CA2167698A1 - Process for combining chlorine-containing molecules to synthesize fluorine-containing products - Google Patents
Process for combining chlorine-containing molecules to synthesize fluorine-containing productsInfo
- Publication number
- CA2167698A1 CA2167698A1 CA 2167698 CA2167698A CA2167698A1 CA 2167698 A1 CA2167698 A1 CA 2167698A1 CA 2167698 CA2167698 CA 2167698 CA 2167698 A CA2167698 A CA 2167698A CA 2167698 A1 CA2167698 A1 CA 2167698A1
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- Canada
- Prior art keywords
- cfc
- group
- catalyst
- chosen
- fluorine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C19/00—Acyclic saturated compounds containing halogen atoms
- C07C19/01—Acyclic saturated compounds containing halogen atoms containing chlorine
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C19/00—Acyclic saturated compounds containing halogen atoms
- C07C19/08—Acyclic saturated compounds containing halogen atoms containing fluorine
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C19/00—Acyclic saturated compounds containing halogen atoms
- C07C19/08—Acyclic saturated compounds containing halogen atoms containing fluorine
- C07C19/10—Acyclic saturated compounds containing halogen atoms containing fluorine and chlorine
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C21/00—Acyclic unsaturated compounds containing halogen atoms
- C07C21/02—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds
- C07C21/18—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds containing fluorine
Abstract
Alternatives to chlorofluorocarbons are provided by the inventive process for synthesizing fluorine-containing products RCFbHc+a1Hf+d-1FeCR' which may optionally be carried out without the isolation of any intermediate in a single reactor or a series of reactors. The process comprises combining chlorine-containing reactants RCClaFbHc and R'CCldFeHf in the presence of hydrogen and at least one catalyst. R and R' are chosen from the group consisting of halogens, halogenated hydrocarbons, and hydrocarbons, and at least one of R and R' contains fluorine, a and d are integers from 1 to 3, b, c, e, and f are integers from 0 to 2, the sum of a, b, and c is 3, and the sum of d, e, and f is 3, and further treating the coupled products in the presence of an optional catalyst with hydrogen or a fluorinating agent.
Description
7 .. ~ ^ 21 ~7~9~
Process for Combining Chlorine-Containing Molecules to SynthesiZe Fluorine-Containing Products BACKGROUND OF THE INVENTION
The global effort to replace chlorofluorocarbons with alternative products has resulted in an intensive search for such_ products. Currently, chlorofluorocarbons (CFCs) are widely used for applications such as blowing agents, solvents, 10 refrigerants, propellants, cooling fluids, working fluids, and rinse agents. Unfortunately, CFCs are sufficiently stable to diffuse into the stratosphere, where they are eventually decomposed into ~eactive chlorine-containing radicals. These radicals have been 15 found to catalytically decompose the protective ozone layer.
EP 0 499 984 A1 (Daikin Industries) discloses dimerization of certain fluorine-containing ethanes by hydrogenation over a nic~el on silica catalyst.~In 20 comparative examples it is shown that a chromium on silica catalyst is not effective for the reaction.
EP 0 442 087 A1 (Bayer AG) discloses the preparation of chlorine-free fluorocarbons by gas-phase hydrogenation of unsaturated fluorocarbons over 25 a suitable catalyst.
SUMMARY OF THE INVENTION
Alternatives to chlorofluorocarbons are provided by the inventive process for synthesizing fluorine-cont~;ning products RCF~+a_lHf+t_lF~CR' which may 30 optionally be carried out without the isolation of any intermediate in a single reactor or a series of .J reactors. The process comprises combining chlorine-~; cont~i n ing reactants RCClaF~ and R'CCldFeHf in the presence of hydrogen and at least one catalyst. R and ~ 35 R' are chosen from th~e group consisting of halogens, S~
1~ A~END~ S~-~EET
halogenated hydrocarbons, and hydrocarbons, and at least one of R and R' contains fluorine, a and d are integers from 1 to 3, b, c, e, and f are integers from 5 O to 2, the sum of a, b, and c is 3, and the sum of d, e, and f is 3, and further treating the coupled products with hydrogen or a fluorinating agent.
Examples of the chlorine-containing reactants, RcclaFbHc and R~CCldFeHf, are FCl2C-CClF2, F3C-CCl3, F3C-CF2-CCl3, 10 F3C-CF2-CHC12, CF2C12, F3C-CHC12, F3C-CH2Cl. Examples of the fluorine-containing product, RcFbHc~a-lHf~d-lFecR~ are F3C-CH2-CH2-CF3, F2CH-CHF-CHF-CHF2, F3C-CF2-CH2-CH2-CF3, F3C CH2-CHF2, and F3C-CF2-CH2-CH2-CF2-CF3.
BRIEF DESCRIPTION OF THE FIGURES
Figure 1 is the gas chromatographic spectrum of the products of the synthesis of CFC-151-10 from CFC-215. The ordinant shows the total ion current from the mass spectroscopy detector and the abscissa represents the retention time of the gas chromatograph.
Figure 2 shows the mass spectroscopy fragmentation pattern for one of the products in the spectrum in Figure 1.
Figure 3 provides an interpretation of the mass spectroscopy fragmentation pattern of Figure 2 to 25 verify the intermediate product composition.
Figure 4 is the gas chromatographic spectrum of the products of the synthesis of HFC-55-10 from CFC-215~
Figure 5 is the mass fragmentation pattern for the 30 peak in Figure 4 that has been assigned to HFC-55-10.
DETAILED DESCRIPTION OF THE INVENTION
The detriments to the use of chlorofluorocarbons ca~ be abated by substituting relatively more fluorine and less chlorine into the compounds and by introducing 35 hydrogen to make the compounds more reactive at lower ~ 1 6 7 ~ 9 8~
, . .. .. .......
e 2a altitudes. Substituting fluorine for the chlorine of traditional CFC products decreases the boiling point.
It is therefore generally necessary to increase the ! 5 number of carbon atoms in the molecule to achieve the / product boiling points required by the applications.
/ The synthesis of the traditional CFC molecules such as ; dichlorodifluoromethane (CFC-12), ~ .
~E~
~ 09s/05353 pcT~s94lo8s86 ~ 1 67698 chlorotrifluoromethane (CFC-13), and trichlorofluoro-methalne (CFC-ll) are relatively easy and can be produced in concert with each other. However, synthesizing the more advanced higher carbon number hydrofluorocarbons (HFC's) greatly complicates the manufacturing process. This invention discloses an efficient method for manufacturing advanced HFC and other products such as blowing agents, solvents, refrigerants, propellants, cooling fluids, working fluids, and rinse agents.
The inventive process involves preparing the fluorine-cont~in;ng product RCFbH~.1Hf~1F,CR' by coupling two chlorine c~"~in~ng reactants, RCCl,FbHc and X'CCldF.Hf in the pre~en~e of hydrogen and a first catalyst, and further treating the coupled product~
with hydrogen or a fluorinating agent, optionally in the presence of a ~qcon~ cataly~t, to form the fluorine _G..~n~ng product. R and R' are cho~n from the group consisting of halogens, halogenated hydrocarbons, and hydrocarbons, and at least one of R
and R' contains fluorine, a and d Are integers from 1 to 31 b, c, e, and f are integers from 0 to 2, the sum of a" b, and c is 3, and the sum of d, e, and f i8 3 .
R An~ R' may have functional y,oU~L or other moieties that contAin oxygen, nitrogen, sulfur, phosphorous, iodine, bromine, or other components which are not directly involved in the coupling. These funct~onAl yLo~ or moieties may be used to enhance application properties or to mask certain reactive sites during the ~ynthesis ~.. -^~. Examples of R and R' are -CF~, -CCl2F, -CF2CF3, -F, or -Cl, chlorine- and fluorine-containing alkyl groups, chlorine- ~nd fluorine-containing aromatic compounds. There is no known upper limit to the molecular weight of the react~nts.
