5595-10-8

A method of producing a hydrofluoroolefin, wherein said method comprises: reacting a fluoroolefin with XZmH3-m●L, wherein X is a group III element, L is a nitrogen, phosphorus, oxygen or sulphur-based ligand, m is from 0 to 2, and Z is a halogen, and wherein the fluoroolefin is either a fully-fluorinated fluoroolefin, or a fluoroolefin that is fully-fluorinated except from one olefinic hydrogen.

The invention belongs to the technical field of preparation of pentafluoropropylene, and particularly relates to a method for preparing 1,2,3,3,3-pentafluoropropylene from hexafluoropropylene. According to the method, hexafluoropropylene and hydrogen are taken as raw materials, and 1,2,3,3,3-pentafluoropropylene is prepared through direct one-step reaction under the action of a solid mixture catalyst; the solid mixture catalyst is a mixture of one or more of oxyhalides of transition metals, IIA and IIIA group metals or derivatives thereof and a VIII group metal-based compound. Compared with amethod for preparing 1,2,3,3,3-pentafluoropropylene from hexafluoropropylene through a hydrogenation and HF removal two-step method, the solid mixture catalyst used in the method provided by the invention has higher pentafluoropropylene selectivity and reaction stability.

The selective hydrodefluorination of hexafluoropropene to HFO-1234ze and HFO-1234yf can be achieved by reaction with simple group 13 hydrides of the form EH3 ? L (E=B, Al; L=SMe2, NMe3). The chemoselectivity varies depending on the nature of the group 13 element. A combination of experiments and DFT calculations show that competitive nucleophilic vinylic substitution and addition-elimination mechanisms involving hydroborated intermediates lead to complementary selectivities. (Figure presented.).

The transition to more economically friendly small-chain fluorinated groups is leading to a resurgence in the synthesis and reactivity of fluoroalkenes. One versatile method to obtain a variety of commercially relevant hydrofluoroalkenes involves the catalytic hydrodefluorination (HDF) of fluoroalkenes using silanes. In this work it is shown that copper hydride complexes of tertiary phosphorus ligands (L) can be tuned to achieve selective multiple HDF of fluoroalkenes. In one example, HDF of the hexafluoropropene dimer affords a single isomer of heptafluoro-2-methylpentene in which five fluorines have been selectively replaced with hydrogens. DFT computational studies suggest a distinct HDF mechanisms for L2CuH (bidentate or bulky monodentate phosphines) and L3CuH (small cone angle monodentate phosphines) catalysts, allowing for stereocontrol of the HDF of trifluoroethylene.

Provided is an efficient method for producing a fluorine-containing compound without the need for a rectification column involving numerous stages, extractive distillation, etc. The method for producing a fluorine-containing compound includes the step of supplying a composition containing a mixture to a dehydrohalogenation step, the mixture being at least one member selected from the group consisting of mixtures of at least one fluoroolefin and at least one hydrofluorocarbon, the boiling points of which are close to each other, azeotropic mixtures of at least one fluoroolefin and at least one hydrofluorocarbon, and pseudo-azeotropic compounds of at least one fluoroolefin and at least one hydrofluorocarbon.

In the present invention from a number 1, 2, 3, 3, 3 - pentafluoropropene (HFO provided 1225ye) hexafluoropropylene (HFP) method for bath a number [...] substrate. The upper index 2, 3, 3, 3 - 1, 2, 3, 3, 3 - pen hit [phul [phul] base oro pro pen phenolic resin foam which is very low it is a coolant 1234ze (HFO provided 1234yf) HFP H2S-free capacity as an intermediate of a hydrogenating catalyst 1, 1, 2, 3, 3, 3 - hexafluoropropane (HFC-a 236ea) is patterned to expose a hydrogen on generating; reacting a hydrogen fluoride catalyst obtained in said HFC provided 236ea and subjected to a high pressure liquid coolant bath of hydrogen fluoride in an HFO provided 1225ye number number 2000. Reacting a number when a HFC-a 236ea HFP hydrogen and vapor phase high pressure liquid coolant, reaction properly time to prevent the hydrogen consumed only unreacted hydrogen separation and circulating process can be eliminated, such as returning excess of hydrogen by a prefilled billion number. In hydrogenation of the resulting gaseous products another separation step (HFC-a 236ea) followed by a high pressure liquid coolant vapor reaction directly without a perhalogenated alkyl HFO provided 1225ye number 2000. In addition in the present invention HFP hydrogenation reaction temperature and number of stand-alone Dichlorethane efficiently number for the HFC-a 236ea perhalogenated reactions the method generates a control hydrogenation cycled in an HFC-a 236ea surfaces have diameters less than 2000. (by machine translation)

