EP1235774A1 - Dehydrohalogenation of halogenated alkanes using rare earth halide or oxyhalide catalyst - Google Patents
Dehydrohalogenation of halogenated alkanes using rare earth halide or oxyhalide catalystInfo
- Publication number
- EP1235774A1 EP1235774A1 EP00980431A EP00980431A EP1235774A1 EP 1235774 A1 EP1235774 A1 EP 1235774A1 EP 00980431 A EP00980431 A EP 00980431A EP 00980431 A EP00980431 A EP 00980431A EP 1235774 A1 EP1235774 A1 EP 1235774A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- rare earth
- catalyst
- chloride
- lanthanum
- oxyhahde
- 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.)
- Withdrawn
Links
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 90
- 239000003054 catalyst Substances 0.000 title claims abstract description 73
- 150000001335 aliphatic alkanes Chemical class 0.000 title claims abstract description 56
- -1 rare earth halide Chemical class 0.000 title claims abstract description 51
- 238000006704 dehydrohalogenation reaction Methods 0.000 title abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 101
- 150000001336 alkenes Chemical class 0.000 claims abstract description 55
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 44
- CFXQEHVMCRXUSD-UHFFFAOYSA-N 1,2,3-Trichloropropane Chemical compound ClCC(Cl)CCl CFXQEHVMCRXUSD-UHFFFAOYSA-N 0.000 claims abstract description 30
- KNKRKFALVUDBJE-UHFFFAOYSA-N 1,2-dichloropropane Chemical compound CC(Cl)CCl KNKRKFALVUDBJE-UHFFFAOYSA-N 0.000 claims abstract description 23
- UOORRWUZONOOLO-OWOJBTEDSA-N (E)-1,3-dichloropropene Chemical compound ClC\C=C\Cl UOORRWUZONOOLO-OWOJBTEDSA-N 0.000 claims abstract description 19
- OWXJKYNZGFSVRC-NSCUHMNNSA-N (e)-1-chloroprop-1-ene Chemical compound C\C=C\Cl OWXJKYNZGFSVRC-NSCUHMNNSA-N 0.000 claims abstract description 18
- UOORRWUZONOOLO-UHFFFAOYSA-N telone II Natural products ClCC=CCl UOORRWUZONOOLO-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000006227 byproduct Substances 0.000 claims abstract description 11
- PNLQPWWBHXMFCA-UHFFFAOYSA-N 2-chloroprop-1-ene Chemical compound CC(Cl)=C PNLQPWWBHXMFCA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims description 42
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 claims description 32
- 229910052746 lanthanum Inorganic materials 0.000 claims description 22
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 22
- 239000000047 product Substances 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 16
- 239000001307 helium Substances 0.000 claims description 16
- 229910052734 helium Inorganic materials 0.000 claims description 16
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 16
- 239000001301 oxygen Substances 0.000 claims description 16
- 229910052760 oxygen Inorganic materials 0.000 claims description 16
- 230000008929 regeneration Effects 0.000 claims description 15
- 238000011069 regeneration method Methods 0.000 claims description 15
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical group Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 9
- 229910052779 Neodymium Inorganic materials 0.000 claims description 8
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 8
- 150000001805 chlorine compounds Chemical group 0.000 claims description 8
- 239000003085 diluting agent Substances 0.000 claims description 8
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 8
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 8
- 150000008282 halocarbons Chemical class 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 6
- 229910052727 yttrium Inorganic materials 0.000 claims description 6
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 5
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 5
- 229910052691 Erbium Inorganic materials 0.000 claims description 5
- 229910052693 Europium Inorganic materials 0.000 claims description 5
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 5
- 229910052765 Lutetium Inorganic materials 0.000 claims description 5
- 229910052772 Samarium Inorganic materials 0.000 claims description 5
- 229910052771 Terbium Inorganic materials 0.000 claims description 5
- 229910052775 Thulium Inorganic materials 0.000 claims description 5
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 5
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims description 5
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims description 5
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 5
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 5
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical group I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 5
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 5
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims description 5
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims description 5
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical group [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 2
- KNKRKFALVUDBJE-VMIGTVKRSA-N 1,2-dichloropropane Chemical group [13CH3][13CH](Cl)[13CH2]Cl KNKRKFALVUDBJE-VMIGTVKRSA-N 0.000 claims 1
- JEROREPODAPBAY-UHFFFAOYSA-N [La].ClOCl Chemical group [La].ClOCl JEROREPODAPBAY-UHFFFAOYSA-N 0.000 claims 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 abstract description 11
- 238000005660 chlorination reaction Methods 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000006283 soil fumigant Substances 0.000 abstract description 3
- 238000007033 dehydrochlorination reaction Methods 0.000 description 14
- 150000002367 halogens Chemical group 0.000 description 13
- 239000002585 base Substances 0.000 description 11
