Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • 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
• • 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
• • 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

Definitions

• the subject of the invention is a process for preparing fluorinated compounds, namely the 2,3,3,3-tetrafluoro-1-propene fluoride compound (1234yf).
• Hydrofluorocarbons and in particular hydrofluoroolefins (HFOs), such as 2,3,3,3-tetrafluoro-1-propene (HFO 1234yf), are compounds known for their properties as coolants and coolants, fire extinguishers, propellants , foaming agents, blowing agents, gaseous dielectrics, polymerization medium or monomer, carrier fluids, abrasive agents, drying agents and power generating unit fluids.
• coolants and coolants such as 2,3,3,3-tetrafluoro-1-propene (HFO 1234yf)
• HFOs hydrofluoroolefins
• HFOs 2,3,3,3-tetrafluoro-1-propene
• WO2007 / 056194 describes the preparation of 1234yf by dehydrofluorination of 1, 1, 1, 2, 3-pentafluoropropane (HFC 245eb) either with potassium hydroxide or in the gas phase in the presence of a catalyst, in particular on a nickel-based catalyst, of carbon or a combination thereof.
• WO2008 / 030440 discloses the preparation of 1234yf by hydrogenation of 1,2,3,3,3-pentafluoropropene-1 (1225ye) in the presence of a hydrogenation catalyst to give 245eb which is then subjected to a step of dehydrofluorination, either with a basic aqueous solution in the presence of a non-aqueous and non-alcoholic solvent and a phase transfer catalyst, or in the gaseous phase in the presence of a catalyst chosen in particular from alumina, fluorinated alumina , oxide, fluoride or oxyfluoride magnesium, zinc and mixtures of magnesium and zinc and / or aluminum.
• This document describes the hydrogenation of 1, 2, 3, 3, 3-pentafluoropropene-1 (1225ye) into 1, 1, 1, 2, 3-pentafluoropropane (245eb) on a palladium catalyst supported on alumina. During this hydrogenation there is also a hydrogenolysis reaction, a significant amount of 1,1,1,2-tetrafluoropropane being produced.
• This document describes the dehydrofluorination of 1, 1, 1, 2, 3-pentafluoropropane (245eb) into 2,3,3,3-tetrafluoro-1-propene (HFO 1234yf) by passage through a suspension of KOH.
• US-P-5679875 discloses the preparation of 1,1,1,2,3-pentafluoropropane by catalytic dehydrofluorination of 1,1,1,2,3,3-hexafluoropropane (236ea) in 1, 2, 3, 3 , 3-pentafluoropropene-1 (1225ye), followed by hydrogenation to produce the desired compound.
• the reactions are carried out in the gas phase.
• the document WO2008 / 040969 describes the preparation of a (hydro) fluoroalkene having from three to six carbon atoms by dehydrohalogenation of a hydro (halo) fluoroalkane having from three to six carbon atoms in the presence of a catalyst comprising a compound of chromium and / or zinc.
• dehydrofluorination can be carried out in the absence of HF (hydrofluoric acid) but that it is preferable to use HF to avoid or delay the decomposition of the organic charge and / or the coking (fouling by coke deposition) of the catalyst.
• WO2008 / 008350 describes the preparation of a mixture of E and Z isomers of 1,2,3,3,3-pentafluoropropene-1
• Example 1 of this document illustrates the dehydrofluorination reaction of 1,1,1,2,2,3-hexafluoropropane (HFC 236cb) to 1,2,3,3,3-pentafluoropropene-1 (1225ye) and shows that after 26 hours of operation, the 236cb conversion decreases sharply as well as the 1225ye selectivity.
• this document teaches to regenerate the catalyst by treatment with air and HF.
• the invention thus provides a process for the preparation of 2,3,3,3-tetrafluoro-1-propene comprising the following steps:
• step (iii) dehydrofluorination of 1,1,1,2,3-pentafluoropropane obtained in the previous step to 2,3,3,3-tetrafluoro-1-propene.