Cp3Ln (Ln = Ce, Nd, Sm, Er, Yb) are applied as precatalysts in the presence of LiAlH4 for the C–F bond activation of hexafluoropropene, 1,1,3,3,3-pentafluoropropene, trifluoropropene, chlorotrifluoroethene, and octafluorotoluene. 100 % conversion and TONs up to 155 could be observed for the hydrodefluorination reaction (HDF). For chlorotrifluoroethene hydrodefluorination occurs with high chemoselectivity favoring the C–F bond activation versus C–Cl bond activation.

The invention refers to a process for producing a fluorinated alkene, in particular X1n—CFmCF═CH2 comprising the steps of a) providing a at least one fluorinated alkene of the general formula (I) X1n—CFmCF═CF2, wherein n is 0, 1, 2, 3; X1 is H, substituted or unsubstituted C1-C5 alkyl, m is 1, 2 or 3, preferably 2 or 3, in at least one donor solvent; b) adding at least one reducing agent selected from the group of organic aluminum hydrides (alanes), gallium hydrides (gallanes) or boron hydrides (boranes); and c) reacting the mixture of the fluorinated alkene according to formula (I) and the at least one reducing agent.

The gallium hydrides (iBu)2GaH (1 a), LiGaH4 (1 b) and Me3N?GaH3 (1 c) hydrodefluorinate vinylic and aromatic C?F bonds when O and N donor molecules are present. 1 b exhibits the highest reactivity. Quantitative conversion to the hydrodefluorination (HDF) products could be observed for hexafluoropropene and 1,1,3,3,3-pentafluoropropene, 94 % conversion of pentafluoropyridine and 49 % of octafluorotoluene. Whereas for the HDF with 1 b high conversions are observed when catalytic amounts of O donor molecules are added, for 1 a, the addition of N donor molecules lead to higher conversions. The E/Z selectivity of the HDF of 1,1,3,3,3-pentafluoropropene is donor-dependent. DFT studies show that HDF proceeds in this case via the gallium hydride dimer–donor species and a hydrometallation/elimination sequence. Selectivities are sensitive to the choice of donor, as the right donor can lead to an on/off switching during catalysis, that is, the hydrometallation step is accelerated by the presence of a donor, but the donor dissociates prior to elimination, allowing the inherently more selective donorless gallium systems to determine the selectivity.

Hydrodefluorination reactions (HDF) of per- and polyfluorinated olefins and arenes by cheap aluminum alkyl hydrides in non-coordinating solvents can be catalyzed by O and N donors. TONs with respect to the organocatalysts of up to 87 have been observed. Depending on substrate and concentration, high selectivities can be achieved. For the prototypical hexafluoropropene, however, low selectivities are observed (E/Z≈2). DFT studies show that the preferred HDF mechanism for this substrate in the presence of donor solvents proceeds from the dimer Me4Al2(μ-H)2?THF by nucleophilic vinylic substitution (SNV)-like transition states with low selectivity and without formation of an intermediate, not via hydrometallation or σ-bond metathesis. In the absence of donor solvents, hydrometallation is preferred but this is associated with inaccessibly high activation barriers at low temperatures. Donor solvents activate the aluminum hydride bond, lower the barrier for HDF significantly, and switch the product preference from Z to E. The exact nature of the donor has only a minimal influence on the selectivity at low concentrations, as the donor is located far away from the active center in the transition states. The mechanism changes at higher donor concentrations and proceeds from Me2AlH?THF via SNV and formation of a stable intermediate, from which elimination is unselective, which results in a loss of selectivity.

