer.
According to another embodiment, 236cb is by 2,2,3,3, and 3-five fluorine propyl alcohol obtain by fluoridizing.This fluorination step can directly be carried out, and perhaps carries out via tosylate (ester) approach, perhaps carries out in the presence of SULPHURYL CHLORIDE or carbonyl chloride.
Look back (recall):
-transformation efficiency is the per-cent (mole number of the raw material of the mole number/introducing of the raw material of reaction) of the raw material that reacted;
-to required product selectivity the ratio of mole number of raw material of the mole number/reacted of formed required product;
The productive rate of-required product is the ratio of mole number of raw material of the mole number/introducing of formed required product, and the productive rate of required product also may be defined as transformation efficiency and product optionally;
Be the inverse of gas hourly space velocity (GHSV)-duration of contact;
-space velocity is the total volume throughput of gaseous stream under the standard temperature and pressure (STP) condition and the ratio of the volume of catalyst bed;
-throughput is expressed as the quality of the required product that the catalyzer of every (quality or the volume) unit of time per unit obtains; This throughput is relevant with duration of contact.
Embodiment
The following example illustrates the present invention and does not limit the present invention.
Embodiment 1 236cb dehydrofluorination generates 1225ye
The preparation of Dehydrofluorination catalyst
The catalyzer that uses is Ni-Cr/AlF
3Catalyzer, it is prepared as follows.
To place rotatory evaporator as fixed bed by using air and hydrofluoric acid (the aerial volumetric concentration of this acid is 5%～10%) that Grace HSA aluminum oxide is fluoridized the carrier that obtains down in the 343g step in front at about 280 ℃.Grace HSA initial oxidation aluminium has following physics-chem characteristic:
-shape: diameter is the pearl of 0.5～2mm
-BET surface-area: 220m
2/ g
-pore volume: 1.3cm
3/ g
Prepare two kinds of independent aqueous solution respectively:
(a) augment the chromium-containing solution of nickelous chloride, it contains:
(b) methanol solution, it contains:
Under 40 ℃ temperature, under atmospheric pressure under agitation these two kinds of solution are incorporated on the carrier simultaneously with about 2 hours.After the maturation stage under the nitrogen, catalyzer is dry under nitrogen, then under vacuum 65 ℃ dry down, then under vacuum about 90 ℃ dry 6 hours down.
500g is placed the Inconel tubular reactor through the solid of dipping.At first that catalyzer is dry at low temperatures under nitrogen gas stream, under atmospheric pressure dry under up to 320 ℃ temperature then.Then, this catalyzer is descended and fluoridizes under up to 390 ℃ temperature then at 320 ℃ in the presence of hydrofluoric acid/nitrogen mixture (volumetric concentration of this acid in nitrogen is 5%～10%).Stop the HF charging then.Use nitrogen continual rinsing 15 minutes down at 390 ℃, then this catalyzer is cooled to 60 ℃ under nitrogen gas stream.
The characteristic of the catalyzer after the activation is as follows:
-BET surface-area: 40m
2/ g
-pore volume: 0.4cm
3/ g
-by weight chemical constitution:
■ Al：25％
■ F：58％
■ Cr：5.3％
■ Ni：6.4％
Use contains 23cm
3The reactor of the 20g catalyzer of fixed bed form.Pressure is that 1 crust and temperature are 375 ℃.
In reactor, introduce the 236cb of 100mmol/h and the hydrogen of 450mmol/h.H
2/ 236cb mol ratio is 4.5.Be 6.7 seconds duration of contact.
The transformation efficiency of 236cb and after 100 hours operation, be still stable to the selectivity of 1225ye.
Embodiment 2 1225ye hydrogenation generate 245eb
Use contains 16cm
3The reactor of the 10g catalyzer of fixed bed form (identical) with the catalyzer that uses among the embodiment 1.Pressure is 1 crust.
Obtain following result (MR represents mol ratio) then.
Embodiment 3 245eb dehydrofluorinations generate 1234yf
Use contains 12cm
3The reactor of the 10g catalyzer of fixed bed form (identical) with the catalyzer that uses among the embodiment 2.Pressure is 1 crust.
