CN102065999A - Method for preparing fluorinated compounds - Google Patents

Method for preparing fluorinated compounds Download PDF

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Publication number
CN102065999A
CN102065999A CN2009801233114A CN200980123311A CN102065999A CN 102065999 A CN102065999 A CN 102065999A CN 2009801233114 A CN2009801233114 A CN 2009801233114A CN 200980123311 A CN200980123311 A CN 200980123311A CN 102065999 A CN102065999 A CN 102065999A
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Prior art keywords
catalyst
hfc
dehydrofluorination
carry out
chromium
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CN2009801233114A
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米歇尔·德维克
安妮·皮加莫
劳伦特·温德琳格
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Arkema France SA
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Arkema France SA
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/22—Halogenating
    • B01J37/26—Fluorinating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/86—Chromium
    • B01J23/866—Nickel and chromium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0203—Impregnation the impregnation liquid containing organic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0207—Pretreatment of the support
    • 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
    • B01J35/613—
    • B01J35/633—
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

Abstract

The invention relates to a method for dehydrofluorinating 1, 1, 1, 2, 2, 3-hexafluoropropane in 1, 2, 3, 3, 3-pentafluoropropene-1 in the presence of hydrogen.

Description

The method for preparing fluorinated compound
Technical field
The present invention relates to be used to prepare fluorine compounds, particularly fluorine compounds 1,2,3,3, the method for 3-five fluoro-1-propylene (1225ye).
Background technology
Hydrogen fluorohydrocarbon (HFC) and particularly HF hydrocarbon (HFO) are because of the well-known compound of its character as following purposes: cold-producing medium and heat exchanging agent, extinguishing chemical, propellant, blowing agent, swelling agent, dielectric gas, polymerization or monomer medium, carrying object (support fluid), grinding agent, drier and energy producing unit fluid.Be different from the CFC and the HCFC that ozone layer are had potential threat, HFO is not chloride and thereby do not bring problem to ozone layer.
Document WO 2008/040969 has been described hydrogen (halo) the fluoroalkane dehydrohalogenation and prepare (hydrogen) fluoroolefins that contains 3～6 carbon atoms in the presence of the catalyst that comprises chromium and/or zinc compound 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 catalyst (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 isomers and the Z mixture of isomers of 3-five fluoro-1-propylene (1225ye).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 conversion ratio 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 allow the method that is used for preparing 1225ye of the stability of passing in time by 236cb.
Summary of the invention
Thereby, the invention provides in the presence of hydrogen and make 1,1,1,2,2,3-HFC-236fa dehydrofluorination is to produce 1,2,3,3, the method for 3-five fluoro-1-propylene.
According to some embodiments:
-described being reflected at has 0.3～30 H 2/ 1,1,1,2,2, carry out in the gas phase of 3-HFC-236fa mol ratio.
-described being reflected at has 0.5～20 and advantageously be 1～10 H 2/ 1,1,1,2,2, carry out in the gas phase of 3-HFC-236fa mol ratio.
-described method is carried out in the presence of Dehydrofluorination catalyst.
-described Dehydrofluorination catalyst is the catalyst based on chromium.
-described method is at 150 ℃～500 ℃ and be preferably under 300 ℃～400 ℃ the temperature and carry out.
-described method was with 0.1～100 second, preferred 1～50 second and advantageously carry out 5～40 seconds time of contact.
The specific embodiment
The present invention is based on following discovery: when the dehydrofluorination of 236cb was carried out in the presence of hydrogen, it provided about conversion ratio with to the stability of passing in time of the selectivity of 1225ye.
Generally speaking, hydrogen along with initial charge (charge) is injected, is for example injected continuously or in an alternating manner.H 2/ initial charge mol ratio can change in wide scope, is in particular 0.3～30, especially is 0.5～20 and advantageously is 1～10.
The use of the dehydrofluorination in the presence of hydrogen provides the high stability of passing in time.The also feasible generation that can reduce heavy product between the stage of reaction of the existence of hydrogen.
Use Dehydrofluorination catalyst to carry out dehydrofluorination.This catalyst is, for example, and based on the metal catalyst of oxide, halide or the oxyhalide derivative of transition metal or such metal particularly.Catalyst is for example FeCl 3, fluorine chromium oxide, Ni (comprising the Ni lattice), NiCl 2, CrF 3, and composition thereof.Other possible catalyst for load on catalyst on the charcoal (charcoal), based on the catalyst of antimony, based on the catalyst of aluminium (AlF for example 3, Al 2O 3, fluorine alumina and the aluminium oxide fluoridized), palladium, platinum, rhodium and ruthenium.The list that provides during but the list that list of references 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, use the mixed catalyst that 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 catalyst 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, halide or oxyhalide), and these derivatives (particularly halide and oxyhalide) are that the activation via catalytic metal obtains.Though the activation of described metal is optional, it is preferred.
Carrier is based on aluminium.Can mention several possible carriers, for example aluminium oxide, activated aluminium 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 catalyst can be included in the activated form on the carrier or the chromium and the nickel of not activated form, and described carrier has also experienced the activation of described metal, does not perhaps experience the activation of described metal.