Alkene metathesis with directly fluorinated alkenes is challenging, limiting its application in the burgeoning field of fluoro-organic chemistry. A new nickel tris(phosphite) fluoro(trifluoromethyl)carbene complex ([P3Ni]=CFCF3) reacts with CF2=CF2 (TFE) or CF2=CH2 (VDF) to yield both metallacyclobutane and perfluorocarbene metathesis products, [P3Ni]=CF2 and CR2=CFCF3 (R=F, H). The reaction of [P3Ni]=CFCF3 with trifluoroethylene also yields metathesis products, [P3Ni]=CF2 and cis/trans-CFCF3=CFH. However, unlike reactions with TFE and VDF, this reaction forms metallacyclopropanes and fluoronickel alkenyl species, resulting presumably from instability of the expected metallacyclobutanes. DFT calculations and experimental evidence established that the observed metallacyclobutanes are not intermediates in the formation of the observed metathesis products, thus highlighting a novel variant of the Chauvin mechanism enabled by the disparate four-coordinate transition states.

We present herein the utilization of NHC-stabilized alane adducts of the type (NHC)·AlH3 [NHC = Me2Im (1), Me2ImMe (2), iPr2Im (3), iPr2ImMe (4), Dipp2Im (5)] and (NHC)·AliBu2H [NHC = iPr2Im (6), Dipp2Im (7)] as novel hydride transfer reagents in the hydrodefluorination (HDF) of different fluoroaromatics and hexafluoropropene. Depending on the alane adduct used, HDF of pentafluoropyridine to 2,3,5,6-tetrafluoropyridine in yields of 15–99 % was observed. The adducts 1, 2, and 5 achieved a quantitative conversion into 2,3,5,6-tetrafluoropyridine at room temperature immediately after mixing the reactants. Studies on the HDF of fluorobenzenes with the (NHC)·AlH3 adducts 1, 3, and 5 and (Dipp2Im)·AliBu2H (7) showed the decisive influence of the reaction temperature on the H/F exchange and that 135 °C in xylene afforded the best product distribution. Although the HDF of hexafluorobenzene yielded 1,2,4,5-tetrafluorobenzene in moderate yields with traces of 1,2,3,4-tetrafluorobenzene and 1,2,4-trifluorobenzene, pentafluorobenzene was converted quantitatively into 1,2,4,5-tetrafluorobenzene, with (Dipp2Im)·AliBu2H (7) showing the highest activity and reaching complete conversion after 12 h at 135 °C in xylene. The HDF of hexafluoropropene with (Me2Im)·AlH3 (1) occurred even at low temperatures and preferably at the CF2 group with the formation of 1,2,3,3,3-pentafluoropropene (with 0.4 equiv. of 1) or 2,3,3,3-tetra-fluoropropene (with 0.9 equiv. of 1) as the main product.

2, 3, 3, 3-hexafluoro propylene, the 1, 3, 3, 3-and -1234z3 (HFO-1234yf) (HFP) from -1234z3 (HFO-1234ze, E-form) simultaneous manufacturing method is provided. (by machine translation)

Provided is a manufacturing method of 2,3,3,3-tetrafluoropropene (HFO-1234yf) and 1,3,3,3- tetrafluoropropene (HFO-1234ze, E-form) from hexafluoropropylene (HFP) at the same time. According to the present invention, hydrogen fluoride as a byproduct can be obtained as at least 35 wt% of hydrofluoric acid or a hydrofluoric acid solution using an absorption tower without a complex distillation process for commercialization.(AA) First hydrogenation(BB) First de-hydrogen fluoride(CC) First de-hydrogen fluoride adsorption(DD) First distillation(EE) Second hydrogenation(FF) Second distillation(GG) Second de-hydrogen fluoride(HH) Second de-hydrogen fluoride adsorption(II) Third distillation(JJ) EfiningCOPYRIGHT KIPO 2015

The subject matter of the invention is a process for preparing fluoroolefin compounds. The invention relates more particularly to a process for producing a (hydro)fluoroolefin compound, which comprises (i) bringing at least one compound comprising from three to six carbon atoms, at least two fluorine atoms and at least one hydrogen atom, on the condition that at least one hydrogen atom and one fluorine atom are located on adjacent carbon atoms, into contact with a solid reactant comprising calcium hydroxide.

