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    • 专利摘要:
    The present invention relates to compositions based on F-1230za (1,1,3,3-tetrachloropropene), or a mixture consisting of F-1230za and F-1230zd (1,3,3,3-tetrachloropropene) , their manufacture and their use, in particular for the production of F-1233zE (trans-1-chloro-3,3,3-trifluoropropene), F-1234zeE (trans-1,3,3,3-tetrafluoropropene), and / or F-245fa (1,1,1,3,3-pentafluoropropane).
    公开号:FR3036398A1
    申请号:FR1554655
    申请日:2015-05-22
    公开日:2016-11-25
    发明作者:Anne Pigamo；Bertrand Collier
    申请人:Arkema France SA；
    IPC主号:
    专利说明:

    [0001] FIELD OF THE INVENTION The present invention relates to compositions based on F-1230za (1,1,3,3-tetrachloropropene), or a mixture consisting of F-1230za and F-1230zd (1,3,3,3-tetrachloropropene), their manufacture, and their use in particular for the production of F-1233zdE (trans-1-chloro-3,3,3-trifluoropropene) , F-1234zeE (trans-1,3,3,3-tetrafluoropropene), and / or F-245fa (1,1,1,3,3-pentafluoropropane). BACKGROUND OF THE INVENTION Fluoroolefins and in particular F-1233zdE are compounds of major interest for refrigeration and air-conditioning systems, in view of the new environmental regulations. It is known to produce hydrofluoroolefins such as F-1233zdE by fluorination of hydrochloro-olefins or hydrochlorocarbons in particular. This fluorination is generally a fluorination using hydrofluoric acid as fluorinating agent.
    [0002] Among the routes for obtaining F-1233zdE, it is in particular known to use F-240fa (1,1,1,3,3-pentachloropropane) as the starting compound. Reference is made, for example, to 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. . The document US2014 / 0221704 teaches the low miscibility between F-240fa and hydrogen fluoride, and proposes the addition of a phase transfer agent in the reaction medium to solve this problem.
    [0003] US2013 / 0211154 suggests increasing the pressure in the reaction medium to improve the conversion rate of F-240fa. Another possible method is the liquid phase fluorination of F1230za, in the absence of catalyst and under much less severe conditions, this olefinic raw material does not have these difficulties of low conversion rate. However, it is known that a liquid phase fluorination process can generate several undesired compounds such as oligomeric compounds, high boilers, toxic or corrosive compounds, or more generally impurities difficult to separate. In particular, these oligomeric compounds have the consequence of reducing the efficiency of the fluorination process and must be separated by purging, in a continuous system or in a batch system, from the reactor and reprocessed. High boilers can also prevent the reaction. . The detrimental effects of the impurities on the fluorination processes have also been observed in the reaction of F-1230za mentioned above. Stabilization of tetrachloropropenes by inhibitors, generally antioxidants, is taught in 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. However, the impact of these impurities in a liquid phase fluorination process is not described. It is desirable to produce F-1233zdE under good industrial scale production conditions by means of a process that is simple to implement, in particular in the liquid phase and in the absence of a catalyst, which makes it possible to an improvement of the yield and / or which does not have difficulties of separation of undesired compounds. SUMMARY OF THE INVENTION 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 mixed with F-1230zd, is significantly more effective. 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 35 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 ( s) in the composition in a weight content of less than or equal to 0.5% In one embodiment, said additional compound is present in the composition in a weight content of less than or equal to 1000ppm and all of said compounds is less than or equal to equal to 0.5% Selo n an embodiment, 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.
    [0004] Secondly, the invention relates to a process for obtaining the composition as defined above. Next, the invention generally relates to the use of said composition in the preparation of F-1233zd, and provides a particular process for producing 1-chloro-3,3,3-trifluoropropene, especially in trans form, comprising: - providing a composition as defined above; the reaction of this composition with hydrofluoric acid. F-1230zd or a mixture of F-1230za and F-1230zd can also be used as the starting reagent. According to the preferred embodiment, the process comprises a single step of fluorination in the liquid phase and in the absence of catalyst. During the fluorination reaction (s), some of the F-1230za impurities may be converted to 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. More particularly, it provides compositions based on F-1230za whose specific impurity content is controlled, making it possible to minimize the generation of harmful oligomers in the reaction medium of the F-1233zdE manufacturing process.
