Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C17/00—Preparation of halogenated hydrocarbons
  • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
  • C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
  • C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
  • C07C17/206—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction the other compound being HX
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C17/00—Preparation of halogenated hydrocarbons
  • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
• • 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
  • C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
  • C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
  • C07C17/266—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions of hydrocarbons and halogenated hydrocarbons
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C17/00—Preparation of halogenated hydrocarbons
  • C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
  • C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
  • C07C17/269—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions of only halogenated hydrocarbons
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  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C17/00—Preparation of halogenated hydrocarbons
  • C07C17/38—Separation; Purification; Stabilisation; Use of additives
  • C07C17/383—Separation; Purification; Stabilisation; Use of additives by distillation
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  • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
  • C09K5/02—Materials undergoing a change of physical state when used
  • C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
  • C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
  • C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
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  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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  • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
  • C09K5/02—Materials undergoing a change of physical state when used
  • C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
  • C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
  • C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
  • C09K5/045—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds containing only fluorine as halogen
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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  • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
  • C09K2205/10—Components
  • C09K2205/12—Hydrocarbons
  • C09K2205/126—Unsaturated fluorinated hydrocarbons
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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  • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
  • C09K2205/24—Only one single fluoro component present

Definitions

• the present invention relates to compositions based on F-1230za
• F-1230za and F-1230zd (1, 3,3,3-tetrachloropropene), their manufacture, and their use especially for the production F-1233zdE (frans-1-chloro-3,3,3-trifluoropropene), F-1234zeE (frans-1, 3,3,3-tetrafluoropropene), and / or F-245fa (1, 1, 1, 3,3-pentafluoropropane).
• Fluoroolefins and in particular F-1233zdE are compounds of major interest for refrigeration and air conditioning systems, given the new environmental regulations.
• hydrofluoroolefins such as F-1233zdE
• F-1233zdE fluorination of hydrochloro-olefins or hydrochlorocarbons in particular.
• This fluorination is generally a fluorination using hydrofluoric acid as fluorinating agent.
• F-240fa (1, 1, 1, 3,3-pentachloropropane)
• US Pat. No. 8,704,017 in this regard, which describes a process for fluorinating in the liquid phase in the absence of a catalyst but requiring several reactors in series and / or stirring of the reaction medium to counter the low conversion rate.
• a liquid phase fluorination process can generate several undesired compounds such as oligomeric compounds, high boilers, toxic or corrosive, or more generally, impurities difficult to separate.
• these oligomeric compounds have the effect of reducing the efficiency of the fluorination process and must be separated by purging, in a continuous system or batch system, from the reactor and reprocessed.
• High boilers can also prevent the reaction. .
• inhibitors generally antioxidants
• US2012 / 0226081, US2012 / 0190902 or US2014 / 0213831 These inhibitors prevent the formation of oxygenated impurities, mainly phosgene which is toxic, during the transport and storage phases.
• oxygenated impurities mainly phosgene which is toxic
• the invention is based on the surprising discovery that when the starting material does not contain, or contains very few specific impurities, fluorination in the absence of F-1230za catalyst, or F-1230za in mixture with F-1230zd, is significantly more efficient.
• the product stream is richer in F-1233zdE and contains fewer unwanted compounds.
• the invention firstly relates to a composition comprising at least 99.5% by weight of 1, 1, 3,3-tetrachloropropene or a mixture of 1, 1, 3,3-tetrachloropropene and 1, 3,3 , 3-tetrachloropropene, and comprising at least one compound selected from a list of additional compounds consisting of pentachloropropanes (especially F-240fa), tetrachloropropenes other than F-1230za and F-1230zd (especially 1, 1, 2,3-tetrachloroprene (F-1230xa), chlorobutenes, chlorobutanes and oxygenates (for example, acids, esters, aldehydes or oxychlorides), said compound or all of said compounds being present in the composition in a weight content of less than or equal to 0.5%.
• pentachloropropanes especially F-240fa
• tetrachloropropenes other than F-1230za and F-1230zd especially
• said additional compound is present in the composition in a weight content of less than or equal to 1000 ppm and all of said compounds is less than or equal to 0.5%.