The invention relates to a method for preparing olefin fluorine compounds. Specifically, the invention relates to a method for producing a (hydro)fluoroolefin compound, including: (i) in an agitated reactor provided with at least one reactant inlet and at least one outlet, contacting, with potassium hydroxide in an aqueous reaction medium, at least one compound containing three to six carbon atoms, at least two fluorine atoms, and at least one hydrogen atom, with the proviso that at least one hydrogen atom and one fluorine atom are located on adjacent carbon atoms, so as produce the (hydro)fluoroolefin compound, separated in a gaseous state from the reaction medium and from potassium fluoride; (ii) in an aqueous medium, contacvting the potassium fluoride formed in step (i) with calcium hydroxide in a second reactor so as to produce potassium hydroxide and to precipitate calcium fluoride; (iii) separating the calcium fluoride precipitated in step (ii) from the reaction medium; and (iv) optionally recirculating the reaction medium after optionally recirculating the reaction medium after optionally adjusting the concentration of potassium hydroxide in step (i), characterized in that potassium hydroxide, with regard to the reaction medium of step (ii), is between 10 and 35 wt % of the weight of the water/potassium hydroxide mixture of the medium.

The invention relates to a method for preparing fluoropropenes of formula (I) CF3CF═CHR, where R is a hydrogen or a fluorine atom from at least one compound of formula (Ia) CF3CF═CFR, where R has the same meaning as in formula (I), said method including the following steps: (i) hydrogenating at least one compound of formula (Ia) in an adiabatic reactor in the presence of a catalyst with a superstoichiometric amount of hydrogen so as to produce a hydrofluoropropane; (ii) partially condensing the flow from the adiabatic reactor of step (i) so as to produce a gaseous phase fraction, including unreacted hydrogen and a portion of the formed hydrofluoropropane, which is recirculated to step (i), and a liquid phase fraction including the residue of the hydrofluoropropane; (iii) dehydrofluorinating hydrofluoropropane from the liquid fraction of step (ii) using potassium hydroxide in an aqueous reaction medium contained in an agitated reactor so as to produce the fluoropropene of formula (I); and (iv) purifying the fluoropropene obtained in step (iii).

The hydrodefluorination (HDF) of fluoroalkenes in the presence of a variety of titanium catalysts was studied with respect to scope, selectivity, and mechanism. Optimization revealed that the catalyst requires low steric bulk and high electron density; secondary silanes serve as the preferred hydride source. A broad range of substrates yield partially fluorinated alkenes, such as previously unknown (Z)-1,2-(difluorovinyl)ferrocene. Mechanistic studies indicate a titanium(III) hydride as the active species, which forms a titanium(III) fluoride by H/F exchange with the substrate. The HDF step can follow both an insertion/elimination and a σ-bond metathesis mechanism; the E/Z selectivity is controlled by the substrate. The catalysts' ineffieciency towards fluoroallenes was rationalized by studying their reactivity towards Group 6 hydride complexes. The broad application of the catalytic hydrofluorination of fluoroalkenes by the system [Cp2TiF 2]/silane is demonstrated. Isolated yields up to 79 % could be obtained for various substrates. Mechanistic studies indicate two competing reaction mechanisms. Copyright

A subject-matter of the invention is a process for the preparation of 2,3,3,3-tetrafluoro-1-propene which comprises the following stages: (i) hydrogenation of hexafluoropropylene to give 1,1,1,2,3,3-hexafluoropropane; (ii) dehydrofluorination of the 1,1,1,2,3,3-hexafluoropropane obtained in the preceding stage to give 1,2,3,3,3-pentafluoro-1-propene; (iii) hydrogenation of the 1,2,3,3,3-pentafluoro-1-propene obtained in the preceding stage to give 1,1,1,2,3-pentafluoropropane; and (iv) dehydrofluorination of the 1,1,1,2,3-pentafluoropropane obtained in the preceding stage to give 2,3,3,3-tetrafluoro-1-propene. Stages (ii) and (iv) are carried out using a water and potassium hydroxide mixture with the potassium hydroxide representing between 58 and 86% by weight of the mixture and at a temperature of between 110 and 180° C.