• the hydrogen is introduced during step (ii) in a superstoichiometric molar ratio.
• step (i) is carried out in the presence of hydrogen, preferably with a H 2 / product molar ratio to be reacted of between 0.3 and 30, in particular between 0.5 and 20, advantageously between 1 and 10, and step (iii) is carried out in the absence of hydrogen.
• step (i) is carried out in the presence of hydrogen, preferably with a H 2 / product molar ratio to be reacted of between 0.3 and 30, in particular between 0.5 and 20, advantageously between 1 and 10, and step (iii) is carried out in the presence of hydrogen, preferably with a molar ratio ⁇ / product to be reacted between
• the total amount of hydrogen is introduced during step (i).
• the molar ratio H 2 / l, 2, 3, 3, 3- pentafluoro-1 is between 2.3
• the molar ratio H 2 / l, 2, 3, 3, 3- pentafluoro-1 is about 2. 1, 1, 1, 2, 2, 3-hexafluoropropane n having not reacted in step (i) is separated
• step (i) or after step (ii), but before step (iii), and optionally recycled to step (ii) and / or step (i). 1, 1, 1, 2, 2, 3-hexafluoropropane not having
• step (i) Reacted during step (i) is not separated before steps (ii) and (iii), additional 1,2,3,3,3-pentafluoropropene-1 is obtained in step (iii) from 1, 1, 1, 2, 2, 3-hexafluoropropane
• dehydrofluorination steps (i) and (iii) are carried out in the same reactor, preferably with the same catalyst, and wherein the process further comprises a separating step separating the products from said reactor, in particular into a fraction containing 2,3,3,3-tetrafluoro-1-propene. the flow of step (i) containing the
• 1, 2, 3, 3, 3-pentafluoropropene-1 is sent directly without separation to step (ii) during which hydrogenation occurs.
• steps (i) and (ii) are carried out in the same reactor, on different catalyst beds.
• steps (i) and (ii) are carried out in two reactors immediately in series without intermediate separation.
• a separation is carried out, a flow of 1, 1, 1, 2, 2, 3-hexafluoropropane and optionally a flux of HF are recovered which are recycled at the inlet of the process and a stream of 1,1,1,2,3-pentafluoropropane and optionally hydrogen which are sent to step (i ⁇ ) is recovered.
• 1, 1, 1, 2, 2, 3-hexafluoropropane is obtained at Starting from tetrafluoroethylene and difluoromethane by the addition reaction, 1,1,2,2,3,3-hexafluoropropane is obtained from 2-fluoro-1,1,1,2,3-pentachloropropane or 2-fluoro-1,1,2,2-pentachloropropane. , 2-difluoro-
• 1, 1, 1, 3-tetrachloropropane by hydrofluorination in the presence of a catalyst 1, 1, 1, 2, 2, 3-hexafluoropropane is obtained from 1,1-dichloro-hexafluoropropane or 1-dichloro-1,2,2,3,3,3-hexafluoropropane by hydrogenolysis in the presence of a catalyst.
• 1, 1, 1, 2, 2, 3-hexafluoropropane is obtained from 1,3-dichloro-1,1,2,2,2-tetrafluoropropane by hydrofluorination in the presence of a catalyst.
• - 1, 1, 1, 2, 2, 3-hexafluoropropane is obtained from 2, 2, 3, 3, 3-pentafluoropropanol by fluorination.
• the invention uses three reactions in series, implemented continuously or semi-continuously, the reaction products being sent to the next step, possibly after having undergone a treatment for example separation, if necessary.
• reaction steps are advantageously carried out continuously on gas phase flows.
• An economical process for the preparation of the compound 1234yf is thus obtained.
• the hydrogenation step of 1225ye is carried out in a conventional manner for the skilled person. Those skilled in the art may choose the operating conditions so that the reactions are substantially quantitative.