Process for Combining Chlorine-Containing Molecules to SynthesiZe Fluorine-Containing Products BACKGROUND OF THE INVENTION
The global effort to replace chlorofluorocarbons with alternative products has resulted in an intensive search for such_ products. Currently, chlorofluorocarbons (CFCs) are widely used for applications such as blowing agents, solvents, 10 refrigerants, propellants, cooling fluids, working fluids, and rinse agents. Unfortunately, CFCs are sufficiently stable to diffuse into the stratosphere, where they are eventually decomposed into ~eactive chlorine-containing radicals. These radicals have been 15 found to catalytically decompose the protective ozone layer.
EP 0 499 984 A1 (Daikin Industries) discloses dimerization of certain fluorine-containing ethanes by hydrogenation over a nic~el on silica catalyst.~In 20 comparative examples it is shown that a chromium on silica catalyst is not effective for the reaction.
EP 0 442 087 A1 (Bayer AG) discloses the preparation of chlorine-free fluorocarbons by gas-phase hydrogenation of unsaturated fluorocarbons over 25 a suitable catalyst.
SUMMARY OF THE INVENTION
Alternatives to chlorofluorocarbons are provided by the inventive process for synthesizing fluorine-cont~;ning products RCF~+a_lHf+t_lF~CR' which may 30 optionally be carried out without the isolation of any intermediate in a single reactor or a series of .J reactors. The process comprises combining chlorine-~; cont~i n ing reactants RCClaF~ and R'CCldFeHf in the presence of hydrogen and at least one catalyst. R and ~ 35 R' are chosen from th~e group consisting of halogens, S~
1~ A~END~ S~-~EET
halogenated hydrocarbons, and hydrocarbons, and at least one of R and R' contains fluorine, a and d are integers from 1 to 3, b, c, e, and f are integers from 5 O to 2, the sum of a, b, and c is 3, and the sum of d, e, and f is 3, and further treating the coupled products with hydrogen or a fluorinating agent.
Examples of the chlorine-containing reactants, RcclaFbHc and R~CCldFeHf, are FCl2C-CClF2, F3C-CCl3, F3C-CF2-CCl3, 10 F3C-CF2-CHC12, CF2C12, F3C-CHC12, F3C-CH2Cl. Examples of the fluorine-containing product, RcFbHc~a-lHf~d-lFecR~ are F3C-CH2-CH2-CF3, F2CH-CHF-CHF-CHF2, F3C-CF2-CH2-CH2-CF3, F3C CH2-CHF2, and F3C-CF2-CH2-CH2-CF2-CF3.
BRIEF DESCRIPTION OF THE FIGURES
Figure 1 is the gas chromatographic spectrum of the products of the synthesis of CFC-151-10 from CFC-215. The ordinant shows the total ion current from the mass spectroscopy detector and the abscissa represents the retention time of the gas chromatograph.
Figure 2 shows the mass spectroscopy fragmentation pattern for one of the products in the spectrum in Figure 1.
Figure 3 provides an interpretation of the mass spectroscopy fragmentation pattern of Figure 2 to 25 verify the intermediate product composition.
Figure 4 is the gas chromatographic spectrum of the products of the synthesis of HFC-55-10 from CFC-215~
Figure 5 is the mass fragmentation pattern for the 30 peak in Figure 4 that has been assigned to HFC-55-10.
DETAILED DESCRIPTION OF THE INVENTION
The detriments to the use of chlorofluorocarbons ca~ be abated by substituting relatively more fluorine and less chlorine into the compounds and by introducing 35 hydrogen to make the compounds more reactive at lower ~ 1 6 7 ~ 9 8~
, . .. .. .......
e 2a altitudes. Substituting fluorine for the chlorine of traditional CFC products decreases the boiling point.
It is therefore generally necessary to increase the ! 5 number of carbon atoms in the molecule to achieve the / product boiling points required by the applications.
/ The synthesis of the traditional CFC molecules such as ; dichlorodifluoromethane (CFC-12), ~ .
~E~
~ 09s/05353 pcT~s94lo8s86 ~ 1 67698 chlorotrifluoromethane (CFC-13), and trichlorofluoro-methalne (CFC-ll) are relatively easy and can be produced in concert with each other. However, synthesizing the more advanced higher carbon number hydrofluorocarbons (HFC's) greatly complicates the manufacturing process. This invention discloses an efficient method for manufacturing advanced HFC and other products such as blowing agents, solvents, refrigerants, propellants, cooling fluids, working fluids, and rinse agents.
The inventive process involves preparing the fluorine-cont~in;ng product RCFbH~.1Hf~1F,CR' by coupling two chlorine c~"~in~ng reactants, RCCl,FbHc and X'CCldF.Hf in the pre~en~e of hydrogen and a first catalyst, and further treating the coupled product~
with hydrogen or a fluorinating agent, optionally in the presence of a ~qcon~ cataly~t, to form the fluorine _G..~n~ng product. R and R' are cho~n from the group consisting of halogens, halogenated hydrocarbons, and hydrocarbons, and at least one of R
and R' contains fluorine, a and d Are integers from 1 to 31 b, c, e, and f are integers from 0 to 2, the sum of a" b, and c is 3, and the sum of d, e, and f i8 3 .
R An~ R' may have functional y,oU~L or other moieties that contAin oxygen, nitrogen, sulfur, phosphorous, iodine, bromine, or other components which are not directly involved in the coupling. These funct~onAl yLo~ or moieties may be used to enhance application properties or to mask certain reactive sites during the ~ynthesis ~.. -^~. Examples of R and R' are -CF~, -CCl2F, -CF2CF3, -F, or -Cl, chlorine- and fluorine-containing alkyl groups, chlorine- ~nd fluorine-containing aromatic compounds. There is no known upper limit to the molecular weight of the react~nts.
2 1 6:7 6 ~ 8 ~
- .. .....
The invention also contemplates a process for preparing the fluorine-containing products comprising combining the two chlorine-containing reactants in the 5 presence of hydrogen and a catalyst to form at least i one intermediate, RCFqHhCliCl~HkFlR', and subsequently treating the intermediate in the presence of an optional second catalyst with either a fluorinating agent, or with hydrogen and a catalyst to form the 10 fluorine-containing product, wherein the sum of g, h, and i is an integer from 1 to 2, the sum of j, k, and l is an integer from 1 to 2, g, h, i, ~, k, and l are integers from 0 to 1.
The catalyst used in the coupling reaction is a 15 group VIII metal and may be chosen from the group consisting of nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, iron, or cobalt. The catalyst may be dispersed on a high surface area support such as alumina, carbon, chromium oxide, 20 chromium oxyfluoride, chromium fluoride, or may be used as an unsupported high surface area metal oxide, metal fluoride, or elemental metal. The preferred catalys.
for the coupling reaction is a reduced ruthenium catalyst dispersed on a high surface area support such 25 as alumina or carbon.
- The molar ratio of hydrogen to reactant in the coupling reaction may vary from 0.5 to 10. The pressure may vary from ambient to 6895 kPa gauge (1,000 psig), and the li~uid hourly space velocity (LHSV) may t 30 vary from 0.1 to 10. The reaction may be carried out at temperatures in the range of from 20C to 500C, preferably in the range of from 100C to 250C, and most preferably in the range of from I50c to 200C.
Substantial reaction occurs to produce substantlal 35 conversion and selectivity at temperatures below 200C.
