US20060178541A1 - Conversion of fluorocarbons - Google Patents
Conversion of fluorocarbons Download PDFInfo
- Publication number
- US20060178541A1 US20060178541A1 US10/548,589 US54858905A US2006178541A1 US 20060178541 A1 US20060178541 A1 US 20060178541A1 US 54858905 A US54858905 A US 54858905A US 2006178541 A1 US2006178541 A1 US 2006178541A1
- Authority
- US
- United States
- Prior art keywords
- process according
- reaction
- fluorocarbon
- feed
- hydrocarbon
- 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.)
- Abandoned
Links
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 claims abstract description 44
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 30
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 29
- 239000000203 mixture Substances 0.000 claims abstract description 29
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 26
- 150000001875 compounds Chemical class 0.000 claims abstract description 26
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 26
- 150000007513 acids Chemical class 0.000 claims abstract description 5
- 239000002253 acid Substances 0.000 claims abstract description 4
- 238000001816 cooling Methods 0.000 claims abstract description 4
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 claims description 10
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 claims description 9
- RJCQBQGAPKAMLL-UHFFFAOYSA-N bromotrifluoromethane Chemical compound FC(F)(F)Br RJCQBQGAPKAMLL-UHFFFAOYSA-N 0.000 claims description 9
- -1 CFCl2Br Chemical compound 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- VOPWNXZWBYDODV-UHFFFAOYSA-N Chlorodifluoromethane Chemical compound FC(F)Cl VOPWNXZWBYDODV-UHFFFAOYSA-N 0.000 claims description 4
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 claims description 4
- 229910020314 ClBr Inorganic materials 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- RWRIWBAIICGTTQ-UHFFFAOYSA-N difluoromethane Chemical compound FCF RWRIWBAIICGTTQ-UHFFFAOYSA-N 0.000 claims description 3
- QYSGYZVSCZSLHT-UHFFFAOYSA-N octafluoropropane Chemical compound FC(F)(F)C(F)(F)C(F)(F)F QYSGYZVSCZSLHT-UHFFFAOYSA-N 0.000 claims description 3
- 239000012433 hydrogen halide Substances 0.000 claims description 2
- 229910000039 hydrogen halide Inorganic materials 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 14
- 239000000178 monomer Substances 0.000 abstract description 6
- 239000012707 chemical precursor Substances 0.000 abstract description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 31
- 229920004449 Halon® Polymers 0.000 description 10
- 239000007789 gas Substances 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000003345 natural gas Substances 0.000 description 6
- MEXUFEQDCXZEON-UHFFFAOYSA-N bromochlorodifluoromethane Chemical compound FC(F)(Cl)Br MEXUFEQDCXZEON-UHFFFAOYSA-N 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 235000019404 dichlorodifluoromethane Nutrition 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- WFLOTYSKFUPZQB-OWOJBTEDSA-N (e)-1,2-difluoroethene Chemical compound F\C=C\F WFLOTYSKFUPZQB-OWOJBTEDSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 239000004338 Dichlorodifluoromethane Substances 0.000 description 1
- 229910002637 Pr6O11 Inorganic materials 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000011021 bench scale process Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000005695 dehalogenation reaction Methods 0.000 description 1
- 238000006704 dehydrohalogenation reaction Methods 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- AZSZCFSOHXEJQE-UHFFFAOYSA-N dibromodifluoromethane Chemical compound FC(F)(Br)Br AZSZCFSOHXEJQE-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 239000003930 superacid Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
- C07C17/266—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions of hydrocarbons and halogenated hydrocarbons
Definitions
- the present invention relates to a process for the conversion of fluorocarbons, being organic compounds having C—F bonds—and including hydrofluorocarbons, halofluorocarbons, hydrohalofluorcarbons—and in particular to their conversion into fluorinated unsaturated compounds having economic use, such as monomers.
- Fluorocarbons have been found to have many uses, for example the use of fluorocarbons, halofluorocarbons and hydrofluorocarbons as refrigerants and propellants, halons (ie. chlorinated and/or brominated saturated fluorocarbons) as flame suppressants used in fire fighting and perfluorocarbons as foam blowing agents
- halons ie. chlorinated and/or brominated saturated fluorocarbons
- CFCs chlorofluorocarbons
- Techniques for disposal of these fluorocarbon pollutants include destructive processes such as incineration and argon plasma destruction. Such processes are expensive to run, result in incomplete destruction of the fluorocarbons and produce compounds of no particular economic value. Plasma destruction is suitable for dilute concentrations of some fluorocarbons, but not for halons in view of their flame suppressive properties.
- Other proposed disposal processes include hydrolysis, steam reforming, dehalogenation and dehydrohalogenation.
- incineration remains the most widely adopted technology for fluorocarbon disposal.
- WO 99/07443 disclosed a method of conversion of halons 1301 (CF 3 Br) and 1211 (CFCl 2 Br) by reaction with methane to produce CF 3 H, CH 3 Br and a range of minor products.
- fluorocarbons can be reacted with a hydrocarbon to produce as a major reaction product fluorinated unsaturated C 2 or higher compounds useful as chemical precursors, and especially as monomers.
- the present invention thus aims to provide a process for converting fluorocarbon pollutants—such as halons, fluorocarbons, hydrofluorocarbons, halofluorocarbons or perfluorocarbons—into a source of fluorinated unsaturated compounds useful in their own right or as precursors for production of other molecules, including polymers.
- fluorocarbon pollutants such as halons, fluorocarbons, hydrofluorocarbons, halofluorocarbons or perfluorocarbons
- the present invention provides a process for production of fluorinated C 2 or higher unsaturated compounds from reaction of a hydrocarbon with a fluorocarbon feed, including the steps of:
- the invention further includes the steps of
- step (f) recycling at least a portion of the remainder of said reaction product mixture from step (e) to said reactor.