Described catalyst can (be generally " activated " aluminium oxide by aluminium oxide; This activated aluminium oxide is the aluminium oxide of high porosity, and is different from the aluminium oxide that experiences the metal activation processing) preparation.In first step, aluminium oxide is converted into aluminum fluoride or is converted into aluminum fluoride and the mixture of aluminium oxide by using air and hydrofluoric acid to fluoridize, the conversion ratio that aluminium oxide is converted into aluminum fluoride depends primarily on the temperature of fluoridizing of carrying out aluminium 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 chloride, or other salt for example oxalates, formates, acetate, nitrate and sulfate, or dichromic acid nickel, dissolve in the water of the amount that suppressed by vector absorbs but condition is these salt.Described catalyst also can carry out direct impregnation to aluminium oxide (it is normally activated) via the solution by means of above-mentioned chromium compound and nickel compound and prepare.In this case, during the activation step of the metal of described catalyst, proceed to of the conversion of the aluminium oxide of small part (for example 70% or more) to aluminum fluoride or fluorine alumina.
The activated aluminium oxide that can be used for preparing described catalyst 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, catalyst is nursed one's health (condition) or activation, be about to it and be converted into composition active and stable (under reaction condition) 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 steps.This drying steps flows down usually under high temperature (250 ℃～450 ℃, and preferred 300 ℃～350 ℃) at nitrogen or air and carries out.In the phase I, before this drying steps, can randomly have in the presence of air or nitrogen under low temperature (100 ℃～150 ℃, and preferred 110 ℃～120 ℃) and carry out dry first step.The duration of this drying steps can be 1～50 hour.
-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 duration of this fluorination step can be 1～50 hour.
-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 duration of this purification step can be 1～15 hour.
In this operating period, catalyged precursor (for example halide of nickel and chromium, chromic acid nickel or dichromic acid nickel, chromium oxide) is converted into corresponding fluoride and/or oxyfluoride, and this causes discharging water outlet and/or hydrochloric acid.The chemical analysis of the element after this activation (chromium, nickel, fluorine, aluminium, oxygen) can be confirmed the inorganic composition of catalyst.
Such catalyst is described among the EP-A-486333, and the 3rd page of the 11st～48 row particularly is among embodiment 1A, 2A and the 4A, with reference to these paragraphs.
Described dehydrofluorination is carried out in gas phase usually.
Described catalyst can any suitable form, and for example the form with fixed bed or fluid bed exists, and preferably exists as fixed bed.The direction that flows can be downward or makes progress.
Temperature can be 150 ℃～600 ℃, is preferably 300 ℃～500 ℃ and advantageously be 300 ℃～450 ℃.
Pressure can be atmospheric pressure, perhaps is below or above this atmospheric pressure.
Be generally 0.1～100 second the time of contact ratio of total feed rate (volume of catalyst with), is preferably 1～50 second and advantageously is 5～40 seconds.
Can in described reaction, use diluent gas (nitrogen, helium or argon gas).
Described being reflected in the reactor that is 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, described reactor also can comprise heat-exchange device.
The end product that separates described reaction in a usual manner, and advantageously unreacted reactant is recycled in the described method.Look back (recall):
-conversion ratio is the percentage (molal quantity of the raw material of the molal quantity/introducing of the raw material of reaction) of the raw material that reacted;
-to required product selectivity the ratio of molal quantity of raw material of the molal quantity/reacted of formed required product;
The productive rate of-required product is the ratio of molal quantity of raw material of the molal quantity/introducing of formed required product, and the productive rate of required product also may be defined as conversion ratio and product optionally;
Be the inverse of gas hourly space velocity (GHSV)-time 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;
-production capacity is expressed as the quality of the required product that the catalyst of time per unit per unit (quality or volume) obtains; This production capacity is relevant with time of contact.
Embodiment
The following example illustrates the present invention but does not limit the present invention.
Embodiment 1 Preparation of catalysts
The catalyst that uses is Ni-Cr/AlF 3Catalyst, it is prepared as follows.
To place rotary evaporator as fixed bed by using air and hydrofluoric acid (the aerial volumetric concentration of this acid is 5%～10%) that Grace HSA aluminium oxide is fluoridized the carrier that obtains down in the 343g step in front at about 280 ℃.Grace HSA initial oxidation aluminium has following physicochemical characteristics:
-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 solution of nickel chloride, it contains:
Figure BPA00001278660600051
(b) methanol solution, it contains:
Figure BPA00001278660600052
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, catalyst 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 catalyst is flowed down at low temperatures dry, under atmospheric pressure dry under up to 320 ℃ temperature then at nitrogen.Then, this catalyst 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 ℃, this catalyst is flowed down at nitrogen be cooled to 60 ℃ then.
The characteristic of the catalyst after the activation is as follows:
-BET surface area: 40m 2/ g
-pore volume: 0.4cm 3/ g
-by weight chemical composition:
■Al：25％
■F：58％
■Cr：5.3％
■Ni：6.4％
Embodiment 2236cb dehydrofluorination generates 1225ye
Use volume to be 50cm 3And diameter is the reactor of 2.1cm, and it contains highly is the 20g catalyst of the fixed bed form of 6.6cm.Pressure is 1 crust.Temperature is 375 ℃.
In described reactor, introduce 236cb and the hydrogen of 450mmol/h, i.e. hydrogen/236cb mol ratio=4.5 of 100mmol/h.
Be 6.7 seconds time of contact.
After 100 hours operation, the conversion ratio of 236cb and the selectivity of 1225ye remained unchanged.