• the catalysts that can be used in these reactions are those known for this purpose. Mention may especially be made of catalysts based on a group VIII metal or rhenium. This catalyst may be supported, for example on carbon, alumina, aluminum fluoride, etc., or may not be supported, such as Raney nickel. As a metal, platinum or palladium can be used, in particular palladium, advantageously supported on carbon or alumina. This metal can also be associated with another metal such as silver, copper, gold, tellurium, zinc, chromium, molybdenum and thallium. These hydrogenation catalysts are known.
• the catalyst may be present in any suitable form, for example in the form of a fixed or fluidized bed, preferably in a fixed bed.
• the direction of flow can be from top to bottom or from bottom to top.
• the catalyst bed may also include a particular catalyst distribution to manage the heat fluxes generated by the exothermic reaction.
• the hydrogenation step is exothermic.
• the reaction temperature can be controlled by means provided for this purpose in the reactor, if necessary.
• the temperature can vary from a few tens of degrees during the reaction.
• the inlet temperature can vary from 20 ° C. to 150 ° C.
• the temperature gain can vary from 5 ° C. to 100 ° C.
• the contact time (ratio between the volume of catalyst and the total flow of the charge) is generally between 0.1 and 100 seconds, preferably between 1 and 50 seconds and advantageously between 2 and 10 seconds.
• the amount of hydrogen injected can vary widely.
• the ratio H 2 / charge can vary widely, especially between 1 (the stoichiometric amount) and 30, especially between 1.5 and 20, advantageously between 3 and 10. A high ratio will lead to a dilution, and therefore a better one. management of the exothermicity of the reaction.
• Dehydrofluorination reactions are also carried out in a conventional manner by those skilled in the art.
• the dehydrofluorination reaction may be carried out by passing through a basic solution, in particular KOH.
• the dehydrofluorination reaction is preferably carried out in the gas phase in the presence of a dehydrofluorination catalyst.
• This catalyst is, for example, a catalyst based on a metal, especially a transition metal, or an oxide or halide or oxyhalide derivative of such a metal.
• Catalysts are, for example, FeCl 3, chromium oxyfluoride, Ni (including Ni lattice), NiCl 2 , CrF 3 , and mixtures thereof.
• Other possible catalysts are carbon supported catalysts, antimony catalysts, aluminum catalysts (such as AlF 3 and Al 2 O 3 and aluminum oxyfluoride and fluorinated alumina), palladium, platinum, rhodium and ruthenium. Reference may be made to the list given in US-P-5396000, column 1, line 50 to column 2, line 2 or to the list given in WO2007 / 056194, page 16, lines 13-23.
• a mixed catalyst is used.
• This catalyst contains both chromium and nickel.
• the molar ratio Cr: Ni, with respect to the metallic element, is generally between 0.5 and 5, for example between 0.7 and 2, in particular close to 1.
• the catalyst may contain, by weight, from 0.5 to 20% of chromium and from 0.5 to 20% of nickel and preferably from 2 to 10% of each of the metals.
• the metal may be present in metallic form or in the form of derivatives, in particular oxide, halide or oxyhalide, these derivatives, in particular halide and oxyhalide, being obtained by activation of the catalytic metal. Although activation of the metal is not necessary, it is preferred.
• the support is based on aluminum. There may be mentioned several possible supports such as alumina, activated alumina or aluminum derivatives. These aluminum derivatives are in particular aluminum halides or oxyhalides, for example described in US-P-4902838, or obtained by the activation method described below.
• the catalyst may comprise chromium and nickel in a non-activated form or in activated form, on a support which has also undergone activation of the metal or not.
• the catalyst can be prepared from alumina (generally so-called activated alumina, this activated alumina is a high porosity alumina, and is distinct from the alumina having undergone the metal activation treatment).