- fluorocarbon refers to organic compounds having C—F bonds, including hydrofluorocarbons, halofluorocarbons, hydrohalofluorcarbons.
- Suitable fluorocarbons for conversion according to the invention include CCl 2 F 2 , CFCl 2 Br, CF 3 Br, CF 3 H, CHClF 2 , C 4 F 10 , CH 2 F 2 , CF 3 H, C 3 F 8 and C 3 F 8 O.
- the fluorocarbon feed includes a halofluorocarbon selected from CF 3 Br, CF 2 ClBr or CCl 2 F 2 .
- Preferred fluorinated unsaturated C 2 or higher reaction compounds are those adapted for use as monomers, such as CF 2 CFH, C 2 H 3 F and C 2 H 2 F 2 , most preferably C 2 H 2 F 2 .
- the fluorocarbon is at least 30% concentrated, more preferably at least 50% concentrated and most preferably 90% or higher concentrated.
- the reaction is conducted at a temperature of about 950-1300K, more preferably about 1050-1200K, and most preferably from 1050-1150K.
- FIG. 1 is a process flow diagram according to first preferred embodiment of the invention
- FIG. 2 is a process flow diagram of a second embodiment
- FIG. 3 is a graph of Selectivity against Temperature for Example 1
- FIG. 4 is a graph of Conversion against Temperature for Example 1.
- FIG. 5 is a graph of Yield against Temperature for Example 1.
- a fluorocarbon feed 10 which, as previously described, may include halofluorocarbons or hydrofluorocarbons—is fed via a decanting manifold 12 , feed buffer tank 14 and fluorocarbon feed compressor 16 to a reaction feed pre-heater 18 .
- the hydrocarbon feed 20 which may be a single hydrocarbon such methane, ethane or propane, or a mixed hydrocarbon source such as natural gas—is optionally pre-processed by removal of CO 2 and H 2 O at 22 and fed via a hydrocarbon feed compressor 24 to the feed pre-heater 18 .
- the fluorocarbon 10 and hydrocarbon 20 feeds may be brought together prior to or at the feed pre-heater 18 , as shown in FIG. 1 , providing the temperature of the preheated mixture is kept below about 850-900K to prevent premature initiation of the reaction.
- the hydrocarbon is fed to the reactor in excess, for example at a molar ratio of hydrocarbon to fluorocarbon of less than about 2:1, more preferably less than about 1.5:1.
- Reactor 26 may be a gas phase or a catalytic reactor, heated by electric heating elements or similar to sustain a reaction temperature sufficient to initiate reaction of the fluorocarbon and hydrocarbon feed mixture but insufficient to cause instant polymerisation of the fluorinated unsaturated reaction product.
- the optimum reaction temperature will depend on the particular fluorocarbon and hydrocarbon being reacted, and the reactor residence time.
- a suitable reaction temperature will be about 1050-1100K, whereas for chlorofluorocarbons slightly higher temperatures, such as about 1100-1150K, will be suitable to optimise the balance between conversion of the fluorocarbon to unsaturated fluorinated product against uncontrolled polymerisation of the product.
- a generic reaction mechanism is: C a H b hydrocarbon ⁇ C a H b-x +x H C c F m Y n ⁇ C c F (m-1,2,or 3) +n Y+( m ⁇ 1,2,or 3)F C a H b-x +C c F (m-1,2,or 3) ⁇ C a+c H b-x F (m-1,2,or 3) +n HY+( m ⁇ 1,2,or 3)HF
- Each reaction step may be gas phase or catalytic, or a combination thereof.
- Suitable gas phase reactors 26 include plug flow reactors, such as an alumina tubular plug flow reactor having a relatively low volume compared to the flow rate of reaction gases, so that residence time of the fluorocarbon feed at reaction temperature is short.
- plug flow reactors such as an alumina tubular plug flow reactor having a relatively low volume compared to the flow rate of reaction gases, so that residence time of the fluorocarbon feed at reaction temperature is short.
- a reactor volume of about 1 cm with a fluorocarbon feed flow of 10 cm 3 /s will give a residence time of about 100 ms.
- Preferred residence times range from about 0.01 s to 0.5 s, more preferably about 0.02-0.15 s, and most preferably under about 0.1 s, based on the fluorocarbon feed rate.
- the optimal residence time will depend on the temperature and the particular reaction, so that the use of temperatures at the lower end of the preferred range will require higher residence time. The use of higher temperatures and shorter residence times is preferred, as this will assist in maximising the yield of C 2 H 2 F 2 or other unsaturated fluorinated compound as the major component of the reaction product mixture.
- Suitable catalyst systems for catalytic reactors include rare earth oxides (eg. Sm 2 O 3 , La 2 O 3 , Pr 6 O 11 ), alkali earth metal oxides (eg. BaO, CaO, MgO), zeolite catalysts (eg. HZSM5), metal ion exchanged zeolites (eg, REY) and known methane activation catalysts (eg. Li/MgO, PbO). It is also expected that super acid catalysts (eg. ZrO 2 ) and AlF 3 and other fluorinated metals will be suitable. Again, the reactor volume is small, to give a short residence time.
- rare earth oxides eg. Sm 2 O 3 , La 2 O 3 , Pr 6 O 11
- alkali earth metal oxides eg. BaO, CaO, MgO
- zeolite catalysts eg. HZSM5
- metal ion exchanged zeolites eg, REY
- the reaction product mixture 28 from the reactor 26 passes immediately to the feed pre-heater 18 , which is a heat exchanger which cools the product mixture to a point at which further reaction of the product mixture, and in particular polymerisation of the C 2 H 2 F 2 , CH 3 F or other fluorinated unsaturated components of the reaction product mixture 28 , is inhibited.
- the feed pre-heater 18 which is a heat exchanger which cools the product mixture to a point at which further reaction of the product mixture, and in particular polymerisation of the C 2 H 2 F 2 , CH 3 F or other fluorinated unsaturated components of the reaction product mixture 28 , is inhibited.