• the composition comprises at least 99.5% by weight, and preferably at least 99.7% by weight, and particularly preferably at least 99.8% by weight, of F-1230za, or a mixture of F-1230za and F-1230zd.
• the invention relates to a process for obtaining the composition as defined above.
• the invention relates generally to the use of said composition in the preparation of F-1233zd, and provides a particular method for producing 1-chloro-3,3,3-trifluoropropene, especially in trans form, comprising :
• F-1230zd or a mixture consisting of F-1230za and F-1230zd as starting reagent.
• the process comprises a single step of fluorination in the liquid phase and in the absence of catalyst.
• F-1230za impurities may be converted into different impurities in the reaction liquid medium operated under standard temperature and pressure conditions and accumulate within the reactor.
• These oligomers are detrimental to the reactivity because they occupy the reactor volume and deteriorate the reaction yield. They may also consist of compounds having some toxicity, or corrosivity, which causes difficulties in handling them for destruction. They must be removed using a purge system before being treated and the final residue removed.
• the present invention overcomes the disadvantages of the state of the art. It more particularly provides compositions based on F-1230za whose content of specific impurities is controlled, making it possible to minimize the generation of harmful oligomers in the reaction medium of the F-1233zdE manufacturing process. DESCRIPTION OF EMBODIMENTS OF THE INVENTION
• compositions according to the invention are provided.
• the invention provides compositions based on F-1230za or mixture F-1230za and F-1230zd.
• the content of F-1230za or the sum of the contents of F-1230za and F-1230zd is greater than or equal to 99.5%.
• it is greater than or equal to 99.6%, or 99.7%, or 99.8%, or 99.9%, or 99.95%.
• compositions according to the invention also comprise at least one compound chosen from a list of additional compounds which consists of pentachloropropanes (in particular 1, 1, 1, 3,3-pentachloropropane or F-240fa), tetrachloropropenes (especially 1, 1, 2,3-tetrachloroprene or F-1230xa), chlorobutenes, chlorobutanes and oxygenates, said compound being present in the composition in a content of less than or equal to 0.5% by weight; or less than or equal to 1000 ppm; or less than or equal to 500 ppm; or less than or equal to 450 ppm; or less than or equal to 400 ppm; or less than or equal to 350 ppm; or less than or equal to 300 ppm; or less than or equal to 250 ppm; or less than or equal to 200 ppm; or less than or equal to 150 ppm; or less than or equal to 100 ppm; or less than or equal to 75 ppm; or less than or
• oxygenated compound reference is made to any compound containing an oxygen heteroatom, such as acids, esters, aldehydes or oxychlorides, such as, for example, phosgene.
• Particularly undesirable impurities mixed in the reaction medium are:
• the molecules of the F-240 series such as F-240fa (1, 1, 1, 3,3-pentachloropropane), F-240da (1, 1, 2,3,3-pentachloropropane), F-240 ⁇ -240db (1,1,1,2,3-pentachloropropane), F-240ab (1,1,1,2,2-pentachloropropane), and more particularly F-240db and F-240fa;
• the molecules of the F-1230 series other than F-1230za and 1230zd, such as F-1230xa (1, 1, 2,3-tetrachloropropene), F-1230xd (1, 2,3,3 tetrachloropropene), F-1230xf (2,3,3,3-tetrachloropropene) and more particularly the aforementioned F-1230xa;
• the molecules F-240fa, F-240db, and F-1230xa are chlorinated impurities which have undesired behavior in the reaction medium in the presence of HF and in the absence of catalyst.
• F-240fa has a low conversion rate and has a certain stability in the reaction medium. It can lead to weakly fluorinated compounds such as F-241fa (1, 1, 3,3-tetrachloro-1-fluoropropane) of high boiling point. They tend to encumber the volume of the reaction medium without reacting sufficiently. It is substantially the same for the F-240db.
• the F-1230xa molecule generates significantly oligomers when heated in the presence of HF and in the absence of catalyst.
• compositions according to the invention so as to limit the presence of these chlorinated impurities.