    [0005] DESCRIPTION OF EMBODIMENTS OF THE INVENTION The invention is now described in more detail and in a nonlimiting manner in the description which follows.
    [0006] All the contents indicated are contents by weight unless otherwise indicated. Compositions According to the Invention The invention provides compositions based on F-1230za or blend 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%. According to some embodiments, it is greater than or equal to 99.6%, or 99.7%, or 99.8%, or 99.9%, or 99.95%. The compositions according to the invention also comprise at least one compound chosen from a list of additional compounds which is constituted by 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 at a level 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 equal to 50 ppm; or less than or equal to 25 ppm; or less than or equal to 10 ppm; or less than or equal to 5 ppm. By 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-240db (1,1,1,2,3-pentachloropropane), F-240ab (1,1,1,2,2pentachloropropane), and more particularly F -240db and the F-240fa; - the F-1230 series molecules, other than F-1230za and 1230zd, such as F-1230xa (1,1,2,3-tetrachloropropene), F1230xd (1,2,3,3 tetrachloropropene), F-1230xf (2,3,3,3-tetrachloropropene) and more particularly the aforementioned F-1230xa; The F-240fa, F-240db, and F-1230xa molecules 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.
    [0007] 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. In contrast, the F1230xa molecule generates significantly oligomers when heated in the presence of HF and in the absence of catalyst. Therefore, it is desirable to adjust the compositions according to the invention so as to limit the presence of these chlorinated impurities. Thus, advantageous compositions according to the invention: comprise at least one compound from those of the F-240 series, 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; and / or comprise at least one of the F-1230 series, other than F-1230za and 1230zd, 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; or else - comprise at least one of F-1230xa, F-240fa and F-240db, 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.
    [0008] Other particularly undesirable impurities mixed in the reaction medium are also chlorinated molecules containing four carbon atoms. These higher boiling compounds will also accumulate in the reactor, clog up the reaction volume and may lead, to a lesser extent, to fluorination and rearrangement of the molecule to a four-carbon fluorinated compound whose high toxicity is well known, namely perfluoroisobutylene (PFIB). These impurities contained in the raw material are therefore: chlorobutane type molecules, dichlorobutanes, trichlorobutanes and in particular the family of tetrachlorobutanes such as 1,1,4,4-tetrachlorobutane, 1,2,3, 4-tetrachlorobutane, 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-trichloro 2-butene, 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-trichloro-but-1-ene, 1,1,2-trichlorobut-2-ene, 1,2,3-trichlorobut-1-ene; trichloro-but-2-ene, 2-methyl-1, 1, 3-trichloro-1-propene, 1,2,4-trichloro-but-2-ene, 2,3,4-trichlorobut -1-ene.
    [0009] Thus, advantageous compositions according to the invention: comprise at least one compound from the chlorobutane series 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; 30 or 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 one 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 10 to 30 ppm; or from 5 to 10 ppm; or less than or equal to 5 ppm, and for example from 1 to 5 ppm; or else - 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 1000 ppm; 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.
    [0010] 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.
    [0011] Thus, advantageous compositions according to the invention: 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 25 ppm; or from 5 to 10 ppm; or less than or equal to 5 ppm, and for example from 1 to 5 ppm.
    [0012] Preparation of the compositions according to the invention The compositions of the invention can be efficiently obtained from carbon tetrachloride via F-240fa by: - reaction of carbon tetrachloride with vinyl chloride to produce F-240fa; 240fa; dehydrochlorination of F-240fa to obtain F-1230za.