- the cooled reaction product mixture from the heat exchanger 18 passes to a series of water-cooled condensers 30 a , 30 b , to condense and separate high boiling point, oily components 35 from the mixture.
- the gaseous output 36 from the last condenser 30 b passes to a fluidised bed caustic scrubber 32 , in which the mineral acids HCl, HBr and BF are stripped from the mixture.
- the fluidised and reacting media is CaO (lime), with the scrubber operating at approximately 150° C.
- the water 33 from the condensers is passed to a water cooling circuit 34 .
- the gaseous output from the scrubber 32 may be passed through a filtration stage such as bag filter unit 37 then to a product compressor 38 , product buffer tank 40 and discharge 42 .
- FIG. 2 The process of FIG. 2 is similar to FIG. 1 , but with an additional separation step 44 for separation of the C 2 H 2 F 2 following the bag unit 37 .
- the unreacted hydrocarbon and/or other reaction products may optionally be recycled back to the reactor 26 .
- Suitable separation means may include distillation, membrane or solvent separation, a combination thereof, or other suitable methods.
- the fluorinated unsaturated compounds produced by the process are a valuable resource, useful as chemical precursors such as monomers for the production of fluorelastomers.
- difluorethylene C 2 H 2 F 2
- C 2 H 2 F 2 is a monomer which when polymerised forms a temperature and corrosion resistant fluoropolymer.
- Halon 1211 (CF 2 ClBr) of purity >99% and natural gas were mixed and passed through a 1 cm 3 gas phase, alumina plug flow reactor at a molar ratio of approximately 1:1 (feed rates of 14.0 for halon 1211 and 15.0 mmol/h methane) and temperatures of ranging between 773K and 1173K at 50K increments. The residence time was 60 ms. The reaction products were cooled and analysed.
- the experiment was repeated with a molar ratio of approximately 1:2 (feed rates of 14.1 mmol/hr for the halon 1211 and 28.0 mmol/h methane), a residence time of approximately 60 ms, and temperatures from 873K to 1173K.
- Table 1 shows the consumption rates of the feed species and formation rates for both major and minor reaction products, in mmol/hr, and the “missing carbon”—ie. the percentage of the feed carbon which is lost as non-gaseous reaction products.
- Table 2 shows the variation against temperature of the halon conversion, selectivity of C 2 H 2 F 2 (as a proportion of gaseous reaction products, excluding unreacted halon and natural gas) and C 2 H 2 F 2 yield figures for the 1:1 feed reaction, and FIGS. 3-5 show these graphically.
- Example 1 is described with reference to the thermal hydrodehalogenation of halon 1211 to form difluoroethene, it is believed that the reaction may occur by creation of CF 2 : di-radicals from the fluorocarbon and reaction of those di-radicals with the hydrocarbon moiety, and thus is applicable to conversion of a much broader range of fluorocarbons, with adjustment of optimal reaction temperature and residence times.
- the process is suitable, under generally similar reaction conditions, to conversion of other fluorocarbons, eg.
- halon 1301, and CFC-12 (dichlorodifluoromethane), CF 3 H, CHClF 2 , C 4 F 10 , CH 2 F 2 , CF 3 H, C 3 F 8 and C 3 F 8 O.
- the process may be used to produce other unsaturated fluorinated compounds of economic value, such as C 2 H 3 F.
- the word “comprising” is to be understood in its “open” sense, that is, in the sense of “including”, and thus not limited to its “closed” sense, that is the sense of “consisting only of”.
- a corresponding meaning is to be attributed to the corresponding words “comprise, comprised and comprises where they appear.
Abstract
A process is disclosed for the conversion of fluorocarbons into fluorinated unsaturated compounds useful as monomers or other chemical precursors, such as C2H2F2. The process comprises reacting a hydrocarbon feed (20) and a fluorocarbon feed (10) in a high temperature reactor (26), at sufficiently high temperature and sufficiently short resident time to form a reaction product mixture (28) having the fluorinated unsaturated compound as the major reaction product, and cooling (18) to a temperature sufficiently low to inhibit polymerisation of the unsaturated compound. The reaction product may then be processed by removal of higher molecular weight compounds (35) and acids (32) and optionally separated (44) into product components.
Description
- The present invention relates to a process for the conversion of fluorocarbons, being organic compounds having C—F bonds—and including hydrofluorocarbons, halofluorocarbons, hydrohalofluorcarbons—and in particular to their conversion into fluorinated unsaturated compounds having economic use, such as monomers.
- Fluorocarbons have been found to have many uses, for example the use of fluorocarbons, halofluorocarbons and hydrofluorocarbons as refrigerants and propellants, halons (ie. chlorinated and/or brominated saturated fluorocarbons) as flame suppressants used in fire fighting and perfluorocarbons as foam blowing agents However, many of these useful fluorinated compounds have been found to be damaging to the environment, and/or to humans. The use and production of some fluorocarbons are now restricted or banned under international treaties.
- Enormous stockpiles of halons, chlorofluorocarbons (CFCs) and other fluorocarbon pollutants exist internationally, and there is a need for techniques for their disposal.
- Techniques for disposal of these fluorocarbon pollutants include destructive processes such as incineration and argon plasma destruction. Such processes are expensive to run, result in incomplete destruction of the fluorocarbons and produce compounds of no particular economic value. Plasma destruction is suitable for dilute concentrations of some fluorocarbons, but not for halons in view of their flame suppressive properties. Other proposed disposal processes include hydrolysis, steam reforming, dehalogenation and dehydrohalogenation. However, incineration remains the most widely adopted technology for fluorocarbon disposal.
- Other processes have been proposed for conversion of fluorocarbon pollutants into compounds of economic value.
- WO 99/07443 disclosed a method of conversion of halons 1301 (CF3Br) and 1211 (CFCl2Br) by reaction with methane to produce CF3H, CH3Br and a range of minor products.