• the alumina is converted into aluminum fluoride or a mixture of aluminum fluoride and alumina, by fluorination with air and hydrofluoric acid, the conversion rate of the alumina in aluminum fluoride depending essentially on the temperature at which the fluorination of the alumina is carried out (generally between 200 0 C and 450 0 C, preferably between 250 0 C and 400 0 C).
• the support is then impregnated with aqueous solutions of chromium and nickel salts or with aqueous solutions of chromic acid, nickel salt and methanol (used as a chromium reducing agent).
• chromium and nickel salts chlorides, or other salts such as, for example, oxalates, formates, acetates, nitrates and sulphates or nickel dichromate may be employed, provided that these salts are soluble in the amount of water that can be absorbed by the support.
• the catalyst can also be prepared by direct impregnation of alumina (which in general is activated) using the solutions of the chromium and nickel compounds mentioned above. In this case, the transformation of at least a portion (for example 70% or more) of the alumina into aluminum fluoride or aluminum oxyfluoride is carried out during the activation step of the catalyst metal.
• the activated aluminas that can be used for catalyst preparation are well known, commercially available products. They are generally prepared by calcining alumina hydrates (aluminum hydroxides) at a temperature of between 300 ° C. and 800 ° C. Preferably, but without this being necessary, the catalyst is conditioned or activated, that is to say transformed into active constituents and stable (at the reaction conditions) by a prior operation called activation. This treatment can be carried out either "in situ" (in the dehydrofluorination reactor) or in a suitable apparatus designed to withstand the conditions of activation.
• alumina hydrates aluminum hydroxides
• This activation step generally comprises the following steps: - A drying step.
• This drying step is carried out at high temperature (250 ° C. to 450 ° C., preferably 300 ° C. to 350 ° C.), generally under a stream of nitrogen or air.
• This step can be possibly preceded in a first step by a first drying step at low temperature (100 ° C. to 150 ° C., preferably 110 ° C. to 120 ° C.) in the presence of air or nitrogen.
• the duration of the drying step can be between 10 and
• a fluorination step is carried out at low temperature
• the duration of the fluorination step may be between 10 and 50 hours.
• finishing step under current of hydrofluoric acid pure or diluted with nitrogen at a temperature up to 450 0 C.
• the duration of the finishing step may be between 2 and 15 hours.
• the catalytic precursors for example nickel and chromium halides, chromate or nickel dichromate, chromium oxide
• the catalytic precursors are converted into corresponding fluorides and / or oxyfluorides, resulting in a release of water and / or hydrochloric acid.
• Such a catalyst is described in EP-A-486333, in particular page 3, lines 11-48, examples IA, 2A and 4A, passages to which it is referred.
• the dehydrofluorination steps are carried out at temperatures which may be between 150 ° C. and 600 ° C., preferably between 300 ° and 500 ° C. and advantageously between 300 ° and 450 ° C., especially between 300 ° and 400 ° C.
• the contact time (ratio between the volume of catalyst and the total flow of the charge) is in general between 0.1 and 100 seconds, preferably between 1 and 50 seconds and advantageously between 2 and 20 seconds in the case of the reaction leading to 1234yf and between 5 and 40 seconds in the case of the reaction leading to 1225ye.
• a diluent gas nitrogen, helium, argon
• nitrogen, helium, argon can be used in the reaction.
• the pressure in the different reactions may be atmospheric, or lower or higher than this atmospheric pressure.
• the pressure can vary from one reaction to another, if any.
• the reactions are carried out in one or more reactors dedicated to reactions involving halogens.
• reactors are known to those skilled in the art, and may include interior coatings based for example on Hastelloy®, Inconel®, Monel® or fluoropolymers.
• the reactor may also include heat exchange means, if necessary.
• H 2 / dehydrofluorination feed can vary widely, especially between 0.3 and 30, in particular between 0.5 and
• the supply of reagents is generally continuous, or may be stepped where appropriate. Points for eventual separation (s) and / or recycling (s) are variables at the beginning of the process or at intermediate levels.