• - comprise at least one of the F-240 series in a content of not more than 0.5%; or less than or equal to 1000ppm; or less than or equal to 250 ppm; or from 150 to 200 ppm; or from 100 to 150 ppm; or from 50 to 100 ppm; or from 25 to 50 ppm; or from 10 to 25 ppm; or from 5 to 10 ppm; or less than or equal to 5 ppm, and for example from 1 to 5 ppm; and or
• F-1230 series comprise at least one of the F-1230 series, other than F-1230za and 1230zd, in a content of not more than 0.5%; or less than or equal to 1000ppm; or less than or equal to 250 ppm; or from 150 to 200 ppm; or from 100 to 150 ppm; or from 50 to 100 ppm; or from 25 to 50 ppm; or from 10 to 25 ppm; or from 5 to 10 ppm; or less than or equal to 5 ppm, and for example
• F-1230xa, F-240fa and F-240db comprise at least one of F-1230xa, F-240fa and F-240db, in a content of not more than 0.5%; or less than or equal to 1000ppm; or less than or equal to 250 ppm; or from 150 to 200 ppm; or from 100 to 150 ppm; or from 50 to
• chlorobutane type molecules dichlorobutanes, trichlorobutanes and in particular the family of tetrachlorobutanes such as 1,1,4,4-tetrachlorobutane, 1,2,3,4-tetrachlorobutane and 1,1,1 3-tetrachlorobutane and 1,1,3,3-tetrachlorobutane;
• chlorobutenes-type molecules dichlorobutenes, tetrachlorobutenes and in particular trichlorobutenes such as 1,2,4-trichloro-but-2-ene, 1,3-dichloro-2-chloromethylpropene, 1, 1, 3-trichloro-but-1-ene, 4,4,4-trichloro-but-1-ene, 1,2,3-trichloro-1-butene, 3,4,4-trichloro-1-butene 2-chloromethyl-3,3-dichloropropene, 1,1,4-trichlorobut-2-ene, 3,3,4-trichlorobut-1-ene, 1,1,3-trichlorobut -2-ene, 1,3,3-trichloro-but-1-ene, 1,1,2-trichlorobut-1-ene, 1,1,1-trichloro-but-2-ene, 1 , 1,4-trichloro-but-2-ene, 1,3,4-
• - comprise at least one compound from the chlorobutane series in a content of not more than 0.5%; or less than or equal to 1000ppm; or less than or equal to 250 ppm; or from 150 to 200 ppm; or from 100 to 150 ppm; or from 50 to 100 ppm; or from 25 to 50 ppm; or from 10 to 25 ppm; or from 5 to 10 ppm; or less than or equal to 5 ppm, and for example from 1 to 5 ppm; or
• - include a compound from those of the chlorobutenes series, the total content of all these compounds being less than or equal to 0.5%; or less than or equal to 1000ppm; or less than or equal to 250 ppm; or from 150 to 200 ppm; or from 100 to 150 ppm; or from 50 to 100 ppm; or from 25 to 50 ppm; or from 10 to 25 ppm; or from 5 to 10 ppm; or less than or equal to 5 ppm, and for example from 1 to 5 ppm; or
• - comprise at least one compound among chlorobutanes and chlorobutenes, in a content of less than or equal to 0.5%; or less than or equal to 1000ppm; or less than or equal to 250 ppm; or from 150 to 200 ppm; or from 100 to 150 ppm; or from 50 to 100 ppm; or from 25 to 50 ppm; or from 10 to 25 ppm; or from 5 to 10 ppm; or less than or equal to 5 ppm, and for example from 1 to 5 ppm.
• Other particularly undesirable impurities mixed in the reaction medium are also molecules containing an oxygen heteroatom such as acids, esters, aldehydes or oxychlorides, especially phosgene.
• This compound is particularly known for its toxicity. In the presence of hydrogen fluoride, these oxygenated compounds are likely to decompose to form water. Water is an element whose content must be minimized because it can accentuate corrosion phenomena in HF medium.