- Li, K., Kennedy, E. M., and Dlugogorski B. Z., Experimental and Computational Studies of the Pyrolysis of CBrF3, and the Reaction of CBrF3 with CH4 , Chemical Engineering Science, 55 (2000) 4067-4078, compared theoretical and experimental reaction product profiles from the hydrodehalogenation reaction of halon 1301 with methane. The primary reaction product found was CHF3, with CH3Br and C2H2F2 produced in lesser quantities. The authors used the experimental results to refine the theoretical reaction modelling for the hydrodehalogenation reaction.
- The present inventors have now discovered that, under certain process conditions, fluorocarbons can be reacted with a hydrocarbon to produce as a major reaction product fluorinated unsaturated C2 or higher compounds useful as chemical precursors, and especially as monomers.
- The present invention thus aims to provide a process for converting fluorocarbon pollutants—such as halons, fluorocarbons, hydrofluorocarbons, halofluorocarbons or perfluorocarbons—into a source of fluorinated unsaturated compounds useful in their own right or as precursors for production of other molecules, including polymers.
- In one form, the present invention provides a process for production of fluorinated C2 or higher unsaturated compounds from reaction of a hydrocarbon with a fluorocarbon feed, including the steps of:
- (a) reacting a hydrocarbon or hydrocarbon mixture with a fluorocarbon feed under non-oxidative conditions in a high temperature reactor, at sufficiently high temperature and sufficiently short residence time to form a reaction product mixture having a fluorinated unsaturated compound as the major reaction component thereof,
- (b) rapidly cooling said reaction product mixture to a temperature sufficiently low to substantially inhibit polymerisation of said fluorinated unsaturated compound.
- In one preferred form, the invention further includes the steps of
- (c) condensing higher boiling point compounds from said cooled reaction product mixture,
- (d) removing hydrogen halide acids from the reaction product mixture, optionally
- (e) separating said fluorinated unsaturated C2 or higher compound from said reaction product mixture, and optionally
- (f) recycling at least a portion of the remainder of said reaction product mixture from step (e) to said reactor.
- As used herein, the term “fluorocarbon” refers to organic compounds having C—F bonds, including hydrofluorocarbons, halofluorocarbons, hydrohalofluorcarbons.
- Suitable fluorocarbons for conversion according to the invention include CCl2F2, CFCl2Br, CF3Br, CF3H, CHClF2, C4F10, CH2F2, CF3H, C3F8 and C3F8O. Preferably, the fluorocarbon feed includes a halofluorocarbon selected from CF3Br, CF2ClBr or CCl2F2. Preferred fluorinated unsaturated C2 or higher reaction compounds are those adapted for use as monomers, such as CF2CFH, C2H3F and C2H2F2, most preferably C2H2F2.
- It is strongly preferred that the fluorocarbon is at least 30% concentrated, more preferably at least 50% concentrated and most preferably 90% or higher concentrated.
- Preferably, the reaction is conducted at a temperature of about 950-1300K, more preferably about 1050-1200K, and most preferably from 1050-1150K.
- Further preferred forms of the invention will now be described with reference to the Examples and to the accompanying drawings, in which:
-
FIG. 1 is a process flow diagram according to first preferred embodiment of the invention; -
FIG. 2 is a process flow diagram of a second embodiment; -
FIG. 3 is a graph of Selectivity against Temperature for Example 1; -
FIG. 4 is a graph of Conversion against Temperature for Example 1; and -
FIG. 5 is a graph of Yield against Temperature for Example 1; - With reference to
FIG. 1 , afluorocarbon feed 10—which, as previously described, may include halofluorocarbons or hydrofluorocarbons—is fed via adecanting manifold 12,feed buffer tank 14 andfluorocarbon feed compressor 16 to a reaction feed pre-heater 18. - The
hydrocarbon feed 20—which may be a single hydrocarbon such methane, ethane or propane, or a mixed hydrocarbon source such as natural gas—is optionally pre-processed by removal of CO2 and H2O at 22 and fed via ahydrocarbon feed compressor 24 to the feed pre-heater 18. - The
fluorocarbon 10 andhydrocarbon 20 feeds may be brought together prior to or at the feed pre-heater 18, as shown inFIG. 1 , providing the temperature of the preheated mixture is kept below about 850-900K to prevent premature initiation of the reaction. Preferably, the hydrocarbon is fed to the reactor in excess, for example at a molar ratio of hydrocarbon to fluorocarbon of less than about 2:1, more preferably less than about 1.5:1. - Reactor 26 may be a gas phase or a catalytic reactor, heated by electric heating elements or similar to sustain a reaction temperature sufficient to initiate reaction of the fluorocarbon and hydrocarbon feed mixture but insufficient to cause instant polymerisation of the fluorinated unsaturated reaction product. The optimum reaction temperature will depend on the particular fluorocarbon and hydrocarbon being reacted, and the reactor residence time.
- For halons, a suitable reaction temperature will be about 1050-1100K, whereas for chlorofluorocarbons slightly higher temperatures, such as about 1100-1150K, will be suitable to optimise the balance between conversion of the fluorocarbon to unsaturated fluorinated product against uncontrolled polymerisation of the product.
- A generic reaction mechanism is:
CaHb hydrocarbon→CaHb-x +xH
CcFmYn→CcF(m-1,2,or 3) +nY+(m−1,2,or 3)F
CaHb-x+CcF(m-1,2,or 3)→Ca+cHb-xF(m-1,2,or 3) +nHY+(m−1,2,or 3)HF -
- Where CcFmYn is any fluorocarbon containing one or more C—F bonds and Y represents any heteroatom, especially halogen(s) such as chlorine, bromine or iodine. Ca+cHb-xF(m-1,2,or 3) is an unsaturated hydrofluorocarbon.
- Each reaction step may be gas phase or catalytic, or a combination thereof.