Obtain following result (MR represents mol ratio) then.
Claims (16)
1. prepare 2,3,3, the method for 3-tetrafluoro-1-propylene comprises the following steps:
(i) make 1,1,1,2,2,3-HFC-236fa dehydrofluorination generates 1,2,3,3,3-five fluoro-1-propylene;
(ii) to obtain in the previous step 1,2,3,3,3-five fluoro-1-propylene carry out hydrogenation to generate 1,1,1,2, the 3-pentafluoropropane;
(iii) make obtain in the previous step 1,1,1,2,3-pentafluoropropane dehydrofluorination generates 2,3,3,3-tetrafluoro-1-propylene.
2. the process of claim 1 wherein and during step (ii), introduce hydrogen with the stoichiometry mol ratio.
3. claim 1 or 2 method, wherein step (i) is carried out in the presence of hydrogen, preferred H
2The mol ratio of the product of/question response is 0.3～30, be in particular 0.5～20 and advantageously be 1～10, and step is (iii) carried out under the situation that does not have hydrogen.
4. claim 1 or 2 method, wherein step (i) is carried out in the presence of hydrogen, preferred H
2The mol ratio of the product of/question response is 0.3～30, be in particular 0.5～20 and advantageously be 1～10, and step is (iii) carried out preferred H in the presence of hydrogen
2The mol ratio of the product of/question response is 0.3～30, be in particular 0.5～20 and advantageously be 1～10.
5. each method in the claim 1～4 is wherein introduced all hydrogen of amount during step (i).
6. the method for claim 5, wherein H
2/ 1,2,3,3, the mol ratio of 3-five fluoro-1-propylene is 2.3～30 and advantageously is 3～20.
7. the method for claim 5, wherein H
2/ 1,2,3,3,3-five fluoro-1-propylene mol ratios are about 2.
8. each method in the claim 1～7 is wherein during step (i) responseless 1,1,1,2,2, the 3-HFC-236fa step (i) or step (ii) after but be separated before (iii) in step, and randomly be recycled to step in (i).
9. each method in the claim 1～7, wherein (ii) and do not isolate during step (i) responseless 1,1,1 (iii) in step, 2,2, the 3-HFC-236fa, during step (iii) by described unreacted 1,1,1,2,2, the 3-HFC-236fa obtains other 1,2,3,3,3-five fluoro-1-propylene, this is other 1,2 years old, 3,3, be separated after the 3-five fluoro-1-propylene and randomly be recycled to step (ii) in and/or randomly be recycled in the step (i).
10. each method in the claim 1～9, dehydrofluorination step (i) and (iii) in same reactor, carrying out wherein, the identical catalyzer of preferred use carries out, wherein said method comprises that also the product that is used for obtaining from described reactor separates, particularly from this product, isolate and contain 2,3,3, the separating step of the fraction of 3-tetrafluoro-1-propylene.
11. each method in the claim 1～9, wherein will from step (i) contain 1,2,3,3, the logistics of 3-five fluoro-1-propylene do not carry out being delivered directly under the isolating situation carry out hydrogenation therebetween step (ii) in.
12. each method in the claim 1～9, wherein step (i) with (ii) in same reactor, on different catalyst beds, carry out.
13. each method in the claim 1～9, wherein step (i) and (ii) two directly series connection and do not have to carry out in the reactor of midfeather.
14. the method for claim 12 or 13 wherein, is separated after (ii) in step, collect 1,1,1,2,2, the logistics of 3-HFC-236fa is recycled to the initial period of described method with optional HF logistics and with it, with collect 1,1,1,2, the logistics of 3-pentafluoropropane and optional hydrogen, this logistics be transported to step (iii) in.
15. each method is characterized in that in the aforementioned claim, 1,1,1,2,2, the 3-HFC-236fa is to obtain by being selected from following at least a compound: 2-fluoro-1,1,1,2,3-pentachloropropane, 2,2-two fluoro-1,1,1,3-tetrachloro propane, 1,1-dichlorohexafluoropr.pane, 1-chloro-1,2,2,3,3,3-HFC-236fa, 1,3-two chloro-1,1,2,2-tetrafluoropropane and 2,2,3,3,3-five fluorine propyl alcohol.