The invention relates to a method for selective dehydrofluorination on a mixed catalyst based on chromium and nickel on a carrier based on aluminium. The invention is used for the synthesis of 2,3,3,3-tetrafluoro-1-propene and 1,2,3,3,3-pentafluoro-1-propene.

A process for the manufacture of halogenated olefins in semi-batch mode by dehydrohalogenation of halogenated alkanes in the presence of an aqueous base such as KOH which simultaneously neutralizes the resulting hydrogen halide. During the process, aqueous base is continuously added to the haloalkane which results in better yields, lower by-product formation and safer/more controllable operation.

Described is a process for separating 1,1,1,2-tetrafluoropropane and hydrogen fluoride from a mixture comprising 1,1,1,2-tetrafluoropropane, 1,1,1,2,3-pentafluoropropane and hydrogen fluoride comprising: subjecting said 1,1,1,2-tetrafluoropropane, 1,1,1,2,3-pentafluoropropane and hydrogen fluoride mixture to a distillation step, forming a column distillate composition comprising an azeotropic or near-azeotropic composition of said 1,1,1,2-tetrafluoropropane and hydrogen fluoride, and a bottoms composition of 1,1,1,2,3-pentafluoropropane. The column distillate may optionally be made essentially free of 1,1,1,2,3-pentafluoropropane and the column bottoms composition may optionally be made essentially free of HF. Also described is a process for separating 1,1,1,2-tetrafluoropropane and hydrogen fluoride from a mixture of 1,1,1,2-tetrafluoropropane and hydrogen fluoride. Also described are azeotropic and azeotrope-like compositions comprising 1,1,1,2-tetrafluoropropane and hydrogen fluoride.

A process is disclosed for reducing the amount of monofluoroacetate. The process involves (a) contacting a hydrofluorocarbon with a reactant basic aqueous solution to produce an organic phase solution containing a hydrofluoroolefin and an aqueous phase solution containing a monofluoroacetate; and (b) heating the aqueous phase solution to an effective temperature to reduce the amount of monofluoroacetate in the aqueous phase solution, wherein fluoride concentration in the aqueous phase solution is substantially high. Another process is disclosed for reducing the amount of monofluoroacetate. The process involves (a) contacting a first batch of hydrofluorocarbon with a first batch of reactant basic aqueous solution to produce a first batch of organic phase solution containing a hydrofluoroolefin and a first batch of aqueous phase solution containing a monofluoroacetate; (b) separating the first batch of organic phase solution from the first batch of aqueous phase solution; (c) mixing a second batch of hydrofluorocarbon and a second batch of reactant basic aqueous solution with the separated first batch of organic phase solution to produce a second batch of organic phase solution containing a hydrofluoroolefin and a second batch of aqueous phase solution containing a monofluoroacetate; (d) combining the first batch of aqueous phase solution with the second batch of aqueous phase solution; and (e) heating the combined aqueous phase solutions to an effective temperature to reduce the amount of monofluoroacetate in the combined aqueous phase solutions, wherein fluoride concentration in the combined aqueous phase solutions is substantially high.

The invention relates to a gas-phase continuous method for preparing 2,3,3,3-tetrafluoro-1-propene, said method comprising the following steps: (i) hydrogenation of hexafluoropropylene to form 1,1,1,2,3,3-hexafluoropropane; (ii) dehydrofluorination of the 1,1,1,2,3,3-hexafluoropropane obtained in the previous step to 1,2,3,3,3-pentafluoropropene-1; (iii) hydrogenation of the 1,2,3,3,3-pentafluoropropene-1 obtained in the previous step to form 1,1,1,2,3-pentafluoropropane; and (iv) dehydrofluorination of the 1,1,1,2,3-pentafluoropropane obtained in the previous step to form 2,3,3,3-tetrafluoro-1-propene.

(Figure Presented) Detox: Air-stable titanocene difluoride efficiently catalyzes the chemoselective hydrodefluorination of fluoroalkenes at room temperature leading to hydrofluoroalkenes in high yields (see scheme: Cp = cyclopentadienyl). This is a rare example of the catalyzed conversion of fluoroalkenes into less-fluorinated compounds, which have a lower climatic impact, and is a potential method for breaking down toxic perfluoroalkenes.