- Suitable gas phase reactors 26 include plug flow reactors, such as an alumina tubular plug flow reactor having a relatively low volume compared to the flow rate of reaction gases, so that residence time of the fluorocarbon feed at reaction temperature is short. For example, at a bench scale, a reactor volume of about 1 cm with a fluorocarbon feed flow of 10 cm3/s will give a residence time of about 100 ms.
- Preferred residence times range from about 0.01 s to 0.5 s, more preferably about 0.02-0.15 s, and most preferably under about 0.1 s, based on the fluorocarbon feed rate. As mentioned above, the optimal residence time will depend on the temperature and the particular reaction, so that the use of temperatures at the lower end of the preferred range will require higher residence time. The use of higher temperatures and shorter residence times is preferred, as this will assist in maximising the yield of C2H2F2 or other unsaturated fluorinated compound as the major component of the reaction product mixture.
- Suitable catalyst systems for catalytic reactors include rare earth oxides (eg. Sm2O3, La2O3, Pr6O11), alkali earth metal oxides (eg. BaO, CaO, MgO), zeolite catalysts (eg. HZSM5), metal ion exchanged zeolites (eg, REY) and known methane activation catalysts (eg. Li/MgO, PbO). It is also expected that super acid catalysts (eg. ZrO2) and AlF3 and other fluorinated metals will be suitable. Again, the reactor volume is small, to give a short residence time.
- The
reaction product mixture 28 from the reactor 26 passes immediately to thefeed pre-heater 18, which is a heat exchanger which cools the product mixture to a point at which further reaction of the product mixture, and in particular polymerisation of the C2H2F2, CH3F or other fluorinated unsaturated components of thereaction product mixture 28, is inhibited. - The cooled reaction product mixture from the
heat exchanger 18 passes to a series of water-cooledcondensers oily components 35 from the mixture. - The
gaseous output 36 from thelast condenser 30 b passes to a fluidised bedcaustic scrubber 32, in which the mineral acids HCl, HBr and BF are stripped from the mixture. The fluidised and reacting media is CaO (lime), with the scrubber operating at approximately 150° C. - The
water 33 from the condensers is passed to awater cooling circuit 34. - Where the product is to be sold as a mixture, for subsequent refining and use by the customer, the gaseous output from the
scrubber 32 may be passed through a filtration stage such asbag filter unit 37 then to aproduct compressor 38,product buffer tank 40 and discharge 42. - The process of
FIG. 2 is similar toFIG. 1 , but with anadditional separation step 44 for separation of the C2H2F2 following thebag unit 37. Depending on the economics of the process, the unreacted hydrocarbon and/or other reaction products may optionally be recycled back to the reactor 26. Suitable separation means may include distillation, membrane or solvent separation, a combination thereof, or other suitable methods. - The fluorinated unsaturated compounds produced by the process are a valuable resource, useful as chemical precursors such as monomers for the production of fluorelastomers. For example, difluorethylene (C2H2F2) is a monomer which when polymerised forms a temperature and corrosion resistant fluoropolymer.
- Halon 1211 (CF2ClBr) of purity >99% and natural gas were mixed and passed through a 1 cm3 gas phase, alumina plug flow reactor at a molar ratio of approximately 1:1 (feed rates of 14.0 for halon 1211 and 15.0 mmol/h methane) and temperatures of ranging between 773K and 1173K at 50K increments. The residence time was 60 ms. The reaction products were cooled and analysed.
- The analysis of the major components of the natural gas used in this experiment was:
CH4 95.1% (88.89) C2H6 0.1% (7.59) C3H8 0.1% (0.14) C4H10 0.01% (0.21) CO2 2.5% (1.88) N2 1.4% (1.23) Argon 0.5% (0.06) - Shown in brackets is a typical natural gas composition as quoted by the gas supplier, The Australian Gas Light Company of North Sydney, Australia. It is not believed that the differences between the gas composition used and the quoted typical composition, and in particular the proportions of methane and ethane, had a substantial effect on the experimental results.
- The experiment was repeated with a molar ratio of approximately 1:2 (feed rates of 14.1 mmol/hr for the halon 1211 and 28.0 mmol/h methane), a residence time of approximately 60 ms, and temperatures from 873K to 1173K.