    [0013] Alternatively, the method of preparing the compositions comprises the following steps: - reaction of carbon tetrachloride with ethylene to produce F-250fb; 5 - chlorination reaction of F-250fb (1,1,1,3-tetrachloropropane) to manufacture predominantly F-240fa; dehydrochlorination of F-240fa to obtain F-1230za. The compositions according to the invention can then be obtained by carrying out one or more steps for separating F-1230za from the other compounds mentioned above, and in particular with respect to F-240fa (which is generally the major by-product of dehydrochlorination) and also other telomerization / dehydrochlorination byproducts such as F-240db and / or F-1230xa.
    [0014] These separation steps can preferably be carried out by absorption / washing and distillation. Alternatively to the 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.
    [0015] 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. Inherently, 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 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 which can be used in the process for purifying F-1230za advantageously have an average pore size of 3.4 to 11 A, preferably 3.4 to 10 A and even more advantageously between 4 and 9. A. If the zeolite or activated carbon has an average pore size greater than 11A, the amount of adsorbed F-1230za increases, whereas if the average pore size is less than 3.4A, the capacity of the adsorbed F-1230za increases. adsorption 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 charcoal 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. To treat F-1230za with zeolite and / or activated carbon in the liquid phase, a batch process or a continuous process may be used. Industrially, a method of continuously passing F-1230za on a fixed bed is preferable. The liquid hourly space velocity (LHSV) may be suitably selected depending on the content of impurities to be removed and the amount of F-1230za to be treated. In general, the space velocity is preferably from 1 to 50 hr-1. Industrially the purification process can alternatively use two adsorption towers. 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 apparatus, whereas 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.
    [0016] A membrane separation technique can also be used in addition to 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 selected pressure, less than 250 ° C, preferably less than 230 ° C and more preferably less than 180 ° C. According to a preferred embodiment, several separation techniques are associated such as extractive distillation or distillation followed by adsorption separation on molecular sieves. The zeolites that can be used in the process for purifying F-1230za advantageously have an average pore size of 3.4 to 11 A, preferably 3.4 to 10 A and even more advantageously between 4 and 9 A. adsorption stage 10 is carried out at a temperature between 0 and 120 ° C, advantageously between 5 and 100 ° C and preferably between 10 and 80 ° C. When the F-1230za containing impurities is contacted with zeolite and / or activated carbon in the liquid phase and / or is purified on a gas phase membrane under the conditions described above, F-1230za can be obtained with a purity greater than 99.9%. Manufacture of F-1233zdE The 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. By adjusting the operating conditions (temperature, pressure), the formation of F-1234ze and / or F-245fa can be promoted to increase their content in the resulting stream. The increase of F-1234ze content can also be achieved in another embodiment by recycling F1233zd 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 fluorination reaction in the liquid phase can be carried out: with a molar ratio of HF / 1,1,3,3-tetrachloropropene preferably between 5 and 15, preferably between 6 and 15, even more preferably between 8 and 15, advantageously between 9 and 14 and preferably between 9 and 12. The HF / 1,1,3,3-tetrachloropropene molar ratio includes the recycled HF portion and is preferably measured at the inlet of the reactor. - at a reaction temperature of preferably between 80 and 120, and preferably between 90 and 110 ° C. at a pressure of between 5 and 20 bar, preferably between 5 and 15 bar, more preferably between 7 and 15 bar and advantageously between 7 and 12 bar. 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 may 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.
    [0017] 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 recoverable organic compounds which are separated by 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 carried out continuously, batchwise or batchwise. In a preferred embodiment, the process is operated continuously.
    [0018] The fluorination product stream may undergo appropriate treatments (distillation, washing, etc.) to recover purified F-1233zdE and separate it from other present compounds (HCI, unreacted HF, cis-1233zd isomer). other organic compounds). One or more streams can be recycled.
    [0019] Thus, the invention relates, in a preferred embodiment, to a manufacturing process carried out by fluorination, in the liquid phase and in the absence of a catalyst, of F-1233zd, and / or F-1234ze and / or F-245fa, comprising the steps of: introducing into a fluorination reactor a stream comprising the composition of 1,1,3,3-tetrachloropropene (F-1230za), or a mixture of 1,1,3,3-tetrachloropropene; tetrachloropropene and 1,3,3,3-tetrachloropropene (F-1230zd) according to the invention.
    [0020] The process is especially useful for preparing trans-1-chloro-3,3,3-trifluoropropene (F-1233zdE) or trans-1,3,3,3-tetrafluoropropene (F1234zeE).
    [0021] Finally, the invention more generally relates 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 specific content of impurities. A particular impurity is the 1233xf (2-chloro-3,3,3-trifluoropropene) isomer derived from the 240db or 1230xa chlorinated compounds. The boiling point of this isomer is relatively close to our final compound and could lead to separation problems. Other impurities whose boiling point is also close to compound F-1233zd and containing four carbons may be derived 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 selected from the following list: 1,1,1-trifluorobutane or F-383mff or CF3-CH2-CH2-CH3 1,1,1,4,4-pentafluorobutane or F-365mff or CF3-CH2 -CH2-CHF2 2,2,3,3-tetrafluorobutane or F-374scc or CH3-CF2-CF2-CH3 1,1,1,2,2,4,4,4-octofluorobutane or F-338mcf or CF3 -CF2-CH2-CF3 1,1,1,2,2,3,3-heptafluorobutane or F-347mcc or CF3-CF2-CF2-CH3 1,1,1,2,2,3,3,4 , 4-nonafluorobutane or F-329mcc or CF3-CF2-CF2-CHF2 Other impurities whose boiling point is also close to the compound F-1233zd and containing three carbons may come from the fluorination of chloropropenes and / or chloropropanes and prove to be troublesome in the process because they are difficult to separate. These impurities are selected from the following list: 1,2-difluoropropane or F-272ea or CH2F-CHF-CH3 1,1,2-trifluoropropane or F-263eb or CHF2-CHF-CH3 1,2,2 Example 3 The following examples illustrate the invention without limiting it. EXAMPLE 3
    [0022] 3036398 13 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.
    [0023] EXAMPLE 1 Preparation of F-1230za by dehydrochlorination of F-240fa 1626.5 g of 1,1,1,3,3-pentachloropropane are introduced into a glass reactor equipped with a jacket and a reflux. purity of 99.6%. The reactor skies are swept by a nitrogen flow rate of 41 / hr 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. 1338.1g 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. Compound (°) / wt) Before reaction After reaction 1230za 0.046 92.25 250fb 0.029 0.024 240fa 99.61 3.10 C2Cl6 0.059 0.066 240db 0.157 0.187 chlorobutenes + chlorobutanes 0.083 0.127 chloropropenes + chloropropanes 0.003 0.134 Table 1- dehydrochlorination of 240fa : composition of the mixture Chlorobutenes and chlorobutanes could only be identified by their empirical formula such as C4F16Cl2, Cl4H7Cl3, Cl4H2Cl4 or ClF16Cl4. The chloropropenes and chloropropanes are 1230xa and other compounds identified by their empirical formula such as C3H3Cl3, or C3H2Cl4 which are different from 250fb, 240fa or 240db. The complement of the above compositions consists of unidentified products.