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 description 8
- 229910052736 halogen Inorganic materials 0.000 description 8
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 7
- OWXJKYNZGFSVRC-IHWYPQMZSA-N (z)-1-chloroprop-1-ene Chemical compound C\C=C/Cl OWXJKYNZGFSVRC-IHWYPQMZSA-N 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 239000000908 ammonium hydroxide Substances 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 5
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- FALCMQXTWHPRIH-UHFFFAOYSA-N 2,3-dichloroprop-1-ene Chemical compound ClCC(Cl)=C FALCMQXTWHPRIH-UHFFFAOYSA-N 0.000 description 4
- VRTNIWBNFSHDEB-UHFFFAOYSA-N 3,3-dichloroprop-1-ene Chemical compound ClC(Cl)C=C VRTNIWBNFSHDEB-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 239000002316 fumigant Substances 0.000 description 4
- 229910000039 hydrogen halide Inorganic materials 0.000 description 4
- 239000012433 hydrogen halide Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- ZAIDIVBQUMFXEC-UHFFFAOYSA-N 1,1-dichloroprop-1-ene Chemical compound CC=C(Cl)Cl ZAIDIVBQUMFXEC-UHFFFAOYSA-N 0.000 description 2
- OWXJKYNZGFSVRC-UHFFFAOYSA-N 1-chloroprop-1-ene Chemical class CC=CCl OWXJKYNZGFSVRC-UHFFFAOYSA-N 0.000 description 2
- 238000004438 BET method Methods 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- 101150081330 MOC1 gene Proteins 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 101100041989 Schizosaccharomyces pombe (strain 972 / ATCC 24843) sds23 gene Proteins 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000026030 halogenation Effects 0.000 description 2
- 238000005658 halogenation reaction Methods 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- IFTGEZOPUAJVMG-UHFFFAOYSA-N 1,1-dibromobut-1-ene Chemical class CCC=C(Br)Br IFTGEZOPUAJVMG-UHFFFAOYSA-N 0.000 description 1
- HTEJLXYOJZOXKM-UHFFFAOYSA-N 1,1-dibromoprop-1-ene Chemical class CC=C(Br)Br HTEJLXYOJZOXKM-UHFFFAOYSA-N 0.000 description 1
- UAZUEJTXWAXSMA-UHFFFAOYSA-N 1,1-dichlorobut-1-ene Chemical class CCC=C(Cl)Cl UAZUEJTXWAXSMA-UHFFFAOYSA-N 0.000 description 1
- PQBOTZNYFQWRHU-UHFFFAOYSA-N 1,2-dichlorobutane Chemical compound CCC(Cl)CCl PQBOTZNYFQWRHU-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- IUXHPSPHPKXTPA-UHFFFAOYSA-N 1-bromobut-1-ene Chemical class CCC=CBr IUXHPSPHPKXTPA-UHFFFAOYSA-N 0.000 description 1
- NNQDMQVWOWCVEM-UHFFFAOYSA-N 1-bromoprop-1-ene Chemical class CC=CBr NNQDMQVWOWCVEM-UHFFFAOYSA-N 0.000 description 1
- DUDKKPVINWLFBI-UHFFFAOYSA-N 1-chlorobut-1-ene Chemical class CCC=CCl DUDKKPVINWLFBI-UHFFFAOYSA-N 0.000 description 1
- AKQZPPKQVZVYCC-UHFFFAOYSA-N 4,4,4-trichlorobut-1-ene Chemical class ClC(Cl)(Cl)CC=C AKQZPPKQVZVYCC-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910002420 LaOCl Inorganic materials 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical class CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 150000003975 aryl alkyl amines Chemical class 0.000 description 1
- 229910001570 bauxite Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 229910000043 hydrogen iodide Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000003701 inert diluent Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000001069 nematicidal effect Effects 0.000 description 1
- 239000005645 nematicide Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
- B01J27/10—Chlorides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
- B01J27/122—Halides of copper
-
- 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
- C07C17/15—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination
-
- 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
- C07C17/15—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination
- C07C17/152—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination of hydrocarbons
-
- 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
- C07C17/15—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination
- C07C17/152—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination of hydrocarbons
- C07C17/154—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination of hydrocarbons of saturated hydrocarbons
-
- 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
- C07C17/15—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination
- C07C17/152—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination of hydrocarbons
- C07C17/156—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination of hydrocarbons of unsaturated hydrocarbons
-
- 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
- C07C17/15—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination
- C07C17/158—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination of halogenated hydrocarbons
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/22—Halogenating
Definitions
- This invention pertains to a process of catalytically dehydrohalogenating a halogenated alkane, such as 1 ,2-d ⁇ chloropropane or 1 ,2,3-t ⁇ chloropropane, to produce an alkene or a halogenated alkene, such as allyl chloride or 1 ,3-dichloropropene, respectively
- Alkenes such as propylene. find wide utility as monomers in the manufacture of polyolefin polymers and synthetic rubbers. Halogenated alkenes find utility in a variety of basic and specialty chemicals. Allyl chloride, for example, is a valuable starting material in the preparation of epichlorohydrm. from which epoxy polymers are manufactured. 1 ,3- Dichloropropene and other chlorinated alkenes find utility as components in nematocides, soil fumigants, insecticides, and as monomers in the production of plastics, resins, and chemical intermediates.