- Table 1 shows the consumption rates of the feed species and formation rates for both major and minor reaction products, in mmol/hr, and the “missing carbon”—ie. the percentage of the feed carbon which is lost as non-gaseous reaction products. Table 2 shows the variation against temperature of the halon conversion, selectivity of C2H2F2 (as a proportion of gaseous reaction products, excluding unreacted halon and natural gas) and C2H2F2 yield figures for the 1:1 feed reaction, and
FIGS. 3-5 show these graphically.TABLE 2 Conversion, Selectivity and Yield against Temperature Temperature (K) Conversion Selectivity Yield 773 0.025 0.028571 0.000714 823 0.058571 0.021505 0.001429 873 0.152857 0.049342 0.010714 923 0.490714 0.088372 0.054286 973 0.896429 0.208266 0.183571 1073 0.982857 0.640706 0.440714 1123 0.986429 0.699601 0.500714 1173 0.994286 0.728355 0.480714 -
TABLE 1 Thermal hydrodehalogenation of halon 1211 (CBrClF2) with natural gas) Reactant (mmol/h) Consumption Rate of Formation (mmol/h) CBrClF2:CH4 Temperature (mmol/h) Major Products Minor Products ratio (K) CBrClF2 CH4 CHClF2 CH3Br C2H2F2 CHF3 CH3Cl CCl2F2 CBr2F2 14.0:15.0 773 0.35 0.2 0.06 0.16 0.01 0.04 trace 0.05 0.02 823 0.82 0.6 0.28 0.49 0.02 0.01 0.01 0.07 0.02 873 2.14 1.66 1.25 1.36 0.15 0 0.03 0.08 0.01 923 6.87 4.72 3.78 2.8 0.76 0.01 0.08 0.1 0.02 973 12.55 8.75 3.1 3.22 2.57 0.01 0.11 0.12 0.03 1073 13.76 11.44 0.29 0.71 6.17 0.07 0.1 0.12 trace 1123 13.81 12 0.15 0.21 7.01 0.08 0.09 0.11 nd 1173 13.92 12.74 0.12 0.06 6.73 0.05 0.07 0.06 nd 14.1:28.0 873 2.09 1.7 1.53 1.66 0.19 0.04 trace 0.05 0.02 923 7 5 4.01 3.69 0.97 trace 0.01 0.07 0.02 973 12.5 9.2 3.28 4.74 3.25 nd 0.03 0.08 0.01 1023 13.84 11.3 0.71 3.51 6.1 0.01 0.08 0.11 0.02 1073 13.88 12.2 0.18 1.59 7.95 trace 0.11 0.12 0.03 1123 13.93 12.7 0.06 0.42 8.6 0.07 0.11 0.13 nd 1173 14.03 14.23 0.05 0.08 8.83 0.51 0.18 0.05 nd Reactant (mmol/h) Rate of Formation (mmol/h) “Missing CBrClF2:CH4 Temperature Minor Products Carbon” as ratio (K) C2F4 C2H3F C3H3F5 C3H2F6 C2H2ClF C2HClF2 % of Feed 14.0:15.0 773 tarce nd nd nd nd 0.01 0.7 823 0.02 nd nd nd nd 0.01 1.5 873 0.1 nd nd nd nd 0.06 1.6 923 0.47 0.01 trace 0.09 0.05 0.43 3.8 973 1.4 0.05 0.02 0.43 0.22 1.06 9.5 1073 0.25 0.38 0.26 0.92 0.15 0.21 20.9 1123 0.56 0.56 0.28 0.81 0.1 0.06 18.3 1173 0.64 0.66 0.2 0.6 0.03 0.02 26.7 14.1:28.0 873 trace nd nd nd nd 0.01 0.3 923 0.02 nd nd nd nd 0.02 5.2 973 0.1 nd nd nd nd 0.06 16 1023 0.47 0.01 trace trace trace 0.42 15.2 1073 1.4 0.05 0.02 0.43 0.22 1.06 3.2 1123 0.25 0.38 0.25 0.92 0.15 0.21 7.5 1173 trace 1.14 0.19 0.67 0.01 trace 11.5
*nd: not detected
- Referring to Tables 1 and 2 and
FIG. 4 , it can be seen that at temperatures of greater than about 1000-1050K the reaction approaches essentially 100% conversion of the halon. With reference also toFIG. 3 , above about 1050K, C2H2F2 becomes the major reaction product of the reaction with selectivity (as a percentage of gaseous reaction products, excluding unreacted halon and natural gas) exceeding 60%. However, as the reaction temperature increases further, above about 1150K, the percentage of “missing carbon” in the form of solid deposits—believed to be polymerisation products of the C2H2F2 and C2H3F—increases. - With reference to
FIG. 5 , it can be seen that the yield of C2H2F2—calculated as the selectivity multiplied by the conversion—peaks at about 50% at approximately 1100K and then begins to decline with increasing temperature as more of the product is lost to polymerisation. - It can also be seen by comparison of the 1:1 and 1:2 reaction results in Table 1 that feeding the hydrocarbon in slight excess increases the selectivity toward C2H2F2 and reduces the carbon lost as carbon deposits. It is preferred however that the molar ratio of fluorocarbon to hydrocarbon be kept less than about 1:1.5, and more preferably about 1:1.3 due to the cost of raising the excess hydrocarbon to the reaction temperature.
- While Example 1 is described with reference to the thermal hydrodehalogenation of halon 1211 to form difluoroethene, it is believed that the reaction may occur by creation of CF2: di-radicals from the fluorocarbon and reaction of those di-radicals with the hydrocarbon moiety, and thus is applicable to conversion of a much broader range of fluorocarbons, with adjustment of optimal reaction temperature and residence times. In particular, it is known that the process is suitable, under generally similar reaction conditions, to conversion of other fluorocarbons, eg. halon 1301, and CFC-12 (dichlorodifluoromethane), CF3H, CHClF2, C4F10, CH2F2, CF3H, C3F8 and C3F8O. Furthermore, the process may be used to produce other unsaturated fluorinated compounds of economic value, such as C2H3F.
- In this specification, the word “comprising” is to be understood in its “open” sense, that is, in the sense of “including”, and thus not limited to its “closed” sense, that is the sense of “consisting only of”. A corresponding meaning is to be attributed to the corresponding words “comprise, comprised and comprises where they appear.
- While particular embodiments of this invention have been described, it will be evident to those skilled in the art that the present invention may be embodied in other specific forms without departing from the essential characteristics thereof. The present embodiments and examples are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. It will further be understood that any reference herein to known prior art does not, unless the contrary indication appears, constitute an admission that such prior art is commonly known by those skilled in the art to which the invention relates.
Claims (23)
1. A process for production of fluorinated C2 or higher unsaturated compounds from reaction of a hydrocarbon with a fluorocarbon feed, including the steps of:
(a) reacting a hydrocarbon or hydrocarbon mixture with a fluorocarbon feed under non-oxidative conditions in a high temperature reactor, at sufficiently high temperature and sufficiently short residence time to form a reaction product mixture having a fluorinated unsaturated compound as the major reaction component thereof,
(b) rapidly cooling said reaction product mixture to a temperature sufficiently low to substantially inhibit polymerisation of said fluorinated unsaturated compound.
2. A process according to claim 1 , further including the step of:
(c) condensing higher boiling point compounds from said cooled reaction product mixture.
3. A process according to claim 1 , further including the step of:
(d) removing hydrogen halide acids from the reaction product mixture.
4. A process according to claim 1 , further including the step of:
(e) separating said fluorinated unsaturated C2 or higher compound from said reaction product mixture, and optionally
(f) recycling at least a portion of the remainder of said reaction product mixture from step (e) to said reactor.