• hydrogen is present during step (i) of dehydrofluorination.
• This hydrogen can be stored for the hydrogenation stage
• (iii) can also be implemented in the absence of hydrogen.
• the hydrogen may also be introduced in a staged manner, additional hydrogen being introduced before the hydrogenation step and / or before the dehydrofluorination step
• step (iii) if it is desired that this step be carried out in the presence of hydrogen.
• step (i) it is possible to add hydrogen so that the ratio H 2 : 1225ye is at least equal to 1, advantageously greater than 1 (so that the final step (iii) dehydrofluorination is carried out in the presence of hydrogen).
• Hydrogen can also be added to the reaction medium before each step, if desired. It is possible that step (i) dehydrofluorination is carried out in the presence of hydrogen while the last step (iii) is not carried out in the presence of hydrogen.
• the hydrogen which has not been consumed in one or more steps is advantageously separated and recycled in the process, advantageously at the beginning of the process.
• the hydrogenation reaction is preferably substantially quantitative.
• the dehydrofluorination reactions are not necessarily always quantitative, in particular the reaction (i) of 1225ye formation is not necessarily quantitative and 236cb which remains unreacted may remain.
• This unreacted compound 236cb can be separated either after step (i) or after step (ii) (but before step (iii)).
• the separation takes place after step (ii), the boiling temperatures of 236cb and 245eb being -1.4 ° C and 22.7 ° C respectively, therefore with a difference of more than 24 ° C.
• the separation can occur at these two times because the hydrogenation reaction (ii) does not substantially affect the 236cb.
• This separate 236cb can be recycled in the process.
• step (i) can be recycled in step (i) during which it reacts.
• This unreacted compound 236cb may also not be separated and remain in the process, especially up to step (iii).
• step (iii) dehydrofluorination 1,2,3,3,3-pentafluoropropene-1 (1225ye) will be formed from unreacted 236cb.
• the diluting action of 236cb makes it possible to control the exothermicity of the hydrogenation step.
• the two compounds 1225ye and 1234yf can then be separated and the 1225ye recycled.
• the boiling temperatures of the two fluorolefins are certainly close, but it is possible to separate these two compounds. Recycling can be done in step (i) and / or step
• HF dehydrofluorination reaction
• HF can be separated by washing or distillation.
• Azeotropes optionally formed with HF can also be separated after the step in which they are formed or after a later step or at the end of the process. These separation steps are therefore placed in the process according to the different needs. It is also possible to provide for recycling only certain separated compounds (the unreacted 236cb for example), while the other separate components are sent to other processes.
• 1, 2, 3, 3, 3-pentafluoropropene-1 (1225ye) is not separated, which avoids handling this product which is toxic. It is possible to send the stream from step (i) directly to the next step.
• steps (i) and (ii) may be carried out in the same reactor on different catalyst beds.
• a separation is carried out and possible removal of HF, a flow of 1, 1, 1, 2, 2, 3-hexafluoropropane is recovered which is recycled.
• 1, 2, 3, 3, 3-pentafluoropropene-1 (1225ye) is not separated because it is converted in the reactor to 245eb, which avoids handling this 1225ye product which is toxic. It is also possible to provide two reactors directly in series, the flow leaving the first reactor being sent directly into the next reactor without separation.
• the reactor can contain two different catalytic species, with different functions.
• the dehydrofluorination of 236cb is carried out on a first catalytic bed and the 1225ye, HF formed and the hydrogen then pass on a second catalytic bed, at an appropriate temperature (the heating can be electric, by example).
• the reaction products are then 245eb, HF, excess hydrogen and optionally 236cb unreacted.
• an output stream containing 245 eb, optionally excess hydrogen, HF optionally with azeotropes, and optionally 236 cb is obtained. unreacted present before the hydrogenation step.
• the hydrogen which is recycled at the top of the reactor (or at another level in the process) is separated and the 236cb from 245eb is separated off.