16. each method is characterized in that in the claim 1～14,1,1,1,2,2, and the 3-HFC-236fa is obtained via addition reaction by tetrafluoroethylene and methylene fluoride.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR08.54009 | 2008-06-18 | ||
| FR0854009A FR2932799B1 (en) | 2008-06-18 | 2008-06-18 | PROCESS FOR THE PREPARATION OF FLUORINATED COMPOUNDS |
| PCT/FR2009/050969 WO2009153493A1 (en) | 2008-06-18 | 2009-05-26 | Process for the preparation of fluorinated compounds |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102066295A true CN102066295A (en) | 2011-05-18 |
Family
ID=39963930
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009801232906A Pending CN102066295A (en) | 2008-06-18 | 2009-05-26 | Process for the preparation of fluorinated compounds |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP2285762A1 (en) |
| CN (1) | CN102066295A (en) |
| FR (1) | FR2932799B1 (en) |
| WO (1) | WO2009153493A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104311385A (en) * | 2014-11-05 | 2015-01-28 | 华玉叶 | Method of preparing 1,2,3,3,3-pentafluoro-1-propylene |
| US9290424B2 (en) | 2013-03-14 | 2016-03-22 | Honeywell International Inc. | Processes for the hydrogenation of halogenated alkenes and the manufacture of fluorinated olefins |
| CN105960277A (en) * | 2014-02-10 | 2016-09-21 | 霍尼韦尔国际公司 | Reactor design for liquid phase fluorination |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7981311B2 (en) * | 2006-09-05 | 2011-07-19 | E. I. Du Pont De Nemours And Company | Process and methods of purification for the manufacture fluorocarbons |
| GB0808836D0 (en) | 2008-05-15 | 2008-06-18 | Ineos Fluor Ltd | Process |
| TW201247315A (en) * | 2011-05-16 | 2012-12-01 | Du Pont | Catalytic hydrogenation of fluoroolefins, alpha-alumina supported palladium compositions and their use as hydrogenation catalysts |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2523694T3 (en) * | 2006-07-13 | 2014-11-28 | E.I. Du Pont De Nemours And Company | Catalytic production processes to prepare 1,2,3,3,3-pentafluoropropene |
| WO2008030444A2 (en) * | 2006-09-05 | 2008-03-13 | E. I. Du Pont De Nemours And Company | Process for producing 1,2,3,3,3-pentafluoropropene and related azeotropic compositions |
| ES2447037T3 (en) * | 2006-09-05 | 2014-03-11 | E.I. Du Pont De Nemours And Company | Manufacturing process of 2,3,3,3-tetrafluoropropene |
-
2008
- 2008-06-18 FR FR0854009A patent/FR2932799B1/en not_active Expired - Fee Related
-
2009
- 2009-05-26 CN CN2009801232906A patent/CN102066295A/en active Pending
- 2009-05-26 WO PCT/FR2009/050969 patent/WO2009153493A1/en active Application Filing
- 2009-05-26 EP EP09766055A patent/EP2285762A1/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9290424B2 (en) | 2013-03-14 | 2016-03-22 | Honeywell International Inc. | Processes for the hydrogenation of halogenated alkenes and the manufacture of fluorinated olefins |
| CN105960277A (en) * | 2014-02-10 | 2016-09-21 | 霍尼韦尔国际公司 | Reactor design for liquid phase fluorination |
| CN104311385A (en) * | 2014-11-05 | 2015-01-28 | 华玉叶 | Method of preparing 1,2,3,3,3-pentafluoro-1-propylene |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2285762A1 (en) | 2011-02-23 |
| WO2009153493A1 (en) | 2009-12-23 |
| FR2932799A1 (en) | 2009-12-25 |
| FR2932799B1 (en) | 2010-08-13 |
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Application publication date: 20110518 |