5. A process according to claim 1 , wherein said fluorocarbon is selected from the group consisting of hydrofluorocarbons, halofluorocarbons and hydrohalofluorocarbons.
6. A process according to claim 1 , wherein said fluorocarbon is selected from the group consisting of CCl2F2, CFCl2Br, CF3Br, CF3H, CHClF2, C4F10, CH2F2, CF3H, C3F8 and C3F8O.
7. A process according to claim 6 wherein said fluorocarbon is selected from the group consisting of CF3Br and CF2ClBr.
8. A process according to claim 1 , wherein said fluorinated unsaturated C2 or higher reaction compound is selected from the group consisting of CF2CFH, C2H3F and C2H2F2.
9. A process according to claim 8 , wherein said fluorinated unsaturated C2 or higher reaction compound is C2H2F2.
10. A process according to claim 1 , wherein said fluorocarbon feed is at least 30% concentrated.
11. A process according to claim 10 , wherein said fluorocarbon feed is at least 50% concentrated.
12. A process according to claim 11 , wherein said fluorocarbon feed is at least 90% concentrated.
13. A process according to claim 1 , wherein said reaction is conducted at a temperature of about 950-1300K.
14. A process according to claim 13 , wherein said reaction is conducted at a temperature of about 1050-1200K.
15. A process according to claim 14 , wherein said reaction is conducted at a temperature of from 1050-1150K.
16. A process according to claim 1 , wherein said reaction residence time of said fluorocarbon feed is less than 0.5 s.
17. A process according to claim 16 , wherein said reaction residence time is from 0.01 s to 0.5 s.
18. A process according to claim 17 , wherein said reaction residence time is from 0.02-0.15 s.
19. A process according to claim 18 , wherein said reaction residence time is under about 0.1 s.
20. A process according to claim 1 , wherein said hydrocarbon is provided to said reactor in excess of an amount required to react completely with said fluorocarbon feed.
21. A process according to claim 20 , wherein a hydrocarbon to fluorocarbon molar feed ratio is less than 2 to 1.
22. A process according to claim 21 , wherein said hydrocarbon to fluorocarbon molar feed ratio is less than 1.5 to 1.
23. A process according to claim 22 , wherein said hydrocarbon to fluorocarbon molar feed ratio is about 1.3 to 1.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US12/230,177 US20090036719A1 (en) | 2003-03-12 | 2008-08-25 | Conversion of fluorocarbons |
US12/585,401 US7928272B2 (en) | 2003-03-12 | 2009-09-14 | Conversion of fluorocarbons |
US13/053,388 US8088959B2 (en) | 2003-03-12 | 2011-03-22 | Conversion of fluorocarbons |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2003100187 | 2003-03-12 | ||
AU2003100187A AU2003100187A4 (en) | 2003-03-12 | Conversion of ozone-depleting substances (ODS) to useful products | |
PCT/AU2004/000297 WO2004080937A1 (en) | 2003-03-12 | 2004-03-12 | Conversion of fluorocarbons |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US12/230,177 Continuation US20090036719A1 (en) | 2003-03-12 | 2008-08-25 | Conversion of fluorocarbons |
Publications (1)
Publication Number | Publication Date |
---|---|
US20060178541A1 true US20060178541A1 (en) | 2006-08-10 |
Family
ID=32968025
Family Applications (4)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/548,589 Abandoned US20060178541A1 (en) | 2003-03-12 | 2004-03-12 | Conversion of fluorocarbons |
US12/230,177 Abandoned US20090036719A1 (en) | 2003-03-12 | 2008-08-25 | Conversion of fluorocarbons |
US12/585,401 Expired - Fee Related US7928272B2 (en) | 2003-03-12 | 2009-09-14 | Conversion of fluorocarbons |
US13/053,388 Expired - Fee Related US8088959B2 (en) | 2003-03-12 | 2011-03-22 | Conversion of fluorocarbons |
Family Applications After (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US12/230,177 Abandoned US20090036719A1 (en) | 2003-03-12 | 2008-08-25 | Conversion of fluorocarbons |
US12/585,401 Expired - Fee Related US7928272B2 (en) | 2003-03-12 | 2009-09-14 | Conversion of fluorocarbons |
US13/053,388 Expired - Fee Related US8088959B2 (en) | 2003-03-12 | 2011-03-22 | Conversion of fluorocarbons |
Country Status (6)
Country | Link |
---|---|
US (4) | US20060178541A1 (en) |
EP (1) | EP1608609B1 (en) |
JP (1) | JP2006519787A (en) |
AT (1) | ATE533738T1 (en) |
PL (1) | PL1608609T3 (en) |
WO (1) | WO2004080937A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111217669A (en) * | 2018-11-27 | 2020-06-02 | 浙江省化工研究院有限公司 | Method for preparing vinylidene fluoride by resource conversion of trifluoromethane |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1608609B1 (en) * | 2003-03-12 | 2011-11-16 | Pacifitech Pty Limtied | Conversion of fluorocarbons |
US7135601B2 (en) | 2005-03-28 | 2006-11-14 | Honeywell International Inc. | Catalytic method for the production of fluoroalkylenes from chlorofluorohydrocarbons |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2687440A (en) * | 1952-02-08 | 1954-08-24 | Du Pont | Preparation of fluorinated organic compounds |
US3428695A (en) * | 1965-10-12 | 1969-02-18 | Pennsalt Chemicals Corp | High temperature,short contact-time pyrolysis of dichlorofluoromethane with methane |