The present invention aims to reduce an amount of by-products generated in a reaction step for obtaining fluorine-containing olefin, and thereby to obtain fluorine-containing olefin as a target substance with a higher selectivity than that in the conventional method. In a reaction step for generating fluorine-containing olefin by a dehydrohalogenation reaction from fluorine-containing halogenated propane expressed by a general formula CF3CH(2-n)XnCH(3-m)Xm (wherein n = 0, 1 or 2; m = 1, 2 or 3; and n+m ≤ 3; and X is selected from F, Cl and Br, independently), fluorochromium oxide having a fluorine content not less than 30% by weight is used as a catalyst.

Using hexafluoropropene (HFP) as a raw material, 1,1,1,2-tetrafluoropropene (HFC-1234yf) is obtained by hydrogenation, dehydrofluorination and distillation. In a series of reactions comprised of hydrogenating HFP to obtain 1,1,1,2,3,3-hexafluoropropane (HFC-236ea), dehydrofluorinating the HFC-236ea to obtain 1,1,1,2,3-pentafluoropropene (HFC-1225ye), hydrogenating the HFC-1225ye to obtain 1,1,1,2,3-pentafluoropropane (HFC-245eb), and dehydrofluorinating the HFC-245eb to obtain HFC-1234yf, the hydrogenations and the dehydrofluorinations are respectively carried out in the one step, and then distillation is carried out so that HFC-1234yf can be obtained. Alternately, HFC-1234yf can also be obtained by hydrogenating HFP to directly obtain HFC-245eb, and separating the HFC-245eb by distillation and dehydrofluorinating it. Thus, HFC-1234yf can be produced with a high selectivity.

Halogenated alkenes, especially fluorinated alkenes can be prepared from halogenated and fluorinated alkanes, respectively, by dehydrohalogenation or dehydrofluorination in the presence of a high-surface metal fluoride or oxifluoride. Preferably, trifluoroethylene, pentafluoropropene, tetrafluorobutenes or trifluorobutadiene are prepared. Aluminium fluoride is highly suitable. The metal fluoride or oxifluoride can be applied supported on a carrier.

The invention provides a process for the preparation of 1234yf comprising (a) contacting 1,1, 2,3,3, 3-hexafluoropropene (1216) with hydrogen in the presence of a hydrogenation catalyst to produce 1,1,2,3,3,3-hexafluoropropane (236ea); (b) dehydrofluorinating 236ea to produce 1,2,3,3,3-pentafluoropropene (1225ye); (c) contacting 1225ye with hydrogen in the presence of a hydrogenation catalyst to produce 1,2,3,3,3-pentafluoropropane (245eb); and (d) dehydrofluorinating (245eb) to produce (1234yf).

Disclosed is a method for producing fluorinated organic compounds, including petnafluoropropenes, which preferably comprises converting at least one compound of formula (I): [in-line-formulae]CFnXmCFaXbCH2X??(I)[/in-line-formulae]to at least one compound of formula (II) [in-line-formulae]CF3CF═CHF??(II)[/in-line-formulae]where each X is independently Cl, I or Br; n is 2 or 3; m is 0 or 1, a is 1 or 2, b is 0 or 1, m+n=3 and a+b=2.

The invention relates to a process for preparing a C3-6 hydrofluoroalkene comprising dehydrohalogenating a C3-6 hydrohalofluoroalkane in the presence of a zinc/chromia catalyst.

A process for the synthesis of fluorinated olefins of the formula CF3CF=CHX, wherein X is F or H comprising contacting hexafluoropropene with hydrogen chloride in the vapor phase, in the presence of a catalyst, at a temperature in the range from about 200 °C to about 350 °C, wherein the mole ratio of hydrogen chloride to hexafluoropropene is from about 2:1 to about 4:1, separating the 1-chloro-1,2,3,3,3-pentafluoro-1-propene, 1,1-dichloro-2,3,3,3-tetrafluoro-1-propene and hydrogen fluoride products from unreacted hexafluoropropene, and hydrogen chloride by distillation, hydrogenating either the 1-chloro-1,2,3,3,3-pentafluoro-1-propene, 1,1-dichloro-2,3,3,3-tetrafluoro-1-propene or mixture thereof over a catalyst, and dehydrochlorinating the said hydrogenation product to produce either 1225ye or 1234yf.