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Further treating the fluorine-cont~;n;ng product with hydrogen and an optional second catalyst will reduce the product to a hydrofluorocarbon. Treatment 5 with a fluorinating agent will `produce a hydro-fluorocarbon or perfluoroalkane. The catalyst selected for the hydrogen treatment may be the same catalyst used for the coupling reaction or may be selected from metals known to provide substantial hydrogenolysis 10 activity on high surface area supports such as alumina or carbon. The most preferred metals include group VIII metals such as platinum, cobalt, nickel, iridium, ruthenium and palladium which may be modified by promoters including but not limited to rhenium, 15 iridium, cobalt, and nickel. Alternatively, the metals may be attenuated by components including but not limited to sulfur, germanium, or tin. The hydrogenation reaction may be carried out at a liquid hourly space velocity (LHSV) in the range of from ~'.05 20 to 10, preferably in the range of from 0.2 to 1.0, a temperature in the range of from 20C to 550C, preferably 100C to 350C, and a pressure in the range of from 6.895 kPa (0 psig) to 13,78~ kPa (2000 psig), preferably 207 kPa gauge (30 psig) to 2,968 kPa gauge (300 psig).
The fluorinating agent may be chosen from the group consisting of hydrogen fluoride, uranium fluoride, elemental fluorine, or fluoride salts.
Examples of fluoride salts are potassium fluoride, 30 sodium fluoride, and cesium fluoride. The catalysts for hydrofluorination may be a chromium-based heterogeneous system, a catalyst system based on quid-phase contact with antimony pentahalide in ~. .
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`~ 7`~8: ::. ::
hydrogen fluoride, or electrofluorination in hydrogen fluoride. The hydrofluorination reaction may be carried out at a liquid hourly space velocity (LHSV) in 5 the range of from 0.05 to 5, preferably in the range of from 0.1 to 1.0, a temperature in the range of from 100C to 450C, preferably 250C to 350C, and a pressure in the range of from 6.895 kPa gauge (0 psig) to 3,447 kPa (500 psig), preferably 345 kPa gauge (50 10 psig) to 1379 kPa (200 psig). Where the fluorinating agent is elemental fluorine, however, the reaction is preferably carried out without a catalyst and at temperatures in the range of from -50C toi +100C, preferably -20C to +20C.
In addition, the acid nature of the support may be removed with a basic substance such as an alkali metal to avoid unwanted acid-catalyzed isomerizations. For example, lithium, sodium, or potassium may be added, to the alumina for either or both of the reactions.
20 ~ The novel fluorine-containing products may be synthesized by first coupling the chlorine-containing reactants in the presence of hydrogen and a catalyst to form an intermediate compound, isolating the intermediate by procedures such as distillation, 25 membranes, absorbents or other separation devices, and then treating the intermediate with hydrogen, a fluorinating agent such as elemental fluorine, or a hydrofluorinating agent such as hydrogen fluoride with an optional second catalyst to form the fluorine-30 containing product. Alternatively, the fluorine-containing product may be synthesized and further treated with hydrogen- or a fluorinating agent without isolation of an intermediate in a single reactor or a series of reactors A heat exchanger may be used with 35 the series of reactors to adjust temperature.
~..
-~ 095/05353 PCT~S94/08986 2 1 67~98 The reactions leading to the fluorine-containing products produce HCl and are therefore very exothermic. The hydrochloric acid may be neutralized, recovered as a byproduct, discarded, or converted into chlorine using the Deacon reaction for recycle or sale.
The ~xcess heat must be managed in order to control the reac1:or temperature profile. Although very high reacl:or temperatures lead to hiqh reaction rates, they also lead to loss of product selectivity. Heat dispersing t~chn;ques such as quench hydrogen, inert fluids such as nitrogen, and/or product recycle streams may be used to provide adequate thermal management.
As disc~s~^~ above, fluorine-containing products may be synthesized by combining A chlorine-containing reactant using an excess of hydrogen and asuitable catalyst to form an intermediate, then a product, or to form a product directly. An intermediate may be a saturated compound or an olefin.
An olefin may be hydrogenated to form the desired product using catalytic hydrogenation. Examples of possible syn~hec~fi ~re as follows:
Synthesis of HFC-356mff from CFC-113. HFC-356mff (1,1,1,4,4,4-hexafluorobutane) may be synthesized using CFC-113 (1,1,2-trichloro-1,2,2-tri-fluoroethane) in the presence of a catalystsufficiently acidic to cause an isomerization to CFC-113a. For example, the catalyst CrF3 may be phy~ically mixed in with a ruthenium catalyst or itself impregnated with ruthenium. The entire reaction may be carried out without the isolation of any intermediate in a~ single reactor or a series of reactors. CFC-113 rearranges to form CFC-113a and then couples to form the desired HFC-356mff.
W095/05353 PCT~S94/08986 21 67698 ~
Synthesis of HFC-356pee from CFC-113. HFC-356pee (1,1,2,3,4,4-hexafluorobutane) may be synthesized by coupling CFC-113 (1,1,2-trichloro-1,2,2-trifluoroethane) to form a four-carbon olefin (CFC-1316 lyy, F2ClCCF~CFCClF2) as was HFC-356mff above. The four-carbon olefin is hydroqenated to form the desired product using catalytic hydrogenat$on.
Synthesis of HFC-356mff from CFC-113a. HFC-356mff (1,1,1,4,4,4-hexafluorobutane) may be synthesized by coupling CFC-113a (l,l,l-trichloro-2,2,2-trifluoroethane) without isolating any intermediates in a single reactor or a series of reactors.
Synthesis of HFC-356mff from CFC-113a. HFC-356mff (1,1,1,4,4,4-hexafluorobutane) may be synthesized by coupling CFC-113a (l,l,l-trichloro-2,2,2-trifluoroethane) to form the four-carbon olefin CFC-1316mxx (F3CCCl~CClCF3). The olefin may then be hydrogenated to form HFC-356mff or may be converted to a ~?.CQn~ intermediate, HCFC-336 (F3CCHClCHClCF3). The second intermediate can then be reacted with hydrogen to produce the desired HFC-356mff product.
Synthesi~ of HFC-338 from CFC-113a. HFC-338 (1,1,1-2,3,4,4,4-octafluorobutane) may be synthes~zed by coupling CFC-113a (1,1,1-trichloro-2,2,2-trifluoroethane) to form a four-carbon olefin intermediate (CFC-1316mxx, F3CCCl~CClCF3). The intermediate may then be hydrogenated to form a ~e~on~
intermediate product (HCFC-336, F3CCHClCHClCF3) using catalytic hydrogenation and relatively mild conditions.
The second intermediate can then be reacted with HF
over a suitable catalyst such as a Cr-based heterogeneous system, a catalyst system based on liquid-phase contact with antimony pentahalide in HF, r 7 2~67~
. . .
.-,, ..- , .....
I g / or electrofluorination in HF to produce the desired HFC-338 product. H~C-356mff may also be co-produced / with HFC-338 by coupling CFC-113a and the ratio of the / 5 products can be adjusted by varying the reactor process / conditions. Co-production is expected to enhance the economics relative to the production of either product alone.
Synthesis of HFC-356mff and/or FC-31-10 from CFC-10 113a. HFC-356mff and/or FC-31-10 (perfluorobutane) may be synthesized by coupling CFC-113a to produce a substantial amount of CFC-316 (F3CCCl2CCl2CF3). CFC-316 -~ can then be electrofluorinated in HF to producejFC-31-10 or treated with hydrogen to produce HFC-356mff.
15 HFC-356mff and FC-31-1~ may be co-produced by coupling CFC-316 and the ratio of the products can be adjusted by varying the reactor process conditions.
Synthesis of HFC-346mdf from CFC-113a. HFC-346mdf (1,1,1,4,4,4-hexafluoro-2-chlorobutane) may ~e 20 synthesized by coupling CFC-113a (1,1,1-trichloro-2,2,2-trifluoroethane) to form the four-carbon olefin CFC-1316mxx (F3CCCl=CClCF3). The olefin may then be partially hydrodechlorinated to form HFC-346mdf.
Synthesis of CFC-1418 fro~ CFC-113a and CFC-215.