• - comprise at least one oxygenated compound, in a content of less than or equal to 0.5%; or less than or equal to 1000ppm; or less than or equal to 250 ppm; or from 150 to 200 ppm; or from 100 to 150 ppm; or from 50 to 100 ppm; or from 25 to 50 ppm; or from 10 to
• compositions of the invention can be efficiently obtained from carbon tetrachloride, via F-240fa, by:
• the process for preparing the compositions comprises the following steps:
• compositions according to the invention can then be obtained by carrying out one or more steps of separation of F-1230za from the other compounds mentioned above, and in particular from F-240fa (which is in general the major by-product of dehydrochlorination) and also other telomerization / dehydrochlorination by-products such as F-240db and / or F-1230xa.
• separation steps can preferably be carried out by absorption / washing and distillation.
• distillation or in combination with it, it is also possible to provide separation by extractive distillation, physicochemical separations on molecular sieve, alumina or activated carbon or membrane separation.
• a first separation is generally carried out using standard distillation (plate column, packed column) at atmospheric pressure or under reduced pressure.
• the pressure chosen is less than 760 mmHg, preferably less than 450 mmHg and more preferably less than 200 mmHg.
• the pressure of the column determines the temperature conditions for a selected degree of separation.
• F-1230za can be recovered by operating the distillation at a temperature below 180 ° C, preferably below 160 ° C and more preferably below 130 ° C.
• a single column or a distillation train can be used. Under selected conditions, the purity of the F-1230za after distillation reaches at least 99.3%.
• a second separation can be carried out using an adsorption on zeolite or activated carbon.
• the active zeolites or carbons that can be used in the process for purifying F-1230za advantageously have an average pore size of 3.4 to 1 1 A, preferably 3.4 to 10 A and even more advantageously between 4 and 9. AT.
• the zeolite or activated carbon has an average pore size greater than 11A, the amount of F-1230za adsorbed increases, whereas if the average pore size is less than 3.4 A, the adsorption capacity of the zeolite or activated carbon is reduced.
• the zeolite preferably has an Si / Al ratio of 2 or less. If the Si / Al ratio of the zeolite is greater than two, some impurities are likely not to be selectively adsorbed.
• the zeolite is preferably at least one member selected from the group consisting of 4A molecular sieves, 5A molecular sieve, 10X molecular sieve and 13X molecular sieves.
• the zeolite and the activated carbon are preferably used individually for the regeneration of the adsorbent, but these can also be used as a mixture.
• the proportions of zeolite and activated carbon in the mixture are not particularly important.
• LHSV liquid hourly space velocity
• the treatment temperature of F1230za is 0 ° C to 120 ° C, preferably 20 ° C to 80 ° C. If the process temperature is above 120 ° C, the cost of the equipment may increase due to heating of the device, while if the process temperature is below 0 ° C cooling equipment may be required.
• the pressure is 0 to 3 MPa, preferably 0 to 1 MPa. If the pressure is higher than 3 MPa, profitability may decrease due to the pressure requirements of the device.
• a membrane separation technique can also be used in addition to an adsorption on activated carbon or on zeolite, or alternatively to these techniques.
• Membrane separation can be carried out in the gas phase according to a continuous process operated at low pressure or at reduced pressure.
• the pressure chosen is less than 5 bar, preferably less than 2 bar and more preferably less than atmospheric pressure.
• the choice of the membrane depends on the properties of the impurities to be separated from F-1230za (difference in solubility, diffusivity and permeability).
• Membrane separation is performed at a temperature dependent on the chosen pressure, less than 250 ° C, preferably less than 230 ° C and more preferably less than 180 ° C.
• zeolites that can be used in the process for purifying F-1230za advantageously have an average pore size of 3.4 to 1 1 A, preferably 3.4 to 10 A and even more advantageously between 4 and 9 A.
• adsorption step is carried out at a temperature between 0 and 120 ° C, advantageously between 5 and 100 ° C and preferably between 10 and 80 ° C.
• the F-1230za containing impurities When the F-1230za containing impurities is brought into contact with the zeolite and / or activated carbon in the liquid phase and / or is purified on a gas phase membrane under the conditions described above, the F-1230za can be obtained with purity greater than 99.9%.
• compositions according to the invention can be used for the manufacture of F-1233zdE, F-1234zeE and / or F-245fa by one or more fluorination steps, preferably in a single step.