    [0024] EXAMPLE 2 Distillation of 1230za 1230za of low purity 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 distillation result is shown in Table 2. Compound (°) / wt) Before distillation After distillation 1230za 92.25 99.30 250fb 0.024 0.021 240fa 3.10 0.179 C2CI6 0.066 0.012 240db 0.187 0.001 chlorobutenes + chlorobutanes 0.127 0.133 chloropropanes + chloropropanes 0.134 0.245 TABLE 2 Distillation of 1230za: composition of the mixture Example 3: batch fluorination of 1230za The tests carried out are batch pressure-controlled tests. In the 1-liter stainless steel autoclave, equipped with a condenser, a pressure indicator, a thermometric probe and a burst disc, 100 g of 99.6 F-1230za are successively introduced. % purity and 115g HF, a molar ratio of 10.3. 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. At this pressure, 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 remaining 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 3036398 Intermediate compounds such as 1232zd (1,3-dichloro-3,3-difluoropropene) or 1232za (1,1-dichloro-3,3-difluoroprop-1-ene). No trace of 1230za was found illustrating complete conversion of the reagent. The conversion is very high and the final product yield desired E-1233zd close to 95%. Comparative Example 4: Batch Fluoridation in the Liquid Phase of 240fa A test according to Example 3 is carried out by introducing 550 g of F-240fa and 580 g of HF, ie a molar ratio of 11. This results in 570 g of hydracids, 5445 g of organic compounds and 6.1 g of heavy compounds. The weight distribution of the organic compounds is as follows: 75.7% F-240fa, 12.6% F-241fa, 7.1% E-1233zd, 0.2% Z-1233zd, 3.9% 245α and 0.07% intermediate compounds (1232, 242). The conversion rate of F-240fa in the uncatalyzed liquid phase is therefore very low and the yield of the desired product E-1233zd is very low. Comparative Example 5: Liquid Phase Batch Fluoridation of a 240db / 240aa Mixture The procedure of Example 3 is reproduced. The organic compound is a 240db / 240aa mixture (88.5% / 11.5%). 108 g of organic mixture and 101 g of HF are introduced successively into the autoclave, a molar ratio of 10.3. This results in 96 g of hydracids, 90 g of organic compounds and 2.2 g of heavy compounds. The weight distribution of the organic compounds is as follows: 86.2% F-240db, 11.9% F-240aa, 1.3% 241 isomer. The conversion rate of F-240db and F-240aa in the uncatalyzed liquid phase is therefore very low and the yield of desired product E-1233zd does not exist.
    [0025] Comparative Example 6: Liquid Phase Batch Fluoridation of 1230xa The procedure of Example 3 is repeated. 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% 1230xa, 8.7% 1232 isomer and 90% unidentified heavy compounds.
    [0026] The 1230xa conversion rate 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.
    [0027] 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 E1233zd yields are very low.
    权利要求:
    Claims (6)
    [0001]
    REVENDICATIONS1. Composition comprising at least 99.5% by weight of 1,1,3,3-tetrachloropropene (F-1230za), or a mixture of 1,1,3,3-tetrachloropropene and 1,3,3,3 tetrachloropropene (F-1230zd), and at least one additional compound selected from a list of compounds consisting of pentachloropropanes, tetrachloropropenes other than F-1230za and F-1230zd, chlorobutenes, chlorobutanes and oxygenates, said compound and / or all of said compounds being present in the composition in a content less than or equal to 0.5% by weight.
    [0002]
    The composition of claim 1, wherein said additional compound is 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 equal to 50 ppm; or less than or equal to 25 ppm; or less than or equal to 10 ppm; or less than or equal to 5 ppm in the composition.
    [0003]
    The composition of claim 2, wherein said additional compound is or are selected from 1,1,1,3,3-pentachloropropane (F-240fa), 1,1,1,2,3-pentachloropropane (F240db ) and 1,1,2,3-tetrachloropropene (F-1230xa).