A process is disclosed for making CF3CF=CHF or a mixture thereof with CF2=CFCHF2. The process involves (i) contacting CH2ClCF2CF3, and optionally CH2FCF2CClF2, in a reaction zone in the presence of a catalytically effective amount of dehydrofluorination catalyst to produce CHCl=CFCF3, and, if CH2FCF2CClF2 is present, CHF=CFCClF2; (ii) contacting CHCl=CFCF3, and CHF=CFCClF2, if any, formed in (i) with hydrogen fluoride (HF) in a reaction zone, optionally in the presence of a fluorination catalyst, to produce a product mixture comprising CHF=CFCF3, and, if CHF=CFCClF2 is present, CF2=CFCHF2; and (iii) recovering CF3CF=CHF, or a mixture thereof with CF2=CFCHF2, from the product mixture formed in (ii); and optionally (iv) separating at least a portion of any CF3CF=CHF in the product mixture formed in (ii) from the CF2=CFCHF2 in the product mixture formed in (ii). Also disclosed is an azeotropic composition involving CHCl=CFCF3, CHF=CFCClF2 and HF.

A process is disclosed for making CF3CF=CHF or mixtures thereof with CF2=CFCHF2. The process involves (i) contacting CHCl2CF2CF3, and optionally CHClFCF2CClF2, in a reaction zone in the presence of a catalytically effective amount of dehydrofluorination catalyst to produce CCl2=CFCF3, and, if CHClFCF2CClF2 is present, CClF=CFCClF2; (ii) contacting CCl2=CFCF3 and CClF=CFCClF2, if any, formed in (i) with hydrogen fluoride (HF) in a reaction zone, optionally in the presence of a fluorination catalyst, to produce CClF=CFCF3, and if CClF=CFCClF2 is present, CF2=CFCClF2; (iii) contacting CClF=CFCF3 and CF2=CFCClF2, if any, formed in (ii) in a reaction zone with H2 in the presence of a catalyst comprising a catalytically effective amount of palladium supported on a support of chromium oxide, fluorinated chromium oxide, chromium fluoride, aluminum oxide, aluminum fluoride, and/or fluorinated alumina to produce a product mixture comprising CF3CF=CHF, and if CF2=CFCClF2 is present, CF2=CFCHF2; and (iv) recovering CF3CF=CHF, or a mixture thereof with CF2=CFCHF2, from the product mixture formed in (iii); and optionally (v) separating at least a portion of any CF3CF=CHF in the product mixture formed in (iii) from the CF2=CFCHF2 in the product mixture formed in (iii). Also disclosed are azeotropic compositions involving CCl2=CFCF3 and HF; involving CCl2=CFCF3, CClF=CFCClF2 and HF; involving CClF=CFCF3 and HF; involving CClF=CFCF3, CF2=CFCClF2 and HF; or involving CF2=CFCHF2 and HF.

Disclosed herein are azeotrope and near-azeotrope compositions comprising E-1,1,1,2,3-pentafluoropropene (E-HFC-1225ye) and hydrogen fluoride. The azeotrope and near-azeotrope compositions are useful in processes to produce and in processes to purify E-HFC-1225ye and/or Z-1,1,1,2,3-pentafluoropropene (Z-HFC-1225ye). Also disclosed are processes for the extractive distillation to separate E-HFC-1225ye from Z-HFC-1225ye.

The present disclosure relates to a process for separating a fluoroolefin from a mixture comprising hydrogen fluoride and fluoroolefin, comprising azeotropic distillation both with and without an entrainer. In particular are disclosed processes for separating any of HFC-1225ye, HFC-1234ze, HFC-1234yf or HFC-1243zf from HF.

The invention relates to a process for preparing a compound of formula CF3CF=CHX, CHX2CX=CX2 or a linear or branched C4-7 (hydro)fluoroalkene, wherein each X is, independently, H or F provided that in CHX2CX=CX2 at least one X is F, which process comprises dehydrohalogenating a compound of formula CF3CFYCH2X, CF3CFHCYHX, CHX2CXYCX2H, CHX2CXHCX2Y, or a linear or branched C4-7 hydro(halo)fluoroalkane, wherein each X is, independently, H or F provided that in CHX2CXYCX2H and CHX2CXHCX2Y at least one X is F, wherein Y is F, Cl, Br, or I, in the presence of a base.

