AU8614998A - Synthesis of 1,1,1,3,3-pentafluoropropane - Google Patents
Synthesis of 1,1,1,3,3-pentafluoropropane Download PDFInfo
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- AU8614998A AU8614998A AU86149/98A AU8614998A AU8614998A AU 8614998 A AU8614998 A AU 8614998A AU 86149/98 A AU86149/98 A AU 86149/98A AU 8614998 A AU8614998 A AU 8614998A AU 8614998 A AU8614998 A AU 8614998A
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- f240fa
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- titanium
- catalyst
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- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical compound FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 title claims description 5
- 230000015572 biosynthetic process Effects 0.000 title description 4
- 238000003786 synthesis reaction Methods 0.000 title description 4
- 238000000034 method Methods 0.000 claims description 23
- 239000003054 catalyst Substances 0.000 claims description 19
- 239000010936 titanium Substances 0.000 claims description 11
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- VVWFZKBKXPXGBH-UHFFFAOYSA-N 1,1,1,3,3-pentachloropropane Chemical compound ClC(Cl)CC(Cl)(Cl)Cl VVWFZKBKXPXGBH-UHFFFAOYSA-N 0.000 claims description 5
- 229940126062 Compound A Drugs 0.000 claims description 5
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- GVVUPGXFVJLPDE-UHFFFAOYSA-N 1,3,3,3-tetrachloroprop-1-ene Chemical compound ClC=CC(Cl)(Cl)Cl GVVUPGXFVJLPDE-UHFFFAOYSA-N 0.000 claims description 4
- 239000007791 liquid phase Substances 0.000 claims description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 3
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 9
- 239000000543 intermediate Substances 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 229910052787 antimony Inorganic materials 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 238000003682 fluorination reaction Methods 0.000 description 5
- 239000012429 reaction media Substances 0.000 description 5
- -1 3-chlorol1 Chemical class 0.000 description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910010066 TiC14 Inorganic materials 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- CDOOAUSHHFGWSA-OWOJBTEDSA-N (e)-1,3,3,3-tetrafluoroprop-1-ene Chemical compound F\C=C\C(F)(F)F CDOOAUSHHFGWSA-OWOJBTEDSA-N 0.000 description 1
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 1
- BBEAZDGZMVABIC-UHFFFAOYSA-N 1,1,1,3,3,3-hexachloropropane Chemical compound ClC(Cl)(Cl)CC(Cl)(Cl)Cl BBEAZDGZMVABIC-UHFFFAOYSA-N 0.000 description 1
- UMGQVBVEWTXECF-UHFFFAOYSA-N 1,1,2,3-tetrachloroprop-1-ene Chemical compound ClCC(Cl)=C(Cl)Cl UMGQVBVEWTXECF-UHFFFAOYSA-N 0.000 description 1
- XPIGFCKQOOBTLK-UHFFFAOYSA-N 1,1,3,3-tetrachloroprop-1-ene Chemical compound ClC(Cl)C=C(Cl)Cl XPIGFCKQOOBTLK-UHFFFAOYSA-N 0.000 description 1
- FRCHKSNAZZFGCA-UHFFFAOYSA-N 1,1-dichloro-1-fluoroethane Chemical compound CC(F)(Cl)Cl FRCHKSNAZZFGCA-UHFFFAOYSA-N 0.000 description 1
- NPNPZTNLOVBDOC-UHFFFAOYSA-N 1,1-difluoroethane Chemical compound CC(F)F NPNPZTNLOVBDOC-UHFFFAOYSA-N 0.000 description 1
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 description 1
- DYASWFAOCHPTRT-UHFFFAOYSA-N 1,3-dichloro-3,3-difluoroprop-1-ene Chemical compound FC(F)(Cl)C=CCl DYASWFAOCHPTRT-UHFFFAOYSA-N 0.000 description 1
- 229910016569 AlF 3 Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 150000001462 antimony Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- OMRRUNXAWXNVFW-UHFFFAOYSA-N fluoridochlorine Chemical class ClF OMRRUNXAWXNVFW-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000001145 hydrido group Chemical class *[H] 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 244000145841 kine Species 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 230000011514 reflex Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
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
- C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
- C07C17/21—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms with simultaneous increase of the number of halogen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catching Or Destruction (AREA)
- Detergent Compositions (AREA)
- Containers Having Bodies Formed In One Piece (AREA)
Description
Regumaion 32(2)
AUSTRALIA
Patents Act 1990
ORIGINAL
COMPLETE
SPECIFICATION
STANDARD
PATENT
Application Number: Lodged Invention Title: 86149/98 22 SEPTEMBER 1998 SYNTHESIS OF 1,1,1.3,3-PENTAFLUOROPROPANE The following statement is a full description of this invention, including the best method of performing it known to us
DESCRIPTION
The present invention concerns the field of fluorinated hydro.~arbofl5, and relates more particularly to the Production of 1,1,l,3,3-pentafluoropr~rae.e Because of the depletion of the ozone layer, i imitation of the production of fully halogenated chlorofluorocarbons (CFCs) was plann-zd froc '986 (Montreal protocol) and an update (Copenhagen convention in 1992) finalized the principle of phasing out theve products completely by the end of the year Research to find substitutes for these compounds was firstly focused on products containing hydr ogen atoms (HCFCs), and then on products no longer containing chlorine: hydrofluorocarbcns. Among these, there seems to be a growing interest in C 3 compounds.
1,1,1.3,3-PentafluoropDropane, known by the reference EF245fa, is safe for the ozone layer. It therefore belongs to the class of potential substitutes Ifor Csand itsCFs use has been mentioned in various patent applications, in particular as an expansion I agent for foam 5239251), as a propellant gas and cleaning solvent for-.the elec-tronics industry (DD 298419) and, lastly, as a heat-exchange fluid tT (JF 2272086).
l,l,l,3,3-Pentafl~uoropropane can be prepared in different ways, in paritP :34lar: 2 -by catalytic hydrogenation of 1,1!,3,3,3pe-z.afluoro-l-proopene (Knunyants et al., Izvesf-. Akad.
Nauk- Otdel. Kbirn. MJauk. 1960, 1412-1418; C.A. 55:349c and Kine. Katal. 1967 1290-1299; C.A. 69:3510n), -by hydrogenolysis of 1,2,2-trichioro- 1 1 3 3 3 -pentafluoroprooane (US Patent 2942036), by reacting tetrahydrofuran with cobalt trifluoricle [Burdor et al., J. Chem. Soc. C,1969, 13, 10 1739-1746) Since these processes are not industrially viable, it has recently been proposed, in Patent Applications EP 703 205 and WO 9601797, to produce 1,1rl, 3 ,J-pentafluorooropame by reacting hydrogen J ~15 fluoriLde with iilil1, 3 3 -pentachloropropane or a partially fluorinated derivative of l,l,l, 3 ,3-pentachioropropane, in the liquid phase and in the presence off a catalyst. l,1,l, 3 ,3-Pentachloropropane, used as the starting product, can be prepared with ease in a single step) by reacting carbon tetrachloride with vinyl chloride, these being two widely available industrial p products- The term "partially fluorinated derivative off 1,1,l: 3 ,3-pentachloropropane" is here intended to mean intermediate reaction compounds such as 3-chlorol1,lr13-tetrafluoropropane (-7244), 3,3-dichloro-l,l,ltrifluoropropane (F'243), l-chloro-3,3,3-trifiuoropropene (Fl233zd), lri-erclr--fluoropropane (F241,1, 1, 3 ,J-trichloro-1,1-difluoropropane (F242), 1,3,3-trichloro-3-flucropropene (F1231zd), 1,3dichloro-3,3-difluoropropene (F1232zd) and 1,3,3,3tetrafluoropropene (F1234ze).
Although these two publications generally mention that the catalyst may be selected from the metal derivatives, in particular those of the metals belonging to main groups IIIa, IVa and Va and to sub-groups IVb, Vb and VIb, they recommend preferential use of antimony derivatives and, more particularly, 1: 0 antimony pentahalides which lead to a high degree of conversion of the 1,1,1,3,3-pentachloropropane and to a Shigh selectivity with respect to 1,1,1,3,3-pentafluoropropane.
All the examples in these two publications 15 were carried out by using an antimony pentahalide (SbCls or SbFs) as catalyst. Unfortunately, the use of these catalysts is accompanied by significant corrosion phenomena, which makes it difficult to use a process of t this type industrially.
Furthermore, International Application WO 97/08117 describes a process for the two-step preparation of a fluorinated aliphatic compound from a chlorinated olefin, which employs a chlorofluoro-olefin as intermediate.
Thus, example 1 of this patent describes the preparation of F245fa from 1,1,3,3-tetrachloro-lpropene, also referred to as F1230za, necessarily proceeding via l-chloro-3,3,3-trifluoropropene as -y
I_
intermediate. This document teaches that only the step of converting the chlorofluoro-olefin intermediate needs to be catalyzed. The catalyst envisaged for this step is a fluoride of Sb, Sn, Ti and, more particularly, a mixture of Sb(V) and Ti(IV). This process is, however, difficult to employ industrially.
Titanium-based compounds such as titanium ;tetrachloride have already been used as liquid-phase fluorination catalysts for the fluorination reaction of acetylene to form 1,1-difluoroethane (Patent US 2 830 100), that of trichloroethylene to form 1,1,2- Strichloro-1-fluoroethane (Patent US 4 383 128) or the synthesis of l-chloro-2-fluoroethane from vinyl chloride (Patent FR 1 534 403). A.E. Feiring of Fluorine Chemistry 13 (1979) 7-18) has studied the Saddition of HF to tetrachloroethylene catalyzed by TiCl 4 This titanium compound has also been used as a catalyst for the fluorination reaction of vinylidene chloride to form 1,l-dichloro-l-fluoroethane (Patent EP 378 942), that of trifluorcethylene to form 1,1,1,2tetrafluoroethane (Patent EP 574 077) or that of 1,1,1,3,3,3-hexachloropropane to form 1-chloro- S1,1,3,3,3-pentafluoropropane (Patent Application WO 95/04022). Certain synergy effects have also been demonstrated between TiC14 and SbCI 3 (Patent US V 202 509), with a nitrated solvent or a sulphone for the synthesis of 1,1-dichloro-l-fluoroethane from vinylidene chloride (Patent Application WO 94/13607) _11 4 or, recently, with SbCis for the fluorinai.ion of trichloroechylene to form FI34a Chem. So:. Chem.
Communications 1994 867).
A literature survey shows that TiCl 4 is most often used to catalyze the addition of HF to a double bond, and rarely for Cl-F exchange on a saturated substrate.
It has now unexpectedly been found that TiC14 and, more generally, titanium-based compounds are good catalysts of the fluorination reaction of 1,1,1,3,3pentachloropropane, 1,1,3,3-tetrachloro-1-propene (Fl230za) or 1,3,3,3-tetrachloro-l-propene (Fl230zd) to form 1,1,1,3,3-pentafluoropropane. They exhibit a high degree of activity without the drawbacks generated by S 15 antimony-based catalysts in terms of corrosion.
Furthermore, unlike antimony, titanium catalysts are not deactivated by reduction and practically do not lead to the by-production of Cs heavy compounds, which cannot be recycled to give the desired final product (F245fa) The invention therefore relates to a process for the production of 1,1,1,3,3-entafluoropropane (F245fa) by reacting hydrogen fluoride with a compound A selected from: 1,1,1,3,3-pentachloropropane (F240fa), a partially fluorinated derivative of F240fa, 1,1,3,3,tetrachloro-1-propene (Fl230za) or 1,3,3,3-tetrachloro- 1-propene (F1230zd) in the liquid phase, characterized in that a titanium-based compound is used as catalyst.
-230zd and za can be prepared by de-hyrcchicra itn of F240fa at a temperature of between 20 and 100CCC, in the presence of a Lewis acid such as AlF 3 ACi3, FeCl 3 TiC1 4 as catalyst. The partially fluorinated derivatives of 1,1,1,3,3-pentachloropropane can be prepared by reacting 240fa with HF in the presence of a fluorination catalyst, for example based on Sb.
As titanium-based compounds, use is preferably made of titanium halides, such as chlorides, 10 fluorides or chlorofluorides, but use may also be made of oxides or oxyhalides. Titanium tetrachLoride has proved particularly advantageous.
The process according to the invention may be carried out in a manner known per se, in batch, S 15 semi-batch or continuous mode.
In batch mode, the procedure is carried out in a stirred autoclave in which the reactants are introduced beforehand prior to the start of the reaction; the pressure in the autoclave is then the autogenous pressure and therefore changes as the reaction progresses.
When the process is carried out in a semi-batch procedure, the equipment used consists of an autoclave, on top of which is a simple condenser, or on top of which there is a return column and a reflex condenser, also equipped with a pressure-control valve.
As before, all of the reactants are introduced Sbeforehand into the autoclave, but the reaction products with low boiling point (in particular F245fa) are extracted continuously during the reaction.
When the process according to the invention is carried out in continuous mode, use is made of the same equipment in semi-batch mode, and the reactants are introduced continuously, preferably in a medium consisting of a solution of catalyst in HF.
The amount of catalyst to be employed can I vary within wide limits. It is generally between 0.0005 and 0.1 mol, preferably between 0.001 and 0.05 mol, per mole of HF. In any case, it is preferable to work with San amount of catalyst less than its solubility limit in Since the catalyst according to the invention 15 does not generate corrosion, the amount of hydrogen fluoride to be used in batch or semi-batch mode is generally between 0.5 and 50 mol per mole of F240fa and, preferably, between 2 and 20 moles. In the case of the continuous mode, it is preferable to operate by injecting the reactants into a medium consisting of HF.
The temperature for carrying out the process according to the invention may generally be between and 180 0 C. It is preferably selected between 70 and 150*C, and, more particularly, between 100 and 140 0
C.
When the procedure is carried out in semi-batch or continuous mode, the working pressure is selected so as to keep the reaction medium in the ^*O--ait^ 8 ra licuid chase. It generally lies between 5 and 50 bar and, preferably between 10 and 40 bar.
The temperature of the condenser is controlled according to the amount and nature of the products that may be discharged during the reaction. It is generally between -50 and 150 0 C and, preferably, between 0 and 1000C.
In the following example, which illustrates the invention without limiting it, the percentages S"-i 10 indicated are molar percentages.
Example 1 The procedure adopted is the semi-batch mode described above, in a stirred, 1 litre autoclave made of stainless steel 316L, containing a small sample S 15 (mass: 5g; area: 760 mm 2 made of stainless steel 316L Son top of which there is a condenser supplied with q* industrial water at 17'C. 228 g of HF (11.4 mol) and 4 11.8 g of TiCl 4 (0.062 mol) were introduced into this autoclave. The autoclave was then heated to 110°C usina an oil bath flowing in a double jacket. After the temperature of the reaction medium had stabilized, 19 g/hour of F240fa (0.09 mol/h) was supplied continuously, and some of the most volatile products were degassed continuously by means of a pressurecontrol valve set at 20 bar. After passing through a water bubbler and then a drier, these products were collected in a stainless steel trap cooled with liquid nitragen.
?v ~0 9 After 5 hours of reaction, the operation was terminated and the trapped gasses and the reaction medium were analyzed by gas chromatography. This analysis indicates that the conversion of F240fa amounts to 88% with the following selectivities: F245fa 11% F244 36% S- F243 F1233zd: 18% 10 The percentages indicated are molar i :percentages.
After separation of the F245fa, the S. unconverted F240fa and the partially fluorinated intermediates F244, F243 and F1233zd can be recycled to the reactor.
Furthermore, weighing the stainless steel 316L sample kept in the medium throughout the reaction Sdoes not demonstrate any difference in weight from its initial weight. No corrosion was therefore observed.
Example 2 The procedure was carried out using the same operating method, the same equipment and the same conditions as those described in example 1.
245g of HF (12.25 mol) and 12.5g of TiCIl (0.066mol) were introduced into the continuously supplied autoclave. After heating the reaction medium to 110'C and stabilizing the temperature, 18 g/hour of f-a F1230za (0.1 mol/h) was supplied. Some of the most volatile products were degassed continuously by means of a pressure-control valve set at 20 bar.
After passing through a water bubbler and then a drier, these products were collected in a stainless steel trap cooled with liquid nitrogen.
After 5 hours of reaction, the operation was terminated and the trapped gasses and the reaction medium were analyzed by gas chromatography. This 10 analysis indicates that the conversion of F1230za amounts to 90% with the following selectivities: F245fa 8% 2 F244 F243 S F1233zd: 39% heavy components 3% The percentages indicated are molar percentages.
After separation of the F245fa, the unconverted F1230za and the partially fluorinated intermediates F244, F243 and F1233zd can be recycled to the reactor.
Furthermore, weighing the stainless steel 316L sample kept in the medium throughout the reaction does not demonstrate any difference in weight from its initial weight. No corrosion was therefore observed.
I
Claims (7)
1. Process for the production of 1,1,1,3,3-pentafluoropropane by reacting hydrogen fluoride with a compound A selected from: 1,1,1,3,3- pentachloropropane (F240fa), a partially fluorinated derivative of F240fa, 1,1,3,3,-tetrachloro-1-propene F1230za) or 1,3,3,3-tetrachloro-l-propene (F1230zd) in the liquid phase, characterized in that a titanium- 10 based compound is used as catalyst.
2. Process according to Claim 1, in which S. the compound A is F240fa or a partially fluorinated derivative of F240fa.
3. Process according to Claim 1, in which I'1 5 the compound A is F1230za or 1,3,3,3-tetrachloro- 1-propene (F1230zd).
4. Process according to one of Claims 1 to 3, in which the titanium-based compound is a halide, an oxide or an oxyhalide of titanium, preferably titanium tetrachloride.
Process according to one of Claims 1 to 4, in which the HF/compound A molar ratio is between and 50, preferably between 2 and
6. Process according to one of Claims 1 to 5, in which the procedure is carried out at a temperature of between 30 and 180 0 C, preferably between and 150°C, and more particularly between 100 and 140*C. A' U 14 12
7. Process according to one of Claims 1 to 6, in which from 0.0005 to 0.1 mol off catalyst is used per mole of HF, preferably from 0.001 to 0.05. DATED this 22nd day of September 1998. ELF ATCC~al S.A._ wATE.jw PATENT TRADEMLARK A FIRNEYS 290 BURWCOD ROAD HA MhORN. VIC- 3122. O ert!t:f Qli: Preceding -pgo r a LineF T I
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9711794 | 1997-09-23 | ||
| FR9711794A FR2768726A1 (en) | 1997-09-23 | 1997-09-23 | Process for production of 1,1,1,3,3-penta:fluoro:propane |
| FR9801882 | 1998-02-17 | ||
| FR9801882A FR2768727A1 (en) | 1997-09-23 | 1998-02-17 | SYNTHESIS OF 1,1,1,3,3-PENTAFLUOROPROPANE |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| AU8614998A true AU8614998A (en) | 1999-04-15 |
Family
ID=26233816
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU86149/98A Abandoned AU8614998A (en) | 1997-09-23 | 1998-09-22 | Synthesis of 1,1,1,3,3-pentafluoropropane |
Country Status (11)
| Country | Link |
|---|---|
| JP (1) | JPH11158089A (en) |
| KR (1) | KR19990030026A (en) |
| CN (1) | CN1217313A (en) |
| AU (1) | AU8614998A (en) |
| BE (1) | BE1011954A3 (en) |
| CA (1) | CA2245152A1 (en) |
| DE (1) | DE19843681A1 (en) |
| FR (1) | FR2768727A1 (en) |
| GB (1) | GB2329386A (en) |
| IT (1) | IT1302243B1 (en) |
| NL (1) | NL1010169C2 (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100684939B1 (en) * | 1998-12-18 | 2007-02-22 | 솔베이(소시에떼아노님) | Method for separating a mixture comprising atleast an hydrofluoroalkane and hydrogen fluoride, methods for preparing a hydrofluoroalkane and azeotropic compositions |
| JP4617522B2 (en) * | 1999-10-01 | 2011-01-26 | 旭硝子株式会社 | Method for purifying 1,1,1,3,3-pentafluoropropane |
| US6844475B1 (en) * | 2003-08-08 | 2005-01-18 | Honeywell International Business Machines | Low temperature production of 1-chloro-3,3,3-trifluoropropene (HCFC-1233zd) |
| EP2615078A1 (en) * | 2008-11-19 | 2013-07-17 | Arkema Inc. | Process for the manufacture of hydrofluoroolefins |
| CN102216247A (en) * | 2008-11-19 | 2011-10-12 | 阿科玛股份有限公司 | Process for the manufacture of hydrochlorofluoroolefins |
| JP5477011B2 (en) * | 2009-02-03 | 2014-04-23 | セントラル硝子株式会社 | (Z) Purification method of 1-chloro-3,3,3-trifluoropropene |
| US8436217B2 (en) * | 2011-04-25 | 2013-05-07 | Honeywell International Inc. | Integrated process to co-produce 1,1,1,3,3-pentafluoropropane, trans-1-chloro-3,3,3-trifluoropropene and trans-1,3,3,3-tetrafluoropropene |
| CN102491871B (en) * | 2011-12-12 | 2013-12-18 | 南京信息工程大学 | Preparation method of heptafluoropropane |
| CN103044245B (en) * | 2012-12-12 | 2015-06-24 | 巨化集团技术中心 | Method for preparing 2-fluoropropionate |
| WO2015104517A1 (en) | 2014-01-13 | 2015-07-16 | Arkema France | Method for producing e-1-chloro-3,3,3-trifluoropropene from 1,1,3,3-tetrachloropropene |
| US9255045B2 (en) | 2014-01-13 | 2016-02-09 | Arkema France | E-1-chloro-3,3,3-trifluoropropene production process from 1,1,3,3-tetrachloropropene |
| FR3036398B1 (en) | 2015-05-22 | 2019-05-03 | Arkema France | COMPOSITIONS BASED ON 1,1,3,3-TETRACHLOROPROPENE |
| FR3081158B1 (en) | 2018-05-16 | 2020-07-31 | Arkema France | PROCESS FOR THE PRODUCTION OF 1-CHLORO-3,3,3-TRIFLUOROPROPENE. |
| FR3083232B1 (en) | 2018-06-27 | 2021-11-12 | Arkema France | 1-CHLORO-3,3,3-TRIFLUOROPROPENE PRODUCTION PROCESS |
| FR3086287B1 (en) | 2018-09-26 | 2020-09-18 | Arkema France | STABILIZATION OF 1-CHLORO-3,3,3-TRIFLUOROPROPENE |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2166971C (en) * | 1993-07-29 | 2005-09-27 | Michael Van Der Puy | Process for the preparation of 1,1,1,3,3-pentafluoropropane |
| US5395997A (en) * | 1993-07-29 | 1995-03-07 | Alliedsignal Inc. | Process for the preparation of hydrofluorocarbons having 3 to 7 carbon atoms |
| US5880317A (en) * | 1993-09-30 | 1999-03-09 | Alliedsignal Inc. | Preparation of 1,1,2,3,3-pentafluoropropane |
| FR2724928B1 (en) * | 1994-09-26 | 1996-10-31 | Atochem Elf Sa | SYNTHESIS OF 1,1,1,3,3-PENTAFLUOROPROPANE |
| US5616819A (en) * | 1995-08-28 | 1997-04-01 | Laroche Industries Inc. | Process for preparing fluorinated aliphatic compounds |
| FR2740132B1 (en) * | 1995-10-23 | 1997-12-19 | Solvay | PROCESS FOR THE PREPARATION OF 1,1,1,3,3-PENTAFLUOROPROPANE |
| US5763706A (en) * | 1996-07-03 | 1998-06-09 | Alliedsignal Inc. | Process for the manufacture of 1,1,1,3,3-pentafluoropropane and 1,1,1,3,3,3-hexafluoropropane |
| US6023004A (en) * | 1996-11-12 | 2000-02-08 | Alliedsignal, Inc. | Liquid phase catalytic fluorination of hydrochlorocarbon and hydrochlorofluorocarbon |
-
1998
- 1998-02-17 FR FR9801882A patent/FR2768727A1/en not_active Withdrawn
- 1998-09-22 CA CA 2245152 patent/CA2245152A1/en not_active Abandoned
- 1998-09-22 AU AU86149/98A patent/AU8614998A/en not_active Abandoned
- 1998-09-22 IT ITMI982041 patent/IT1302243B1/en active IP Right Grant
- 1998-09-22 JP JP26871798A patent/JPH11158089A/en active Pending
- 1998-09-22 KR KR1019980039217A patent/KR19990030026A/en not_active Application Discontinuation
- 1998-09-23 NL NL1010169A patent/NL1010169C2/en active Search and Examination
- 1998-09-23 CN CN 98124354 patent/CN1217313A/en active Pending
- 1998-09-23 GB GB9820753A patent/GB2329386A/en not_active Withdrawn
- 1998-09-23 BE BE9800682A patent/BE1011954A3/en not_active IP Right Cessation
- 1998-09-23 DE DE1998143681 patent/DE19843681A1/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| IT1302243B1 (en) | 2000-09-05 |
| GB9820753D0 (en) | 1998-11-18 |
| JPH11158089A (en) | 1999-06-15 |
| CA2245152A1 (en) | 1999-03-23 |
| KR19990030026A (en) | 1999-04-26 |
| NL1010169C2 (en) | 1999-03-25 |
| GB2329386A (en) | 1999-03-24 |
| BE1011954A3 (en) | 2000-03-07 |
| ITMI982041A1 (en) | 2000-03-22 |
| DE19843681A1 (en) | 1999-05-20 |
| FR2768727A1 (en) | 1999-03-26 |
| CN1217313A (en) | 1999-05-26 |
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