    [0004]
    A process for producing the composition of any one of claims 1 to 3 comprising the steps of: reacting a carbon tetrachloride with vinyl chloride to produce 1,1,1,3,3-pentachloropropane (F240fa); dehydrochlorination of F-240fa to obtain 1,1,3,3-tetrachloropropene (F-1230za) one or more steps of F-1230za separation. 3036398 18
    [0005]
    5. A process for producing the composition according to any one of claims 1 to 3 comprising the following steps: - the reaction of carbon tetrachloride with ethylene to produce 1,1,1,3-tetrachloropropane (F- 250fb); chlorination of F-250fb to make 1,1,1,3,3-pentachloropropane (F-240fa); dehydrochlorination of F-240fa to obtain 1,1,3,3-tetrachloropropene (F-1230za) one or more steps of F-1230za separation. Process according to claim 4 or 5, in which the separation is carried out by distillation or extraction, and / or by physico-chemical separation on molecular sieve, alumina or activated carbon, and / or by membrane separation, optionally in the gas phase. A process according to claim 6 wherein a first separation step is carried out by one or more distillation (s) and a second separation step is carried out by adsorption on molecular sieve, activated carbon, or a mixture thereof. A process according to claim 6 or 7 wherein the separation step is carried out by adsorption on zeolite, molecular sieve type 4A, 5A, 10X or 13X, and optionally followed by gas phase membrane separation. A process according to claim any of claims 6, 7 or 8 wherein the adsorptive separation step is carried out at a temperature of from 0 to 120 ° C, preferably from 20 to 80 ° C. Use of the composition according to any one of claims 1 to 5 in the manufacture of 1-chloro-3,3,3-trifluoropropene (F-1233zd), 1,3,3,3-tetrafluoropropene (F-1234ze) or 1,1,1,3,3-pentafluoropropane (F-245fa). Process for producing 1-chloro-3,3,3-trifluoropropene (F-1233zd), and / or 1,3,3,3-tetrafluoropropene (F-1234ze) and / or 1,1,1,3 , 3- 5 10
    [0006]
    6. Pentafluoropropane (F-245fa), by fluorination carried out in the liquid phase and in the absence of a catalyst, comprising the steps of: introducing into a fluorination reactor a flow comprising the composition according to any one of claims 1 to 3. 12. The process according to claim 11 for forming trans-1-chloro-3,3,3-trifluoropropene (F-1233zdE) or trans-1,3,3,3-tetrafluoropropene (F-1234zeE). 13. A process according to claim 11 or 12 followed by one or more steps of separating 1-chloro-3,3,3-trifluoropropene (F-1233zd), and / or 1,3,3,3-tetrafluoropropene ( F-1234ze) and / or 1,1,1,3,3-pentafluoropropane (F-245fa) from the product stream. 15 20 25 30 35
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    同族专利:
    公开号 | 公开日
    WO2016189214A1|2016-12-01|
    US20180148394A1|2018-05-31|
    US20190375698A1|2019-12-12|
    EP3297981A1|2018-03-28|
    FR3036398B1|2019-05-03|
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    JP6959144B2|2021-11-02|
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    法律状态:
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    2016-11-25| PLSC| Publication of the preliminary search report|Effective date: 20161125 |
    2017-04-13| PLFP| Fee payment|Year of fee payment: 3 |
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    2021-05-07| TP| Transmission of property|Owner name: SPOLEK PRO CHEMICKOU A HUTNI VYROBU, AKCIOVA S, CZ Effective date: 20210330 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1554655A|FR3036398B1|2015-05-22|2015-05-22|COMPOSITIONS BASED ON 1,1,3,3-TETRACHLOROPROPENE|
    FR1554655|2015-05-22|FR1554655A| FR3036398B1|2015-05-22|2015-05-22|COMPOSITIONS BASED ON 1,1,3,3-TETRACHLOROPROPENE|
    PCT/FR2016/051054| WO2016189214A1|2015-05-22|2016-05-04|Compositions based on 1,1,3,3-tetrachloropropene|
    CN201680029733.5A| CN107646029A|2015-05-22|2016-05-04|Composition based on 1,1,3,3 tetrachloropropylenes|
    JP2017560689A| JP6959144B2|2015-05-22|2016-05-04|Composition based on 1,1,3,3-tetrachloropropene|
    EP16726920.8A| EP3297981A1|2015-05-22|2016-05-04|Compositions based on 1,1,3,3-tetrachloropropene|
    US15/575,980| US10427998B2|2015-05-22|2016-05-04|Compositions based on 1,1,3,3-tetrachloropropene|
    US16/545,294| US20190375698A1|2015-05-22|2019-08-20|Compositions based on 1,1,3,3-tetrachloropropene|
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