A process is disclosed for making CF3CF=CHF. The process involves contacting at least one hexafluoropropane selected from the group consisting of CF3CF2CH2F and CF3CHFCHF2 with a chromium oxyfluoride catalyst in a reactor to obtain a product mixture comprising CF3CF=CHF, and recovering CF3CF=CHF from the product mixture. A process is disclosed for making CF3CH=CHF. The process involves contacting CF3CH2CHF2 with a chromium oxyfluoride catalyst in a reactor to obtain a product mixture comprising CF3CH=CHF, and recovering CF3CH=CHF from the product mixture. A process is disclosed for making CF3CF=CH2. The process involves contacting CF3CF2CH3 with a chromium oxyfluoride catalyst in a reactor to obtain a product mixture comprising CF3CF=CH2, and recovering CF3CF=CH2 from the product mixture.

A process is disclosed for making CF3CF=CHF. The process involves reacting CF3CCIFCCI2F with H2 in a reaction zone in the presence of a catalyst to produce a product mixture comprising CF3CF=CHF. The catalyst has a catalytically effective amount of palladium supported on a support selected from the group consisting of alumina, fluorided alumina, aluminum fluoride and mixtures thereof and the mole ratio of H2 to CF3CCIFCCI2F fed to the reaction zone is between about 1 :1 and about 5:1.. Also disclosed are azeotropic compositions of CF3CCIFCCI2F and HF and azeotropic composition of CF3CHFCH2F and HF.

Disclosed is a process for the co-manufacture of the hydrofluoroolefins HFC-1225ye and HFC-1234yf. The process comprises contacting a blend of 1,1 ,1, 2,3,3-hexafluoropropane and 1,1,1,2,3- pentafluoropropane at a temperature of from about 200 °C to about 500 °C with a catalyst, optionally in the presence of an inert gas. The catalyst includes, but is not limited to, aluminum fluoride; fluorided alumina; metals on aluminum fluoride; metals on fluorided alumina; oxides, fluorides, and oxyfluorides of magnesium, zinc and mixtures of magnesium and zinc and/or aluminum; lanthanum oxide and fluorided lanthanum oxide; chromium oxides, fluorided chromium oxides, and cubic chromium trifluoride; carbon, acid-washed carbon, activated carbon, three dimensional matrix carbonaceous materials; and metal compounds supported on carbon. The metal compounds are oxides, fluorides, and oxyfluorides of at least one metal selected from the group consisting of sodium, potassium, rubidium, cesium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, chromium, iron, cobalt, rhodium, nickel, copper, zinc, and mixtures thereof. The product hydrofluoroolefins are separated from unreacted hydrofluorocarbons and hydrogen fluoride. In another embodiment, the unreacted hydrofluorocarbons optionally may be recirculated back through the process.

Disclosed herein are azeotrope compositions comprising 1,2,3,3,3-pentafluoropropene and hydrogen fluoride. The azeotrope compositions are useful in processes to produce and in processes to purify 1,2,3,3,3-pentafluoropropene.

A process is disclosed for the manufacture of a pentafluoropropene of the formula: CFX═CYCF3where X is selected from H and F and where Y is F when X is H and Y is H when X is F. The process involves contacting a hexafluoropropane of the formula: CF2XCHYCF3at a temperature of from about 200° C. to 500° C. with a catalyst, optionally in the presence of an inert gas. Suitable catalysts include (1) catalysts of (a) at least one compound selected from the oxides, fluorides and oxyfluorides of magnesium, zinc and mixtures of magnesium and zinc, and optionally (b) at least one compound selected from the oxides, fluorides and oxyfluorides of aluminum; provided that the atomic ratio of aluminum to the total of magnesium and zinc in said catalyst is about 1:4, or less (e.g., 1:9), (2) lanthanum fluoride, (3) fluorided lanthanum oxide, (4) activated carbon, and (5) three-dimensional matrix carbonaceous materials.