• the 236cb can also be recycled at the reactor inlet.
• HF and possibly the azeotropes are also separated (possibly partly by washing).
• the flow of this dehydrofluorination reactor contains 1234yf, but also unreacted 236cb and / or 245eb and 1225ye resulting from the dehydrofluorination of 236cb.
• This stream is separated and we get the 1234yf, as well as the 1225ye, 236cb and 245eb.
• the two fluorinated fluids can be separated. It is possible that the 236cb and / or 245eb is recycled at the top of the dehydrofluorination reactor while the 1225ye stream is recycled to the top of the hydrogenation reactor. It is also possible to recycle the stream, after recovery of 1234yf, at the head of the hydrogenation reactor.
• 236cb is obtained from tetrafluoroethylene and difluoromethane by the addition reaction.
• This reaction may be initiated by a radical initiator or with the aid of a catalyst, preferably chosen from a Lewis catalyst or a redox system comprising a salt of copper, iron or chromium optionally in the presence of a co-catalyst.
• 236cb is obtained from 2-fluoro-1,1,1,2,3-pentachloropropane (231bb) or 2,2-difluoro-1,1,1,3-tetrachloropropane.
• the hydrofluorination reaction can be carried out in at least one stage, preferably in two stages and advantageously with a first stage in the liquid phase and a second stage in the gas phase.
• 236cb is obtained from 1,1-dichloro-hexafluoropropane (216cb) or 1-dichloro-1,2,2,3,3,3-hexafluoropropane (226ca) by hydrogenolysis in the presence a catalyst.
• the catalyst preferably comprises palladium or platinum.
• the catalyst is advantageously supported on charcoal.
• 236cb is obtained from 1,3-dichloro-1,1,2,2,2-tetrafluoropropane (234cc) by hydrofluorination in the presence of a catalyst.
• 236cb is obtained from 2,2,3,3,3-pentafluoropropanol by fluorination. This fluorination step may be carried out directly or by the tosylate route or in the presence of sulfuryl chloride or carbonyl chloride.
• the conversion ratio is the% of the reacted starting material (number of mole of reacted starting material / mole number of feedstock introduced);
• the desired product selectivity is the ratio of the number of moles of desired product formed to the number of moles of product that has reacted;
• the desired product yield is the ratio of the number of moles of desired product formed to the number of mole products introduced, the yield of the desired product being able to be further defined as the product of conversion and selectivity.
• the contact time is the inverse of the space velocity VVH (or GHSV in English).
• the space velocity is the ratio between the volumetric flow rate of the total gas flow on the volume of the catalytic bed, under the normal conditions of temperature and pressure.
• Example 1 Dehydrofluorination of 236cb in 1225ye. Preparation of the dehydrofluorination catalyst.
• the catalyst used is a Ni-Cr / AlF 3 catalyst prepared as follows.
• 343 g of a support obtained in a preceding step are placed by fluorination of GRACE HSA alumina in a fixed bed at about 280 ° C. using air and hydrofluoric acid (concentration by volume of from 5 to
• the starting GRACE HSA alumina has the following physicochemical characteristics: shape: beads 0.5-2 mm in diameter BET surface: 220 m 2 / g pore volume: 1.3 cm 3 / g
• two separate aqueous solutions are prepared:
• the characteristics of the catalyst after activation are the following: BET surface area: 40 m 2 / g pore volume: 0.4 cm / g chemical weight composition:
• a reactor containing 20 g of catalyst is used in the form of a fixed bed of 23 cm.
• the pressure is 1 bar and the temperature is 375 ° C.
• a reactor containing 10 g of catalyst (identical to that used in Example 1) is used in the form of a fixed bed of 16 cm 3 .
• the pressure is 1 bar.
• a reactor containing 10 g of catalyst (identical to that of Example 2) is used in the form of a fixed bed of 12 cm 3 .
• the pressure is 1 bar.

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