US5382719A (en) * | 1993-02-23 | 1995-01-17 | E. I. Du Pont De Nemours And Company | Fluoroalkylated fullerene compounds |
US5386068A (en) * | 1991-10-11 | 1995-01-31 | D'elf Atochem S.A. | Stabilization of 1,1-dichloro-1-fluoroethane |
US6096932A (en) * | 1999-07-27 | 2000-08-01 | E. I. Du Pont De Nemours And Company | Fluorocarbon manufacturing process |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB979618A (en) * | 1962-09-27 | 1965-01-06 | Dow Chemical Co | Preparation of 3,3,3-trifluoropropene |
GB8724561D0 (en) | 1987-10-20 | 1987-11-25 | Ici Plc | Production process |
US6204418B1 (en) * | 1994-09-07 | 2001-03-20 | John E. Stauffer | Process for the chlornation of hydrocarbons |
AUPO845897A0 (en) * | 1997-08-07 | 1997-09-04 | University Of Newcastle Research Associates Limited, The | Conversion of chlorinated, brominated and/or iodinated fluorocarbons and hydrofluorocarbons |
EP1608609B1 (en) * | 2003-03-12 | 2011-11-16 | Pacifitech Pty Limtied | Conversion of fluorocarbons |
-
2004
- 2004-03-12 EP EP04719874A patent/EP1608609B1/en not_active Expired - Lifetime
- 2004-03-12 US US10/548,589 patent/US20060178541A1/en not_active Abandoned
- 2004-03-12 WO PCT/AU2004/000297 patent/WO2004080937A1/en active Application Filing
- 2004-03-12 AT AT04719874T patent/ATE533738T1/en active
- 2004-03-12 JP JP2006503960A patent/JP2006519787A/en active Pending
- 2004-03-12 PL PL04719874T patent/PL1608609T3/en unknown
-
2008
- 2008-08-25 US US12/230,177 patent/US20090036719A1/en not_active Abandoned
-
2009
- 2009-09-14 US US12/585,401 patent/US7928272B2/en not_active Expired - Fee Related
-
2011
- 2011-03-22 US US13/053,388 patent/US8088959B2/en not_active Expired - Fee Related
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2687440A (en) * | 1952-02-08 | 1954-08-24 | Du Pont | Preparation of fluorinated organic compounds |
US3428695A (en) * | 1965-10-12 | 1969-02-18 | Pennsalt Chemicals Corp | High temperature,short contact-time pyrolysis of dichlorofluoromethane with methane |
US5386068A (en) * | 1991-10-11 | 1995-01-31 | D'elf Atochem S.A. | Stabilization of 1,1-dichloro-1-fluoroethane |
US5382719A (en) * | 1993-02-23 | 1995-01-17 | E. I. Du Pont De Nemours And Company | Fluoroalkylated fullerene compounds |
US6096932A (en) * | 1999-07-27 | 2000-08-01 | E. I. Du Pont De Nemours And Company | Fluorocarbon manufacturing process |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111217669A (en) * | 2018-11-27 | 2020-06-02 | 浙江省化工研究院有限公司 | Method for preparing vinylidene fluoride by resource conversion of trifluoromethane |
Also Published As
Publication number | Publication date |
---|---|
EP1608609A4 (en) | 2006-09-13 |
ATE533738T1 (en) | 2011-12-15 |
WO2004080937A1 (en) | 2004-09-23 |
US7928272B2 (en) | 2011-04-19 |
US20090036719A1 (en) | 2009-02-05 |
EP1608609A1 (en) | 2005-12-28 |
PL1608609T3 (en) | 2012-09-28 |
US20110172471A1 (en) | 2011-07-14 |
US20100145110A1 (en) | 2010-06-10 |
JP2006519787A (en) | 2006-08-31 |
EP1608609B1 (en) | 2011-11-16 |
US8088959B2 (en) | 2012-01-03 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
NO173985B (en) | CHEMICAL PROCESS | |
US8513458B2 (en) | Process for production of carbonyl fluoride | |
US8088959B2 (en) | Conversion of fluorocarbons | |
CN109748775B (en) | Resource utilization method of by-product trifluoromethane in HCFC-22 production | |
JP5612581B2 (en) | Method for producing fluoroolefin compound | |
US3042727A (en) | Preparation of fluoroform | |
US9139496B2 (en) | Process for manufacturing perfluoroolefins by pyrolysis of perfluorocarbons in the presence of hydrogen | |
US3446858A (en) | Process for the manufacture of hexafluoropropene | |
Han et al. | Mechanistic study of the reaction of CHF3 with CH4 | |
JP6111068B2 (en) | Method for producing fluoroolefin compound | |
JP5274449B2 (en) | Process for producing and purifying 1,2,3,4-tetrachlorohexafluorobutane | |
AU2004220475B2 (en) | Conversion of fluorocarbons | |
AU705724B2 (en) | Methods for purifying refrigerants with aqueous solutions of bases | |
US5547653A (en) | Carbonization of halocarbons | |
JP3159043B2 (en) | Method for producing tetrafluoromethane | |
AU680706B2 (en) | Process for producing difluoromethane and 1,1,1,2-tetrafluoroethane | |
JP7209995B2 (en) | Method for producing fluorine compound | |
JPH07178313A (en) | Method of processing halon or halon-containing fluorocarbon or chlorofluorocarbon | |
EP4053093A1 (en) | Method for producing difluoroethylene | |
US3251890A (en) | Production of hexafluorobenzene | |
CA2373437A1 (en) | Production of 1,1,1,2,3,3,3-heptafluoropropane | |
RU2188814C1 (en) | Process for integrated production of fluorocarbons | |
US3211636A (en) | Preparation of monochlorofluoroalkanes | |
Uddin et al. | Process for Conversion of Surplus Halons, CFCs and Contaminated HFCs into Fluoroelastomer Precursors | |
Katalin | Comparative Study on Decomposition of CFCI3 in Thermal and Cold Plasma |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: PACIFITECH PTY LIMITED, AUSTRALIA Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:KENNEDY, ERIC MILES;DLUGOGORSKI, BOGDAN ZYGMUNT;REEL/FRAME:017707/0323 Effective date: 20050909 |
|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |