WO2003062172A2 - Integrated process for synthesizing alcohols, ethers, and olefins from alkanes - Google Patents
Integrated process for synthesizing alcohols, ethers, and olefins from alkanes Download PDFInfo
- Publication number
- WO2003062172A2 WO2003062172A2 PCT/US2002/022817 US0222817W WO03062172A2 WO 2003062172 A2 WO2003062172 A2 WO 2003062172A2 US 0222817 W US0222817 W US 0222817W WO 03062172 A2 WO03062172 A2 WO 03062172A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- bromine
- methane
- metal oxide
- bromide
- reaction
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 70
- 230000008569 process Effects 0.000 title claims description 47
- 150000001335 aliphatic alkanes Chemical class 0.000 title abstract description 45
- 150000001336 alkenes Chemical class 0.000 title abstract description 22
- 150000001298 alcohols Chemical class 0.000 title abstract description 10
- 150000002170 ethers Chemical class 0.000 title abstract description 10
- 230000002194 synthesizing effect Effects 0.000 title description 8
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 127
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 71
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims abstract description 69
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 57
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 56
- 229910000042 hydrogen bromide Inorganic materials 0.000 claims abstract description 34
- 229910001509 metal bromide Inorganic materials 0.000 claims abstract description 27
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 24
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract 22
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 128
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 90
- 238000006243 chemical reaction Methods 0.000 claims description 90
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 claims description 55
- 239000003054 catalyst Substances 0.000 claims description 32
- 239000006227 byproduct Substances 0.000 claims description 22
- DIKBFYAXUHHXCS-UHFFFAOYSA-N bromoform Chemical compound BrC(Br)Br DIKBFYAXUHHXCS-UHFFFAOYSA-N 0.000 claims description 16
- FJBFPHVGVWTDIP-UHFFFAOYSA-N dibromomethane Chemical compound BrCBr FJBFPHVGVWTDIP-UHFFFAOYSA-N 0.000 claims description 14
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 claims description 11
- 229940102396 methyl bromide Drugs 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 5
- PQLAYKMGZDUDLQ-UHFFFAOYSA-K aluminium bromide Chemical compound Br[Al](Br)Br PQLAYKMGZDUDLQ-UHFFFAOYSA-K 0.000 claims description 4
- 229910021630 Antimony pentafluoride Inorganic materials 0.000 claims description 2
- VBVBHWZYQGJZLR-UHFFFAOYSA-I antimony pentafluoride Chemical compound F[Sb](F)(F)(F)F VBVBHWZYQGJZLR-UHFFFAOYSA-I 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 20
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 9
- 150000001347 alkyl bromides Chemical class 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 description 33
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 29
- 239000000243 solution Substances 0.000 description 27
- 229910001868 water Inorganic materials 0.000 description 25
- 229910052760 oxygen Inorganic materials 0.000 description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 21
- 239000001301 oxygen Substances 0.000 description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 18
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 18
- QPLDLSVMHZLSFG-UHFFFAOYSA-N CuO Inorganic materials [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 17
- 238000003756 stirring Methods 0.000 description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 14
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 14
- 239000007789 gas Substances 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 9
- 239000011521 glass Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 239000001294 propane Substances 0.000 description 9
- 239000000376 reactant Substances 0.000 description 9
- 238000005893 bromination reaction Methods 0.000 description 8
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 8
- 239000006200 vaporizer Substances 0.000 description 8
- NAMYKGVDVNBCFQ-UHFFFAOYSA-N 2-bromopropane Chemical compound CC(C)Br NAMYKGVDVNBCFQ-UHFFFAOYSA-N 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 239000001282 iso-butane Substances 0.000 description 7
- 235000013847 iso-butane Nutrition 0.000 description 7
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 7
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Inorganic materials [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 6
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 6
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 6
- 229910052749 magnesium Inorganic materials 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- 229910001507 metal halide Inorganic materials 0.000 description 6
- 150000005309 metal halides Chemical class 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229910052684 Cerium Inorganic materials 0.000 description 5
- 229910052691 Erbium Inorganic materials 0.000 description 5
- 229910052693 Europium Inorganic materials 0.000 description 5
- 229910052688 Gadolinium Inorganic materials 0.000 description 5
- 229910052765 Lutetium Inorganic materials 0.000 description 5
- 229910052779 Neodymium Inorganic materials 0.000 description 5
- 229910052777 Praseodymium Inorganic materials 0.000 description 5
- 229910052771 Terbium Inorganic materials 0.000 description 5
- 229910052769 Ytterbium Inorganic materials 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 229910052787 antimony Inorganic materials 0.000 description 5
- 229910052796 boron Inorganic materials 0.000 description 5
- 229910052793 cadmium Inorganic materials 0.000 description 5
- 229910052792 caesium Inorganic materials 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 5
- 229910052804 chromium Inorganic materials 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 229910052733 gallium Inorganic materials 0.000 description 5
- 229910052732 germanium Inorganic materials 0.000 description 5
- 229910052737 gold Inorganic materials 0.000 description 5
- 229910052735 hafnium Inorganic materials 0.000 description 5
- 229910052738 indium Inorganic materials 0.000 description 5
- 229910052741 iridium Inorganic materials 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 229910052746 lanthanum Inorganic materials 0.000 description 5
- 229910052745 lead Inorganic materials 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 229910052748 manganese Inorganic materials 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229910052750 molybdenum Inorganic materials 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 229910052758 niobium Inorganic materials 0.000 description 5
- 229910052763 palladium Inorganic materials 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 229910052700 potassium Inorganic materials 0.000 description 5
- 230000008929 regeneration Effects 0.000 description 5
- 238000011069 regeneration method Methods 0.000 description 5
- 229910052702 rhenium Inorganic materials 0.000 description 5
- 229910052703 rhodium Inorganic materials 0.000 description 5
- 229910052707 ruthenium Inorganic materials 0.000 description 5
- 229910052706 scandium Inorganic materials 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 229910052709 silver Inorganic materials 0.000 description 5
- 229910052712 strontium Inorganic materials 0.000 description 5
- 229910052715 tantalum Inorganic materials 0.000 description 5
- 229910052718 tin Inorganic materials 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 229910052721 tungsten Inorganic materials 0.000 description 5
- 229910052720 vanadium Inorganic materials 0.000 description 5
- 229910052727 yttrium Inorganic materials 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- 229910052726 zirconium Inorganic materials 0.000 description 5
- CYNYIHKIEHGYOZ-UHFFFAOYSA-N 1-bromopropane Chemical compound CCCBr CYNYIHKIEHGYOZ-UHFFFAOYSA-N 0.000 description 4
- 125000006416 CBr Chemical group BrC* 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- 229910052772 Samarium Inorganic materials 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 230000031709 bromination Effects 0.000 description 4
- 239000001273 butane Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 4
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 4
- 150000004820 halides Chemical class 0.000 description 4
- -1 methyl halide Chemical class 0.000 description 4
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- RKSOPLXZQNSWAS-UHFFFAOYSA-N tert-butyl bromide Chemical compound CC(C)(C)Br RKSOPLXZQNSWAS-UHFFFAOYSA-N 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- HLVFKOKELQSXIQ-UHFFFAOYSA-N 1-bromo-2-methylpropane Chemical compound CC(C)CBr HLVFKOKELQSXIQ-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910000435 bromine oxide Inorganic materials 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000005660 chlorination reaction Methods 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- 239000011949 solid catalyst Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 229910052716 thallium Inorganic materials 0.000 description 3
- 238000004227 thermal cracking Methods 0.000 description 3
- APQIUTYORBAGEZ-UHFFFAOYSA-N 1,1-dibromoethane Chemical compound CC(Br)Br APQIUTYORBAGEZ-UHFFFAOYSA-N 0.000 description 2
- 125000004810 2-methylpropylene group Chemical group [H]C([H])([H])C([H])(C([H])([H])[*:2])C([H])([H])[*:1] 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 241000282326 Felis catus Species 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- 229910001620 barium bromide Inorganic materials 0.000 description 2
- NKQIMNKPSDEDMO-UHFFFAOYSA-L barium bromide Chemical compound [Br-].[Br-].[Ba+2] NKQIMNKPSDEDMO-UHFFFAOYSA-L 0.000 description 2
- AOJDZKCUAATBGE-UHFFFAOYSA-N bromomethane Chemical compound Br[CH2] AOJDZKCUAATBGE-UHFFFAOYSA-N 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 229960001701 chloroform Drugs 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 229960003280 cupric chloride Drugs 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 230000026030 halogenation Effects 0.000 description 2
- 238000005658 halogenation reaction Methods 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- SIQZJFKTROUNPI-UHFFFAOYSA-N 1-(hydroxymethyl)-5,5-dimethylhydantoin Chemical compound CC1(C)N(CO)C(=O)NC1=O SIQZJFKTROUNPI-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 101100381997 Danio rerio tbc1d32 gene Proteins 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 101100381999 Mus musculus Tbc1d32 gene Proteins 0.000 description 1
- 101150101537 Olah gene Proteins 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 229910001622 calcium bromide Inorganic materials 0.000 description 1
- WGEFECGEFUFIQW-UHFFFAOYSA-L calcium dibromide Chemical compound [Ca+2].[Br-].[Br-] WGEFECGEFUFIQW-UHFFFAOYSA-L 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 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
- 230000008030 elimination Effects 0.000 description 1
- CMICJTGKTMWATP-UHFFFAOYSA-N ethane dihydrobromide Chemical class Br.Br.CC CMICJTGKTMWATP-UHFFFAOYSA-N 0.000 description 1
- VZMCQCHLKUWIFO-UHFFFAOYSA-N ethane;hydrobromide Chemical compound Br.CC VZMCQCHLKUWIFO-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/12—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of mineral acids
- C07C29/124—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of mineral acids of halides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Definitions
- Olah et al (George A. Olah, et al . J. Am . Chem . Soc. 1985, 207, 7097-7105) discloses a method for converting methane to methanol via methyl halides (CH 3 Br and CH 3 C1) , which are then hydrolyzed to prepare methanol.
- CH 3 Br and CH 3 C1 are hydrolyzed over catalysts with excess steam generating a methanol, water, and a HCl or HBr mixture.
- gas phase methane, HBr, and CH 3 Br are sent to a converter 52 through a line 36.
- HBr and CH 3 Br react with metal oxide to form CH 3 OCH 3 , CH 3 OH, and H 2 0, which are sent to a separator 44 along with unreacted methane and CH 3 Br through a line 46.
- CH 2 Br 2 , CHBr 3/ and CBr are sent to a converter 108 where they react with methane to form bromomethane. After the reaction the mixture is sent to the condenser 106.
- the conversion of the by products CH 2 Br 2 , CHBr 3 , and CBr 4 to bromomethane in the converter 108 is facilitated by the use of an electrophilic catalyst such as AlBr 3 , SbF 5 , etc. which provides a low barrier pathway allowing direct four centered exchange of H and Br.
- an electrophilic catalyst such as AlBr 3 , SbF 5 , etc. which provides a low barrier pathway allowing direct four centered exchange of H and Br.
- the reaction may be represented as follows :
- bromomethane reacts with metal oxide to generate dimethyl ether (DME) and metal bromide.
- Metal bromide is sent to the regenerator 120.
- the mixture of bromomethane and DME from the reactor 114 is sent to a separator 116.
- Bromomethane is recycled to the reactor 114, while DME is obtained as a product or directed to reactor 118.
- DME reacts with water (from the separator 112) over a catalyst to form methanol .
- a method and apparatus 200 for synthesizing olefins from alkanes, which have more than two carbon atoms in their molecular structure comprising a second embodiment of the invention.
- the alkane and bromine are directed to a heat zone and vaporizer 202, operating at a temperature above the atmospheric boiling point of bromine, where the now gaseous bromine and methane are allowed to mix.
- the gas mixture is passed into a bromination reactor 204, which contains an appropriate solid catalyst. After the reaction the mixture is directed to a condenser 206.
- the mixture of olefin and unreacted alkane monobromide from the reactor 214 is sent to a separator 216 where they are easily separated due to their wide different boiling points. Unreacted alkane monobromide, if any, is recycled to the reactor 214, while olefin is obtained as a product.
- metal bromide from the converter 210 and the rector 214 reacts with air or oxygen to regenerate metal oxide and bromine . After regeneration metal oxide is sent to the reactor 210 and the reactor 214, while bromine is sent to the vaporizer 202. If air is used as the source of oxygen for regeneration of the metal oxide nitrogen may be purged from the system by a separator 222.
- Zr0 2 (2.0000g) was mixed with H 2 S0 4 (3.000 ml, 96(w)%), then the mixture was heated at 110 °C for 4 hours. . The temperature increased to 500°C within 6 hours, and kept at 500°C for 4 hours. Catalyst C2 was obtained.
- the metal oxide mixture was tested at a CH 3 Br flow rate of 1.0 ml/minute at 230 °C. In the first half hour, the average CH 3 Br conversion was 65%, and the average dimethyl ether selectivity was 90.5%.
- Cu(N0 3 ) 2 (0.5M, 40.000 ml) solution was added into Zr solution (0.5M, 30.000 ml as prepared above). After stirring a few seconds, a gel was obtained. The gel was dried at 110°C for 4 hours, then heated to 500°C within 6 hours, and calcined at 500 °C for 4 hours. M3 was obtained.
- Reactants methane and bromine were fed into the first reactor (methane flow of 1.5 ml/minute, Br 2 flow of 0.07 ml/hour) .
- the reaction temperature was 390°C.
- Rl stabilized by online reaction for more than 8 hours
- the resulting mixture was passed through the trap and a mixture of methane and CH 3 Br (containing 20% mol of CH 3 Br) was obtained.
- This gas mixture was fed directly into reactor R2 at 220 °C.
- an average CH 3 Br conversion of 91% with an average dimethyl ether selectivity of 75% was obtained.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
MXPA04006785A MXPA04006785A (en) | 2002-01-24 | 2002-07-17 | Integrated process for synthesizing alcohols, ethers, and olefins from alkanes. |
CA2471295A CA2471295C (en) | 2002-01-24 | 2002-07-17 | Integrated process for synthesizing alcohols, ethers, and olefins from alkanes |
JP2003562057A JP4309283B2 (en) | 2002-01-24 | 2002-07-17 | Integrated process for the synthesis of alcohols, ethers and olefins from alkenes |
AU2002318266A AU2002318266B2 (en) | 2002-01-24 | 2002-07-17 | Integrated process for synthesizing alcohols, ethers, and olefins from alkanes |
EP02748199A EP1474371B1 (en) | 2002-01-24 | 2002-07-17 | Integrated process for synthesizing alcohols, ethers, and olefins from alkanes |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/054,004 US6486368B1 (en) | 2001-06-20 | 2002-01-24 | Integrated process for synthesizing alcohols, ethers, and olefins from alkanes |
US10/054,004 | 2002-01-24 |
Publications (3)
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WO2003062172A2 true WO2003062172A2 (en) | 2003-07-31 |
WO2003062172A3 WO2003062172A3 (en) | 2004-03-04 |
WO2003062172B1 WO2003062172B1 (en) | 2004-04-08 |
Family
ID=27609131
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PCT/US2002/022817 WO2003062172A2 (en) | 2002-01-24 | 2002-07-17 | Integrated process for synthesizing alcohols, ethers, and olefins from alkanes |
Country Status (9)
Country | Link |
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EP (2) | EP2277847A3 (en) |
JP (1) | JP4309283B2 (en) |
CN (1) | CN1271020C (en) |
AU (1) | AU2002318266B2 (en) |
CA (2) | CA2710351A1 (en) |
MX (1) | MXPA04006785A (en) |
RU (1) | RU2004125653A (en) |
WO (1) | WO2003062172A2 (en) |
ZA (1) | ZA200405085B (en) |
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US7148390B2 (en) | 2001-06-20 | 2006-12-12 | Grt, Inc. | Integrated process for synthesizing alcohols, ethers, aldehydes, and olefins from alkanes |
US7161050B2 (en) | 2001-06-20 | 2007-01-09 | Grt, Inc. | Method and apparatus for synthesizing olefins, alcohols, ethers, and aldehydes |
US7230150B2 (en) | 2001-04-18 | 2007-06-12 | Grt, Inc. | Zone reactor |
US7348464B2 (en) | 2004-04-16 | 2008-03-25 | Marathon Oil Company | Process for converting gaseous alkanes to liquid hydrocarbons |
US7361794B2 (en) | 2001-04-18 | 2008-04-22 | Grt, Inc. | Zone reactor |
WO2008125016A1 (en) * | 2007-04-13 | 2008-10-23 | Microvast Technologies, Ltd. | A PROCESS FOR PURIFYING HBr IN HYDROCARBONS |
US7674941B2 (en) | 2004-04-16 | 2010-03-09 | Marathon Gtf Technology, Ltd. | Processes for converting gaseous alkanes to liquid hydrocarbons |
US7812201B2 (en) | 2008-10-01 | 2010-10-12 | Targa Resources, Inc. | Process and catalyst for converting alkanes |
US7838708B2 (en) | 2001-06-20 | 2010-11-23 | Grt, Inc. | Hydrocarbon conversion process improvements |
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US7883568B2 (en) | 2006-02-03 | 2011-02-08 | Grt, Inc. | Separation of light gases from halogens |
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US4523040A (en) * | 1981-09-01 | 1985-06-11 | Olah George A | Methyl halides and methyl alcohol from methane |
US5243098A (en) * | 1992-11-04 | 1993-09-07 | Energia Andina Ltd. | Conversion of methane to methanol |
US5998679A (en) * | 1998-05-20 | 1999-12-07 | Jlm Technology, Ltd. | Methods for converting lower alkanes and alkanes to alcohols and diols |
IT1302003B1 (en) | 1998-08-05 | 2000-07-20 | Enitecnologie Spa | PROCEDURE FOR THE SELECTIVE TRANSFORMATION OF HYDROCARBONS. |
US6472572B1 (en) * | 2001-06-20 | 2002-10-29 | Grt, Inc. | Integrated process for synthesizing alcohols and ethers from alkanes |
US6465699B1 (en) * | 2001-06-20 | 2002-10-15 | Gri, Inc. | Integrated process for synthesizing alcohols, ethers, and olefins from alkanes |
-
2002
- 2002-07-17 JP JP2003562057A patent/JP4309283B2/en not_active Expired - Fee Related
- 2002-07-17 CN CNB028274989A patent/CN1271020C/en not_active Expired - Fee Related
- 2002-07-17 CA CA2710351A patent/CA2710351A1/en not_active Abandoned
- 2002-07-17 WO PCT/US2002/022817 patent/WO2003062172A2/en active Application Filing
- 2002-07-17 CA CA2471295A patent/CA2471295C/en not_active Expired - Fee Related
- 2002-07-17 RU RU2004125653/04A patent/RU2004125653A/en not_active Application Discontinuation
- 2002-07-17 AU AU2002318266A patent/AU2002318266B2/en not_active Ceased
- 2002-07-17 MX MXPA04006785A patent/MXPA04006785A/en active IP Right Grant
- 2002-07-17 EP EP10176682A patent/EP2277847A3/en not_active Withdrawn
- 2002-07-17 EP EP02748199A patent/EP1474371B1/en not_active Expired - Lifetime
-
2004
- 2004-06-25 ZA ZA200405085A patent/ZA200405085B/en unknown
Non-Patent Citations (2)
Title |
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None |
See also references of EP1474371A4 |
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Also Published As
Publication number | Publication date |
---|---|
EP2277847A2 (en) | 2011-01-26 |
RU2004125653A (en) | 2006-01-20 |
CN1615285A (en) | 2005-05-11 |
MXPA04006785A (en) | 2005-04-19 |
WO2003062172B1 (en) | 2004-04-08 |
CA2710351A1 (en) | 2003-07-31 |
JP4309283B2 (en) | 2009-08-05 |
CN1271020C (en) | 2006-08-23 |
CA2471295C (en) | 2010-08-10 |
EP1474371A2 (en) | 2004-11-10 |
EP2277847A3 (en) | 2011-07-27 |
EP1474371B1 (en) | 2011-12-21 |
ZA200405085B (en) | 2006-03-29 |
WO2003062172A3 (en) | 2004-03-04 |
EP1474371A4 (en) | 2006-04-05 |
AU2002318266B2 (en) | 2009-06-04 |
JP2005515247A (en) | 2005-05-26 |
CA2471295A1 (en) | 2003-07-31 |
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