• Fluorination is a non-catalyzed fluorination in the liquid phase by HF.
• the formation of F-1234ze and / or F-245fa can be promoted to increase their content in the resulting stream.
• the increase in F-1234ze content can also be achieved in another embodiment by recycling F-1233zd and F-245fa to the reactor after separation of F-1234ze.
• the increase in F-245fa content can also be achieved in another embodiment by recycling F-1233zd and F-1234ze to the reactor after separation of F-245fa.
• the liquid phase fluorination reaction can be carried out:
• the molar ratio HF / 1, 1, 3,3-tetrachloropropene includes the recycled HF portion and is preferably measured at the reactor inlet. at a reaction temperature of preferably between 80 and 120, and advantageously between 90 and 110 ° C.
• the fluorination reaction is preferably carried out in an unstirred reactor.
• the reactor is preferably a metal reactor.
• the reactor metal may be steel or stainless steel. However, other materials such as a superaustenitic stainless steel or a passivable nickel base alloy can be used.
• the absence of catalyst for the reaction is an advantage that avoids corrosion phenomena known to those skilled in the art when a fluorination catalyst is used in this type of reactor.
• a sample line is used to purge a quantity of unwanted high molecular weight products that may have formed during the fluorination reaction.
• This stream also contains HF and organic compounds which are separated by a specific treatment before being returned to the reactor, using, for example, decantation or azeotropic distillation, and preferably a combination of both.
• the fluorination process according to the present invention, of the composition thus separated can be implemented continuously, batchwise or batchwise. In a preferred embodiment, the process is operated continuously.
• the fluorination product stream may undergo appropriate treatments (distillation, washing, etc.) to recover purified F-1233zdE and separate it from the other compounds present (HCI, unreacted HF, c / s isomer). 1233zd, other organic compounds). One or more streams can be recycled.
• the invention relates, in a preferred embodiment, to a manufacturing process carried out by fluorination, in the liquid phase and in the absence of catalyst, of F-1233zd, and / or F-1234ze and / or F -245fa, comprising the steps:
• the invention relates more generally to the use of the compositions according to the invention for producing high purity F-1233zdE of the order of 99.9%, and comprising a reduced content of particular impurities.
• a particular impurity consists of the isomer 1233xf (2-chloro-3,3,3-trifluoropropene) which may be derived from chlorinated compounds 240db or 1230xa.
• the boiling point of this isomer is relatively close to our final compound and could lead to separation problems.
• impurities whose boiling point is also close to the compound F-1233zd and containing four carbons can come from the fluorination of chlorobutenes and / or chlorobutanes and prove to be troublesome in the process since they are difficult to separate. These impurities are chosen from the following list:
• impurities whose boiling point is also close to the compound F-1233zd and containing three carbons can come from the fluorination of chloropropenes and / or chloropropanes and prove to be troublesome in the process since they are difficult to separate. These impurities are chosen from the following list:
• a first step is to prepare the raw material.
• 1,1,3,3-Tetrachloropropene is obtained by dehydrochlorinating 1,1,1,3,3-pentachloropropane in the presence of anhydrous ferric chloride.
• Example 1 Preparation of F-1230za by dehydrochlorination of F-
• 1626.5 g of 1,1,1,3,3-pentachloropropane with a purity of 99.6% are introduced into a glass reactor equipped with a jacket and a reflux.
• the reactor sky is swept by a nitrogen flow rate of 4 l / h to inert the atmosphere.
• 17 g of anhydrous ferric chloride are then introduced before stirring is started at 800 rpm.
• the reflux is fed with a fluid maintained at 20 ° C.
• the condenser gas outlet is connected to a water bubbler which traps the HCI released during the dehydrochlorination reaction.
• the mixture is then heated at 80 ° C for 5 hours. 1338, 1 g of the resulting solution are drained from the flask.
• the mixture obtained is filtered to remove ferric chloride in suspension, purified with activated charcoal and analyzed by gas chromatography.
• Chlorobutenes and chlorobutanes could only be identified by their empirical formula as C 4 H 6 Cl 2 , C 4 H 7 C, C 4 HCl 4 or C 4 H 6 Cl 4 .
• the chloropropenes and chloropropanes are 1230xa and other compounds identified by their empirical formula as C3H3Cl3, or CsFteCU which are different from 250fb, 240fa or 240db.
• the low purity 1230za is then subjected to conventional laboratory distillation involving a 10-tray Oldershaw-type column, a refrigerant, a vacuum pump, a flask and receiving flasks.
• the distillation is carried out under a vacuum of 25 mbar, the product 1230za then has a boiling point of 53 ° C.
• the result of the distillation is shown in Table 2.
• the tests carried out are controlled pressure batch tests.
• 100 g of 99.6% F-1230za are successively introduced.
• a cooling circulation is established in the condenser, the reactor is heated to about and the pressure gradually increases to 10 bar (set pressure), the measured temperature is then 85 ° C in the reactor.
• the opening of the control valve eliminates light compounds. Organic products are washed and trapped. After 24 hours, the system is brought back to room temperature.
• the remainder of the organic compounds and hydracids are removed from the reactor by degassing, followed by a helium sweep. This results in 138 g of hydracids, 61 g of entrapped organic compounds and 1.5 g of black heavy compounds at the bottom of the reactor.
• the weight distribution of the organic compounds is as follows: 94.9% of E-1233zd, 3.3% of Z-1233zd, 0.8% of 245fa, 0.3% of E-1234ze, as well as intermediate compounds such as 1232zd (1,3-dichloro-3,3-difluoroprop-1-ene) or 1232za (1,1-dichloro-3,3-difluoroprop-1-ene).
• Example 3 An experiment is carried out according to Example 3 by introducing 550 g of F-240fa and 580 g of HF, ie a molar ratio of 1 1. This results in 570 g of hydracids, 545 g of organic compounds and 6.1 g of heavy compounds.
• the weight distribution of organic compounds is as follows: 75.7% F-240fa, 12.6% F-241fa, 7.1% E-1233zd, 0.2% Z-1233zd, 3.9% 245 ⁇ and 0.07% intermediate compounds (1232, 242).
• Comparative Example 5 Liquid Phase Batch Fluoridation of a 240db / 240aa Mixture
• Example 3 The procedure of Example 3 is reproduced.
• the organic compound is a 240db / 240aa mixture (88.5% / 1, 1.5%).
• 108 g of organic mixture and 101 g of HF are introduced successively into the autoclave, ie a molar ratio of 10.3.
• the weight distribution of the organic compounds is as follows: 86.2% F-240db, 1 1, 9% F-240aa, 1.3% of an isomer 241.
• Example 3 The procedure of Example 3 is reproduced.
• the organic compound is 1230xa.
• 90 g of 1230xa and 80 g of HF are introduced successively into the autoclave, ie a molar ratio of 8. This results in 90.5 g of hydracids and 66.3 g of organic compounds.
• the weight distribution of the organic compounds is as follows: 1.2% of 1230xa, 8.7% of a 1232 isomer and 90% of unidentified heavy compounds.
• the conversion rate of 1230xa in the uncatalyzed liquid phase is high but does not lead to the desired product, E-1233zd. It quickly converts to heavy compounds, difficult to identify.
• Examples 3 to 6 show the results obtained for the uncatalyzed fluorination reaction for the following reagents: 1230za, 240fa, 240db, 240aa and 1230xa. With the exception of 1230za, all other E-1233zd yields are very low.

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• 2015
  • 2015-05-22 FR FR1554655A patent/FR3036398B1/fr active Active
• 2016
  • 2016-05-04 US US15/575,980 patent/US10427998B2/en active Active
  • 2016-05-04 CN CN201680029733.5A patent/CN107646029A/zh active Pending
  • 2016-05-04 JP JP2017560689A patent/JP6959144B2/ja active Active
  • 2016-05-04 WO PCT/FR2016/051054 patent/WO2016189214A1/fr active Application Filing
  • 2016-05-04 EP EP16726920.8A patent/EP3297981A1/de not_active Withdrawn
• 2019
  • 2019-08-20 US US16/545,294 patent/US20190375698A1/en not_active Abandoned

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