Claims (7)

1. make 1,2,2,3-HFC-236fa dehydrofluorination to be producing 1,2,3,3, the method for 3-five fluoro-1-propylene, and it carries out in the presence of hydrogen.
2. the process of claim 1 wherein that described being reflected at has 0.3～30 H 2/ 1,1,1,2,3, carry out in the gas phase of 3-HFC-236fa mol ratio.
3. claim 1 or 2 method, wherein said being reflected at has 0.5～20 and advantageously 1～10 H 2/ 1,1,1,2,3, carry out in the gas phase of 3-HFC-236fa mol ratio.
4. each method in the claim 1～3, it carries out in the presence of Dehydrofluorination catalyst.
5. the method for claim 4, wherein said Dehydrofluorination catalyst are based on the mixed catalyst based on chromium and nickel on the carrier of aluminium.
6. each method in the claim 1～5, it is at 150 ℃～500 ℃ and preferably carry out under 300 ℃～400 ℃ temperature.
7. each method in the claim 1～6, it was with 0.1～100 second, preferred 1～50 second and advantageously carry out 5～40 seconds time of contact.
CN2009801233114A 2008-06-18 2009-05-26 Method for preparing fluorinated compounds Pending CN102065999A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR08.54008 2008-06-18
FR0854008A FR2932798B1 (en) 2008-06-18 2008-06-18 PROCESS FOR THE PREPARATION OF FLUORINATED COMPOUNDS
PCT/FR2009/050968 WO2009153492A1 (en) 2008-06-18 2009-05-26 Method for preparing fluorinated compounds

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6124510A (en) * 1998-07-21 2000-09-26 Elf Atochem North America, Inc. 1234ze preparation
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

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008030440A2 (en) * 2006-09-05 2008-03-13 E. I. Du Pont De Nemours And Company Process to manufacture 2,3,3,3-tetrafluoropropene

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6124510A (en) * 1998-07-21 2000-09-26 Elf Atochem North America, Inc. 1234ze preparation
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

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EP2285489A1 (en) 2011-02-23
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FR2932798A1 (en) 2009-12-25

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Application publication date: 20110518