25 CFC-1418 (2,3-dichlorooctafluoro-2-pentene) may be synthesi~ed by reductively coupling CFC-113a and CFC-215 (CF3CF2CCl3). CFC-1418 may be further treated, e.g., hydrodechlorinated and/or fluorinated, to form other products, e.g., CFC-43-10 (1,1,1,2,2,3,4,5,5,5-30 decafluoropentane), HFC-458 (1,1,1,2,2,5,5,5-octa-fluoropentane), or FC-41-12 ~perfluoropentane).
Synthesis of CFC-1418 from CFC_113a and CFC-225.
CFC-1418 may be synth-esized by reductively coupling CFC-113a and CFC-225 (1,1-dichloro-2,2,3,3,3-_ _ -2 t ~ 7 6 9 8 I pentafluoropropane). CFC-1418 may be further treated / as discussed aboYe~
/ Synthesis of HFC-245fa from CFC-12 and CFC-113a.
/ 5 HFC-245fa (1,1,1,3,3-pentafluoropropane) may be / synthesized by coupling CFC-12 and CFC-113a to form a three-carbon olefin (CFC-1215, F3CCCl=CF2). The olefin is hydrogenated to for~ the desired product using t catalytic hydrogenation. As the reductive coupling 10 reaction of CFC-113a is ~uch faster than the reductive coupling reaction for CFC-12, a high ratio of CFC-12:CFC-113a is preferred in the charge stock to promote cross-coupling and reduce coupling of two CFC-113a molecules.
Synthesis of HFC-356mff and/or HFC-338 from CFC-123. HFC-356mff and/or HFC-338 may be synthesized by coupling CFC-123 (1,1-dichloro-2,2,2-trifluoroethane) to form a four-carbon intermediate (HCFC-336, F3CCHClCHClCF3). The intermediate is then 20 hydrodechlorinated to for~ the desired product using catalytic hydrogenation.
Synthesis of HFC-245fa from CFC-12 and CFC-123.
HFC-245fa may be synthesized by coupling CFC-123 (1,1-dichloro-2,2,2-trifluoroethane) and CFC-12 25 (dichlorodifluoromethane). This molecule is coupled to form a three-carbon olefin (HFC-1225, F3CCH=CF2). The three-carbon olefin is then hydrogenated to form the desired product using catalytic hydrogenation. As the reductive coupling reaction of CFC-123 appears to be ` 30 much faster than the reductive coupling reaction of CFC-12, a high ratio of CFC-12:CFC-123 would be preferably used in the charge stock to promote cross-coupling and reduce coupling of two CFC 123 molecules.
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2 ~ 67698 / Synthesis of HFC-356mff from HCFC-133a. HFC-356mff may be synthesized by reductively coupling HCFC-133a (1-chloro-2,2,2-trifluoroethane).
/ 5 Synthesis of HCFC-558 and HFC-578 from CFC-214.
/ HCFC-558 (ClCF2CF2CH2C~2CF2CF2Cl) and HFC-578 (HCF2CF2CH2CH2CF2CF2H) may be synthesized by coupling CFC-214 (ClCF2CF2CCl3) to form a six-carbon olefin (CFC-1518, ClCF2CF2CCl=CClCF2CF2Cl). The olefin may then be 10 hydrogenated to form the desired products using catalytic hydrogenation.
Synthesis of HFC-55-10 from CFC-215. HFC-55-10 (1,1,1,2,2,5,5,6,6,6-decafluorohexane) may be synthesized by coupling CFC-215 (CF3CF2CCl3) to form a 15 six-carbon olefin (CFC-151-10, F3CF2CCl=CClCF2CF3). The olefin is then hydrogenated to form the desired product using catalytic hydrogenation.
Synthesis of CFC-51-10 from CFC-215. CFC-51-1~
(3,3,4,4-tetrachlorodecafluorohexane) may be 20 synthesized by reductively coupling CFC-215. CFC-51-10 may then be further treated, e.g., hydrodechlorinated, to form another product, e.g., CFC-55-10.
Synthesis of HFC-55-10 from CFC-225. HFC-55-10 may be synthesized by reductively coupling CFC-225 (1,1-dichloro-2,2,3,3,3-pentafluoropropane) to form the intermediate HFC-153-10 (1,1,1,2,2,5,5,6,6,6-deca-fluoro-3-hexene). The olefin is then hydrogenated to form the desired product using catalytic hydrogenation.
Example 1 - Synthesis of HFC-356mff from CFC-113a The following data were obtained using a microreactor consisting of a syringe pump driven liquid feed system, a mass flow meter controlled hydrogen addition system, a reactor, a reactor outlet effluent 35 sampling system, and an on-line/off-line GC/MS
r 2~ 67698 analytical system. The area under the peaks in a plot of the total ion current (TIC) from the GC/MS as a .function of retention time provides an estimate of the 5 concentration of the effluent from the reactor. CFC-113a was the reactant and the catalyst used was 2%
ruthenium on carbon. The results shown in Table I
provide the product analysis. The results show a high yield to CFC 1316mxx, which is the desired four-carbon 10 intermediate. These data were obtained at 2 LHSV, 10:1 H2:CFC-113a molar ratio, and 207 kPa gauge ~30 psig) pressure as a function of temperature. It can be clearly seen that a high yield of CFC-1316mxx can be obtained. Further refinements in the process lS conditions will lead to an increasing concéntration of this product. The product CFC-1316mxx may be further subjected to catalytic hydrogenation to obtain the desired HFC-356mff.
TABLE I - Area % from GC/MS
HFC-143a1 0.34 19.71 19.83 CFC-13262 0 2.67 6.74 CFC-13163 9.15 58.22 30.22 t CFC-316 1.46 0 0 CFC-113a 88.41 0 0 CFC-123 0 5.76 3.79 lF3CCH3 2CFC-1326 (F3CClC=CHCF3) 3CFC-1316mxx (F3CClC=CClCF3) Example 2 - Synthesis of HFC-356mff in a Single Reactor from CFC-113a HFC-356mff was synthesized by loading a single reactor sequentially with io mL of a 2~ ruthenium catalyst on a carbon support and 10 mL of a 2%
palladium catalyst on a carbon support. A quantity ~r 2i67698 /of 4 mL per hour of CFC-113a (Cl3CCF3) was conducted to /this reactor along with a mole ratio of hydrogen gas to CFC-113a equal to 10Ø The reactor effluent was ~ 5 characterized by GC/MS. The data shown in Table II
/ were obtained by maintaining the inlet section of the / reactor containing the ruthenium catalyst at 225C.
The temperature of the butlet section of the reactor was varied. The data pro~ide proof-of-principle that 10 HFC-356 can be synthesized in this manner. Moreover, the primary byproduct of this reactions, F3CCH3 (HFC-143a) is a desirable third-generation refrigeration fluid.
TABLE II - Area ~ from GC/MS
356l 31.05 36.06 37.77 42.79 54.51 62.43 3462 23.3 29.86 28.35 21.67 5.74 0 143a 18.85 23.33 21.28 23.55 26.68 27.39 133a 5.87 7.35 8.02 13.06 10.18 123 4.09 5.25 3.97 0 0 lHFC-356mff 2HCFC-346 (CF3CClHCH2CF3) Example 3 - Synthesis of HFC-356mff from CFC-123 precursor to HFC-356mff was synthesi~ed from 20 CFC-123 using the microreactor of Example 1. The GC/MS
results show a high yield to the four-carbon intermediate. The data shown in Table III provide the conversion and selectivity as functions of temperature.
The reactant was CFC-123 and the catalyst was 10%
25 ruthenium on alumina. These data were obtained at 2 LHSV, 10:1 H2:CFC-l23 molar ratio, and 207 kPa gauge (30 psig) pressure as a function of temperature. It can be clearly seen that HCFC-336 (CF3CHClCHClCF3) can be produced in this manner. Further refinements in the 30 process conditions -.
- .. .....
The invention also contemplates a process for preparing the fluorine-containing products comprising combining the two chlorine-containing reactants in the 5 presence of hydrogen and a catalyst to form at least i one intermediate, RCFqHhCliCl~HkFlR', and subsequently treating the intermediate in the presence of an optional second catalyst with either a fluorinating agent, or with hydrogen and a catalyst to form the 10 fluorine-containing product, wherein the sum of g, h, and i is an integer from 1 to 2, the sum of j, k, and l is an integer from 1 to 2, g, h, i, ~, k, and l are integers from 0 to 1.
The catalyst used in the coupling reaction is a 15 group VIII metal and may be chosen from the group consisting of nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, iron, or cobalt. The catalyst may be dispersed on a high surface area support such as alumina, carbon, chromium oxide, 20 chromium oxyfluoride, chromium fluoride, or may be used as an unsupported high surface area metal oxide, metal fluoride, or elemental metal. The preferred catalys.
for the coupling reaction is a reduced ruthenium catalyst dispersed on a high surface area support such 25 as alumina or carbon.
- The molar ratio of hydrogen to reactant in the coupling reaction may vary from 0.5 to 10. The pressure may vary from ambient to 6895 kPa gauge (1,000 psig), and the li~uid hourly space velocity (LHSV) may t 30 vary from 0.1 to 10. The reaction may be carried out at temperatures in the range of from 20C to 500C, preferably in the range of from 100C to 250C, and most preferably in the range of from I50c to 200C.
Substantial reaction occurs to produce substantlal 35 conversion and selectivity at temperatures below 200C.
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~ 21676~8 : ::
. ", .-:
Further treating the fluorine-cont~;n;ng product with hydrogen and an optional second catalyst will reduce the product to a hydrofluorocarbon. Treatment 5 with a fluorinating agent will `produce a hydro-fluorocarbon or perfluoroalkane. The catalyst selected for the hydrogen treatment may be the same catalyst used for the coupling reaction or may be selected from metals known to provide substantial hydrogenolysis 10 activity on high surface area supports such as alumina or carbon. The most preferred metals include group VIII metals such as platinum, cobalt, nickel, iridium, ruthenium and palladium which may be modified by promoters including but not limited to rhenium, 15 iridium, cobalt, and nickel. Alternatively, the metals may be attenuated by components including but not limited to sulfur, germanium, or tin. The hydrogenation reaction may be carried out at a liquid hourly space velocity (LHSV) in the range of from ~'.05 20 to 10, preferably in the range of from 0.2 to 1.0, a temperature in the range of from 20C to 550C, preferably 100C to 350C, and a pressure in the range of from 6.895 kPa (0 psig) to 13,78~ kPa (2000 psig), preferably 207 kPa gauge (30 psig) to 2,968 kPa gauge (300 psig).
The fluorinating agent may be chosen from the group consisting of hydrogen fluoride, uranium fluoride, elemental fluorine, or fluoride salts.
Examples of fluoride salts are potassium fluoride, 30 sodium fluoride, and cesium fluoride. The catalysts for hydrofluorination may be a chromium-based heterogeneous system, a catalyst system based on quid-phase contact with antimony pentahalide in ~. .
A
`~ 7`~8: ::. ::
hydrogen fluoride, or electrofluorination in hydrogen fluoride. The hydrofluorination reaction may be carried out at a liquid hourly space velocity (LHSV) in 5 the range of from 0.05 to 5, preferably in the range of from 0.1 to 1.0, a temperature in the range of from 100C to 450C, preferably 250C to 350C, and a pressure in the range of from 6.895 kPa gauge (0 psig) to 3,447 kPa (500 psig), preferably 345 kPa gauge (50 10 psig) to 1379 kPa (200 psig). Where the fluorinating agent is elemental fluorine, however, the reaction is preferably carried out without a catalyst and at temperatures in the range of from -50C toi +100C, preferably -20C to +20C.
In addition, the acid nature of the support may be removed with a basic substance such as an alkali metal to avoid unwanted acid-catalyzed isomerizations. For example, lithium, sodium, or potassium may be added, to the alumina for either or both of the reactions.
20 ~ The novel fluorine-containing products may be synthesized by first coupling the chlorine-containing reactants in the presence of hydrogen and a catalyst to form an intermediate compound, isolating the intermediate by procedures such as distillation, 25 membranes, absorbents or other separation devices, and then treating the intermediate with hydrogen, a fluorinating agent such as elemental fluorine, or a hydrofluorinating agent such as hydrogen fluoride with an optional second catalyst to form the fluorine-30 containing product. Alternatively, the fluorine-containing product may be synthesized and further treated with hydrogen- or a fluorinating agent without isolation of an intermediate in a single reactor or a series of reactors A heat exchanger may be used with 35 the series of reactors to adjust temperature.
~..
-~ 095/05353 PCT~S94/08986 2 1 67~98 The reactions leading to the fluorine-containing products produce HCl and are therefore very exothermic. The hydrochloric acid may be neutralized, recovered as a byproduct, discarded, or converted into chlorine using the Deacon reaction for recycle or sale.
The ~xcess heat must be managed in order to control the reac1:or temperature profile. Although very high reacl:or temperatures lead to hiqh reaction rates, they also lead to loss of product selectivity. Heat dispersing t~chn;ques such as quench hydrogen, inert fluids such as nitrogen, and/or product recycle streams may be used to provide adequate thermal management.
As disc~s~^~ above, fluorine-containing products may be synthesized by combining A chlorine-containing reactant using an excess of hydrogen and asuitable catalyst to form an intermediate, then a product, or to form a product directly. An intermediate may be a saturated compound or an olefin.
An olefin may be hydrogenated to form the desired product using catalytic hydrogenation. Examples of possible syn~hec~fi ~re as follows:
Synthesis of HFC-356mff from CFC-113. HFC-356mff (1,1,1,4,4,4-hexafluorobutane) may be synthesized using CFC-113 (1,1,2-trichloro-1,2,2-tri-fluoroethane) in the presence of a catalystsufficiently acidic to cause an isomerization to CFC-113a. For example, the catalyst CrF3 may be phy~ically mixed in with a ruthenium catalyst or itself impregnated with ruthenium. The entire reaction may be carried out without the isolation of any intermediate in a~ single reactor or a series of reactors. CFC-113 rearranges to form CFC-113a and then couples to form the desired HFC-356mff.
W095/05353 PCT~S94/08986 21 67698 ~
Synthesis of HFC-356pee from CFC-113. HFC-356pee (1,1,2,3,4,4-hexafluorobutane) may be synthesized by coupling CFC-113 (1,1,2-trichloro-1,2,2-trifluoroethane) to form a four-carbon olefin (CFC-1316 lyy, F2ClCCF~CFCClF2) as was HFC-356mff above. The four-carbon olefin is hydroqenated to form the desired product using catalytic hydrogenat$on.
Synthesis of HFC-356mff from CFC-113a. HFC-356mff (1,1,1,4,4,4-hexafluorobutane) may be synthesized by coupling CFC-113a (l,l,l-trichloro-2,2,2-trifluoroethane) without isolating any intermediates in a single reactor or a series of reactors.
Synthesis of HFC-356mff from CFC-113a. HFC-356mff (1,1,1,4,4,4-hexafluorobutane) may be synthesized by coupling CFC-113a (l,l,l-trichloro-2,2,2-trifluoroethane) to form the four-carbon olefin CFC-1316mxx (F3CCCl~CClCF3). The olefin may then be hydrogenated to form HFC-356mff or may be converted to a ~?.CQn~ intermediate, HCFC-336 (F3CCHClCHClCF3). The second intermediate can then be reacted with hydrogen to produce the desired HFC-356mff product.
Synthesi~ of HFC-338 from CFC-113a. HFC-338 (1,1,1-2,3,4,4,4-octafluorobutane) may be synthes~zed by coupling CFC-113a (1,1,1-trichloro-2,2,2-trifluoroethane) to form a four-carbon olefin intermediate (CFC-1316mxx, F3CCCl~CClCF3). The intermediate may then be hydrogenated to form a ~e~on~
intermediate product (HCFC-336, F3CCHClCHClCF3) using catalytic hydrogenation and relatively mild conditions.
The second intermediate can then be reacted with HF
over a suitable catalyst such as a Cr-based heterogeneous system, a catalyst system based on liquid-phase contact with antimony pentahalide in HF, r 7 2~67~
. . .
.-,, ..- , .....
I g / or electrofluorination in HF to produce the desired HFC-338 product. H~C-356mff may also be co-produced / with HFC-338 by coupling CFC-113a and the ratio of the / 5 products can be adjusted by varying the reactor process / conditions. Co-production is expected to enhance the economics relative to the production of either product alone.
Synthesis of HFC-356mff and/or FC-31-10 from CFC-10 113a. HFC-356mff and/or FC-31-10 (perfluorobutane) may be synthesized by coupling CFC-113a to produce a substantial amount of CFC-316 (F3CCCl2CCl2CF3). CFC-316 -~ can then be electrofluorinated in HF to producejFC-31-10 or treated with hydrogen to produce HFC-356mff.
15 HFC-356mff and FC-31-1~ may be co-produced by coupling CFC-316 and the ratio of the products can be adjusted by varying the reactor process conditions.
Synthesis of HFC-346mdf from CFC-113a. HFC-346mdf (1,1,1,4,4,4-hexafluoro-2-chlorobutane) may ~e 20 synthesized by coupling CFC-113a (1,1,1-trichloro-2,2,2-trifluoroethane) to form the four-carbon olefin CFC-1316mxx (F3CCCl=CClCF3). The olefin may then be partially hydrodechlorinated to form HFC-346mdf.
Synthesis of CFC-1418 fro~ CFC-113a and CFC-215.
25 CFC-1418 (2,3-dichlorooctafluoro-2-pentene) may be synthesi~ed by reductively coupling CFC-113a and CFC-215 (CF3CF2CCl3). CFC-1418 may be further treated, e.g., hydrodechlorinated and/or fluorinated, to form other products, e.g., CFC-43-10 (1,1,1,2,2,3,4,5,5,5-30 decafluoropentane), HFC-458 (1,1,1,2,2,5,5,5-octa-fluoropentane), or FC-41-12 ~perfluoropentane).
Synthesis of CFC-1418 from CFC_113a and CFC-225.
CFC-1418 may be synth-esized by reductively coupling CFC-113a and CFC-225 (1,1-dichloro-2,2,3,3,3-_ _ -2 t ~ 7 6 9 8 I pentafluoropropane). CFC-1418 may be further treated / as discussed aboYe~
/ Synthesis of HFC-245fa from CFC-12 and CFC-113a.
/ 5 HFC-245fa (1,1,1,3,3-pentafluoropropane) may be / synthesized by coupling CFC-12 and CFC-113a to form a three-carbon olefin (CFC-1215, F3CCCl=CF2). The olefin is hydrogenated to for~ the desired product using t catalytic hydrogenation. As the reductive coupling 10 reaction of CFC-113a is ~uch faster than the reductive coupling reaction for CFC-12, a high ratio of CFC-12:CFC-113a is preferred in the charge stock to promote cross-coupling and reduce coupling of two CFC-113a molecules.
Synthesis of HFC-356mff and/or HFC-338 from CFC-123. HFC-356mff and/or HFC-338 may be synthesized by coupling CFC-123 (1,1-dichloro-2,2,2-trifluoroethane) to form a four-carbon intermediate (HCFC-336, F3CCHClCHClCF3). The intermediate is then 20 hydrodechlorinated to for~ the desired product using catalytic hydrogenation.
Synthesis of HFC-245fa from CFC-12 and CFC-123.
HFC-245fa may be synthesized by coupling CFC-123 (1,1-dichloro-2,2,2-trifluoroethane) and CFC-12 25 (dichlorodifluoromethane). This molecule is coupled to form a three-carbon olefin (HFC-1225, F3CCH=CF2). The three-carbon olefin is then hydrogenated to form the desired product using catalytic hydrogenation. As the reductive coupling reaction of CFC-123 appears to be ` 30 much faster than the reductive coupling reaction of CFC-12, a high ratio of CFC-12:CFC-123 would be preferably used in the charge stock to promote cross-coupling and reduce coupling of two CFC 123 molecules.
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2 ~ 67698 / Synthesis of HFC-356mff from HCFC-133a. HFC-356mff may be synthesized by reductively coupling HCFC-133a (1-chloro-2,2,2-trifluoroethane).
/ 5 Synthesis of HCFC-558 and HFC-578 from CFC-214.
/ HCFC-558 (ClCF2CF2CH2C~2CF2CF2Cl) and HFC-578 (HCF2CF2CH2CH2CF2CF2H) may be synthesized by coupling CFC-214 (ClCF2CF2CCl3) to form a six-carbon olefin (CFC-1518, ClCF2CF2CCl=CClCF2CF2Cl). The olefin may then be 10 hydrogenated to form the desired products using catalytic hydrogenation.
Synthesis of HFC-55-10 from CFC-215. HFC-55-10 (1,1,1,2,2,5,5,6,6,6-decafluorohexane) may be synthesized by coupling CFC-215 (CF3CF2CCl3) to form a 15 six-carbon olefin (CFC-151-10, F3CF2CCl=CClCF2CF3). The olefin is then hydrogenated to form the desired product using catalytic hydrogenation.
Synthesis of CFC-51-10 from CFC-215. CFC-51-1~
(3,3,4,4-tetrachlorodecafluorohexane) may be 20 synthesized by reductively coupling CFC-215. CFC-51-10 may then be further treated, e.g., hydrodechlorinated, to form another product, e.g., CFC-55-10.
Synthesis of HFC-55-10 from CFC-225. HFC-55-10 may be synthesized by reductively coupling CFC-225 (1,1-dichloro-2,2,3,3,3-pentafluoropropane) to form the intermediate HFC-153-10 (1,1,1,2,2,5,5,6,6,6-deca-fluoro-3-hexene). The olefin is then hydrogenated to form the desired product using catalytic hydrogenation.
Example 1 - Synthesis of HFC-356mff from CFC-113a The following data were obtained using a microreactor consisting of a syringe pump driven liquid feed system, a mass flow meter controlled hydrogen addition system, a reactor, a reactor outlet effluent 35 sampling system, and an on-line/off-line GC/MS
r 2~ 67698 analytical system. The area under the peaks in a plot of the total ion current (TIC) from the GC/MS as a .function of retention time provides an estimate of the 5 concentration of the effluent from the reactor. CFC-113a was the reactant and the catalyst used was 2%
ruthenium on carbon. The results shown in Table I
provide the product analysis. The results show a high yield to CFC 1316mxx, which is the desired four-carbon 10 intermediate. These data were obtained at 2 LHSV, 10:1 H2:CFC-113a molar ratio, and 207 kPa gauge ~30 psig) pressure as a function of temperature. It can be clearly seen that a high yield of CFC-1316mxx can be obtained. Further refinements in the process lS conditions will lead to an increasing concéntration of this product. The product CFC-1316mxx may be further subjected to catalytic hydrogenation to obtain the desired HFC-356mff.
TABLE I - Area % from GC/MS
HFC-143a1 0.34 19.71 19.83 CFC-13262 0 2.67 6.74 CFC-13163 9.15 58.22 30.22 t CFC-316 1.46 0 0 CFC-113a 88.41 0 0 CFC-123 0 5.76 3.79 lF3CCH3 2CFC-1326 (F3CClC=CHCF3) 3CFC-1316mxx (F3CClC=CClCF3) Example 2 - Synthesis of HFC-356mff in a Single Reactor from CFC-113a HFC-356mff was synthesized by loading a single reactor sequentially with io mL of a 2~ ruthenium catalyst on a carbon support and 10 mL of a 2%
palladium catalyst on a carbon support. A quantity ~r 2i67698 /of 4 mL per hour of CFC-113a (Cl3CCF3) was conducted to /this reactor along with a mole ratio of hydrogen gas to CFC-113a equal to 10Ø The reactor effluent was ~ 5 characterized by GC/MS. The data shown in Table II
/ were obtained by maintaining the inlet section of the / reactor containing the ruthenium catalyst at 225C.
The temperature of the butlet section of the reactor was varied. The data pro~ide proof-of-principle that 10 HFC-356 can be synthesized in this manner. Moreover, the primary byproduct of this reactions, F3CCH3 (HFC-143a) is a desirable third-generation refrigeration fluid.
TABLE II - Area ~ from GC/MS
356l 31.05 36.06 37.77 42.79 54.51 62.43 3462 23.3 29.86 28.35 21.67 5.74 0 143a 18.85 23.33 21.28 23.55 26.68 27.39 133a 5.87 7.35 8.02 13.06 10.18 123 4.09 5.25 3.97 0 0 lHFC-356mff 2HCFC-346 (CF3CClHCH2CF3) Example 3 - Synthesis of HFC-356mff from CFC-123 precursor to HFC-356mff was synthesi~ed from 20 CFC-123 using the microreactor of Example 1. The GC/MS
results show a high yield to the four-carbon intermediate. The data shown in Table III provide the conversion and selectivity as functions of temperature.
The reactant was CFC-123 and the catalyst was 10%
25 ruthenium on alumina. These data were obtained at 2 LHSV, 10:1 H2:CFC-l23 molar ratio, and 207 kPa gauge (30 psig) pressure as a function of temperature. It can be clearly seen that HCFC-336 (CF3CHClCHClCF3) can be produced in this manner. Further refinements in the 30 process conditions -.
3 PCT/US9~/08986 ~676q8 .
will lead to an increasing concentration of this product. Because the internal carbon atoms are chiral, two peaks are obtained for the products; one peak is the meso compound while the other i8 a d/l pair. This intermediate can be subjected to catalytic hydrodechlorination to obtain the desired HFC-356mff.
TABn~ III - Selectivities and Conversion HFC--13361 2.9 2.7 4.4 12.8 HCFC--336 32.2 53.2 ~7.4 7.9 Coupling 35.1 55.9 51.8 20.7 Selectivity HCFC-123 6.5 16.5 18.6 72.1 Conversion lHFC--1336 ( F3CCH=CHCF3) ~m~le 4 - SYnthesis of HFC-55-10 from CFC-~15 H~C-55-10 was synthesized ~rom CFC-215 using the microreactor of Example 1. CFC-215 was the reactant ~nd the catalyl;t was 15% ruthenium on alumina.
The data shown in Figure 1 represent the total ion ~urLel~ (TIC) from th~ GC/MS at a 197-C maximum reactor temperature. ~igure 2 shows the MS fragmentation pattern for the CF3CF2CCl~CClCF2CF3 intermediate. Both of the peaks between 12. 5 and 14 minutes have essentially the same fragmentation pattern, and have been assigned to the cis and trans isomers. Figure 3 provides an analy~is of the MS fragmentation pattern to verify the intermediate product composition. The GC/MS
results show a high yield to CFC-151-10, which is the desired four-carbon intermediate. These data were obtained at 0.1 LHSV, 10:1 H2:CFC-215 molar ratio, and - . 2 ~ 6 ;~ 6 ~ 8. - ~
2068 kPa gauge (300 psig) pressure as a function of temperature. It can be clearly seen that a high yield of CFC-151-10 can be obtained. Further refinements in 5 the process conditions will lead -to an increasing concentration of this product.
The synthesis of HFC-55-10 was demonstrated by increasing the peak reactor temperature to 269C. the catalyst provided significant hydrogenation and 10 hydrodechlorination activity at this temperature to convert the intermediate CFC-151-10 to HFC-55-10. The data shown in Figure 4 prove that we have prepared the HFC-55-10 by this technique. The mass fragm~ntation pattern in Figure 5 can be assigned to this product.
15 The peak at 8.6 minutes was identified as HFC-151-10 (CF3CF2CH=CHCF2CF3). This product can also be hydrogenated to HFC-55-10.
,_ :
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t
will lead to an increasing concentration of this product. Because the internal carbon atoms are chiral, two peaks are obtained for the products; one peak is the meso compound while the other i8 a d/l pair. This intermediate can be subjected to catalytic hydrodechlorination to obtain the desired HFC-356mff.
TABn~ III - Selectivities and Conversion HFC--13361 2.9 2.7 4.4 12.8 HCFC--336 32.2 53.2 ~7.4 7.9 Coupling 35.1 55.9 51.8 20.7 Selectivity HCFC-123 6.5 16.5 18.6 72.1 Conversion lHFC--1336 ( F3CCH=CHCF3) ~m~le 4 - SYnthesis of HFC-55-10 from CFC-~15 H~C-55-10 was synthesized ~rom CFC-215 using the microreactor of Example 1. CFC-215 was the reactant ~nd the catalyl;t was 15% ruthenium on alumina.
The data shown in Figure 1 represent the total ion ~urLel~ (TIC) from th~ GC/MS at a 197-C maximum reactor temperature. ~igure 2 shows the MS fragmentation pattern for the CF3CF2CCl~CClCF2CF3 intermediate. Both of the peaks between 12. 5 and 14 minutes have essentially the same fragmentation pattern, and have been assigned to the cis and trans isomers. Figure 3 provides an analy~is of the MS fragmentation pattern to verify the intermediate product composition. The GC/MS
results show a high yield to CFC-151-10, which is the desired four-carbon intermediate. These data were obtained at 0.1 LHSV, 10:1 H2:CFC-215 molar ratio, and - . 2 ~ 6 ;~ 6 ~ 8. - ~
2068 kPa gauge (300 psig) pressure as a function of temperature. It can be clearly seen that a high yield of CFC-151-10 can be obtained. Further refinements in 5 the process conditions will lead -to an increasing concentration of this product.
The synthesis of HFC-55-10 was demonstrated by increasing the peak reactor temperature to 269C. the catalyst provided significant hydrogenation and 10 hydrodechlorination activity at this temperature to convert the intermediate CFC-151-10 to HFC-55-10. The data shown in Figure 4 prove that we have prepared the HFC-55-10 by this technique. The mass fragm~ntation pattern in Figure 5 can be assigned to this product.
15 The peak at 8.6 minutes was identified as HFC-151-10 (CF3CF2CH=CHCF2CF3). This product can also be hydrogenated to HFC-55-10.
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Claims (8)
1. A process for preparing the fluorine-containing product RCFbHc+a-1Hf+d-1FeCR' by coupling two chlorine-containing reactants, RCClaFbHc and R'CCldFeHf, in the presence of hydrogen and a first catalyst of ruthenium optionally dispersed on a high surface area support chosen from the group consisting of alumina, carbon, chromium oxide, chromium oxyfluoride, chromium fluoride, and further treating the coupled product with hydrogen or a fluorinating agent, optionally in the presence of a second catalyst, to form the fluorine-containing product, wherein R and R' are chosen from the group consisting of halogens, halogenated hydrocarbons, and hydro-carbons, and at least one of R and R' contains fluorine, a and d are integers from 1 to 3, b, c, e, and f are integers from 0 to 2, the sum of a, b, and c is 3, and the sum of d, e, and f is 3.
2. The process of Claim 1 wherein the fluorine-containing product are chosen from the group consisting of F3C-CH2-CH2-CF3, F2CH-CHF-CHF-CHF2, HF2C-CHF-CHF-CF2H, F3C-CHCl-CH2-CF3, F3C-CF2-CF2-CF3, F3C-CCl2-CH2-CF3, F3C-CF3-CH2-CH2-CF3, F3C-CF2-CHFCHF-CF3, F3C-CF2-CF2-CF2-CF3, F3C-CH2-CHF2, F3C-CF2-CH2-CH2-CF2-CF3, ClF2C-CF2-CH2-CH2-CF2-CF2Cl, and HF2C-CF2-CH2-CH2-CF2-CF2H .
3. The process of Claim 1 wherein the chlorine-containing reactants are chosen from the group consisting of FC12C-CClF2, F3C-CC13, F3C-CF2-CCl3, F3C-CF2-CHCl2, ClCF2CF2Cl3, CF2C12, F3C-CHC12, and F3C-CH2Cl.
4. The process of Claim 1 wherein the first catalyst is reduced ruthenium catalyst dispersed on a high surface area support chosen from the group consisting of alumina and carbon.
5. The process of Claim 1 wherein the fluorinating agent is chosen from the group consisting of hydrogen fluoride, uranium fluoride, elemental fluorine, potassium fluoride, sodium fluoride, and cesium fluoride.
6. The process of Claim 1 wherein the second catalyst is chosen from the group consisting of group VIII metals chosen from the group consisting of platinum, cobalt, nickel, iridium, ruthenium and palladium, optionally modified by a promoter chosen from the group consisting of rhenium, iridium, cobalt, and nickel, and optionally modified by an attenuator chosen from the group consisting of sulfur, germanium, or tin.
7. The process of Claim 1 wherein R and R' are chosen from the group consisting of -CF3, -CCl2F, -CF2CF3, -CF2CF2CF3, -F, -Cl, chlorine-containing alkyl groups, fluorine-containing alkyl groups, chlorine-containing aromatic compounds, and fluorinecontaining aromatic compounds.
8. The process of Claim 1 wherein the twc chlorine-containing reactants are combined in the presence of hydrogen and a catalyst .to form at least one intermediate, RCFgHhClfCljHkFlR', and wherein the intermediate is subsequently treated in the presence of an optional second catalyst with either a fluorinating agent, or with hydrogen and a catalyst to form the fluorine-containing product, wherein the sum of g, h, and i is an integer from 1 to 2, the sum of j, k, and l is an integer from 1 to 2, g, h, i, j, k, are integers from 0 to 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US10726193A | 1993-08-16 | 1993-08-16 | |
| US08/107,261 | 1993-08-16 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2167698A1 true CA2167698A1 (en) | 1995-02-23 |
Family
ID=22315741
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2167698 Abandoned CA2167698A1 (en) | 1993-08-16 | 1994-08-10 | Process for combining chlorine-containing molecules to synthesize fluorine-containing products |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0714384A1 (en) |
| JP (1) | JPH09501676A (en) |
| AU (1) | AU7559194A (en) |
| CA (1) | CA2167698A1 (en) |
| WO (1) | WO1995005353A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110590496A (en) * | 2019-09-24 | 2019-12-20 | 浙江三美化工股份有限公司 | Method for continuously synthesizing cis-1, 1,1,4,4, 4-hexafluoro-2-butene in gas phase |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3304468B2 (en) * | 1993-01-29 | 2002-07-22 | ダイキン工業株式会社 | Methods for producing 1,1,1,4,4,4-hexafluoro-2-butenes and 1,1,1,4,4,4-hexafluorobutane |
| FR2740132B1 (en) | 1995-10-23 | 1997-12-19 | Solvay | PROCESS FOR THE PREPARATION OF 1,1,1,3,3-PENTAFLUOROPROPANE |
| WO1997019751A1 (en) * | 1995-11-29 | 1997-06-05 | E.I. Du Pont De Nemours And Company | Catalysts for halogenated hydrocarbon processing, their precursors and their preparation and use |
| US5919994A (en) * | 1995-11-29 | 1999-07-06 | E. I. Du Pont De Nemours And Company | Catalytic halogenated hydrocarbon processing and ruthenium catalysts for use therein |
| WO1998054117A1 (en) * | 1997-05-28 | 1998-12-03 | Alliedsignal Inc. | Chemical compounds having two terminal trifluoromethyl groups |
| IT1307755B1 (en) * | 1999-02-05 | 2001-11-19 | Ausimont Spa | DIMERIZATION PROCESS OF (CFC-113A). |
| US7795482B2 (en) | 2007-07-03 | 2010-09-14 | E. I. Du Pont De Nemours And Company | Method of hydrodechlorination to produce dihydrofluorinated olefins |
| US8399721B2 (en) | 2008-12-22 | 2013-03-19 | E I Du Pont De Nemours And Company | Method of hydrodechlorination to produce dihydrofluorinated olefins |
| US8604257B2 (en) * | 2010-05-21 | 2013-12-10 | Honeywell International Inc. | Process for the preparation of fluorinated cis-alkene |
| CN106536462B (en) * | 2014-02-07 | 2019-10-18 | 科慕埃弗西有限公司 | It is used to prepare Z-1,1, Isosorbide-5-Nitrae, the integral method of 4,4- hexafluoro -2- butylene |
| CN107262092B (en) * | 2017-06-16 | 2021-03-09 | 巨化集团技术中心 | Catalyst for synthesizing cis-1, 1,1,4,4, 4-hexafluoro-2-butene and preparation method and application thereof |
| US11912639B2 (en) * | 2019-04-05 | 2024-02-27 | The Chemours Company Fc, Llc | Processes for producing Z-1,1,1,4,4,4-hexafluorobut-2-ene and intermediates for producing same |
| MX2022010619A (en) * | 2020-03-04 | 2022-09-21 | Chemours Co Fc Llc | Process to produce (z)-1,1,1,4,4,4-hexafluoro-2-butene and intermediates. |
| CN112745192A (en) * | 2020-12-31 | 2021-05-04 | 山东华夏神舟新材料有限公司 | Continuous preparation method of cis-hexafluoro-2-butene |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4004494A1 (en) * | 1990-02-14 | 1991-08-22 | Bayer Ag | METHOD FOR PRODUCING SATURATED, FLUORINE AND CHLORINE-FREE HYDROCARBONS |
| JP3008510B2 (en) * | 1991-02-16 | 2000-02-14 | ダイキン工業株式会社 | Method for producing dimer of fluorinated ethane |
| DE4215876A1 (en) * | 1992-05-14 | 1993-11-18 | Bayer Ag | Process for the preparation of hexafluorobutane |
| ES2099315T3 (en) * | 1992-05-26 | 1997-05-16 | Solvay | PROCEDURE FOR THE PREPARATION OF FLUORINE-HYDROCARBONS. |
-
1994
- 1994-08-10 WO PCT/US1994/008986 patent/WO1995005353A1/en not_active Application Discontinuation
- 1994-08-10 JP JP7507047A patent/JPH09501676A/en active Pending
- 1994-08-10 EP EP94925790A patent/EP0714384A1/en not_active Withdrawn
- 1994-08-10 CA CA 2167698 patent/CA2167698A1/en not_active Abandoned
- 1994-08-10 AU AU75591/94A patent/AU7559194A/en not_active Abandoned
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110590496A (en) * | 2019-09-24 | 2019-12-20 | 浙江三美化工股份有限公司 | Method for continuously synthesizing cis-1, 1,1,4,4, 4-hexafluoro-2-butene in gas phase |
Also Published As
| Publication number | Publication date |
|---|---|
| WO1995005353A1 (en) | 1995-02-23 |
| JPH09501676A (en) | 1997-02-18 |
| EP0714384A1 (en) | 1996-06-05 |
| AU7559194A (en) | 1995-03-14 |
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