- the manufacture of allyl chloride involves contacting propylene and chlorine rapidly at elevated temperatures, as described, for example, in U S. 4,319,062.
- the by-product stream that is obtained as material of intermediate boiling point, after removing the lower boiling fractions containing the allyl chloride and the higher boiling fractions containing mostly cis- and trans- 1 ,3-d ⁇ chloropropenes by distillation, contains a variety of chlorinated propanes and propenes including 1 ,2-d ⁇ chloropropane, 3,3-d ⁇ chloropropene, 2,3- dichloropropene, 2.2-d ⁇ chloropropane, and other related chlorinated C 3 species.
- 1 ,2-d ⁇ chloropropane is present as a major component, often amounting to approximately 70 to 95 mole percent, and typically 75 to 90 mole percent, of the by-product stream.
- 3,3-d ⁇ chloropropene is present in an amount ranging from 0.1 to 15 mole percent of the by- product stream.
- 3,3-Dichloropropene is typically isome ⁇ zed to yield the above-mentioned 1 ,3-dichloropropene, as described, for example, in US 5,072,063 and 5,510,546.
- 1 ,2- Dichloropropane is not useful per se and must also be up-graded to a product of higher value.
- 1,2-d ⁇ chloropropane has been up-graded via thermal dehydrochlo ⁇ nation to allyl chloride
- thermal dehydrochlo ⁇ nation include cis- and trans- 1 - chloropropene, which can be recycled to the aforementioned allyl chloride manufacturing process, wherein propylene is chlorinated to allyl chloride.
- allyl chloride product can itself be chlorinated to form 1 ,2,3- trichloropropane, a by-product of very limited value and utility, but 1 ,2,3-t ⁇ chloropropane can be dehydrohalogenated to form 1 ,3-d ⁇ chloropropene, which has utility in fumigants
- Conventional dehydrohalogenation processes typically produce unfavorable yields of 2,3-d ⁇ chloropropene, which may be difficult to separate by simple distillation It would be desirable to discover a dehydrohalogenation process that converts 1 ,2,3- trichloropropane to the more desirable cis and trans- 1 ,3-d ⁇ chloropropene products with reduced levels of 2,3-d ⁇ chloropropene
- This invention is a novel process of dehydrohalogenating a halogenated alkane to form an alkene or a halogenated alkene
- the novel process of this invention comprises contacting a halogenated alkane having three or more carbon atoms with a dehydrohalogenation catalyst under reaction conditions sufficient to produce the alkene or halogenated alkene
- the dehydrohalogenation catalyst comprises a rare earth halide or rare earth oxyha de compound
- the novel process of this invention simply and efficiently converts a halogenated alkane via dehydrohalogenation (cracking) in the presence of a rare earth halide or rare earth oxyhahde catalyst to an alkene or a halogenated alkene
- the process of this invention can be advantageously used to up-grade lower valued halogenated alkanes to higher valued alkenes or halogenated alkenes suitable for commercial use.
- 1 ,2- dichloropropane, produced in the chlorination of propylene to allyl chloride can be advantageously dehydrohalogenated by the process of this invention to allyl chloride and 1- chloropropene in high yield.
- 2-Chloropropene an undesirable by-product of the dehydrohalogenation of 1 ,2-dichloropropane, is produced at an advantageously low level in the process of this invention.
- 1 -Chloropropene produced in the cracking process herein of 1 ,2-dichloropropane, can be beneficially recycled to the allyl chloride reactor and chlorinated to 1 ,3-dichloropropene, which is useful in fumigants.
- 1 ,2,3-trichloropropane can be beneficially dehydrohalogenated to produce predominantly 1 ,3-dichloropropene, having the aforementioned utility in fumigants.
- the dehydrohalogenation occurs at a temperature that is lower than the temperatures required of prior art dehydrohalogenation processes. Accordingly, the process of this invention consumes less energy than prior art processes and provides the opportunity for higher conversion at lower operating temperatures.
- the rare earth halide catalyst of this invention is soluble in water. Accordingly, should process equipment, such as filters, transport lines, valves, and intricate small or curved parts of the reactor, become plugged with catalyst particles, the plugged parts need only be washed with water to restore the parts to working order.
- this invention is a novel process comprising the catalytic dehydrohalogenation of a halogenated alkane to form an alkene or a halogenated alkene.
- the novel process of this invention comprises contacting a halogenated alkane having three or more carbon atoms with a dehydrohalogenation catalyst under reaction conditions sufficient to prepare the alkene or halogenated alkene.
- the dehydrohalogenation catalyst used in the novel process of this invention comprises a rare earth halide or rare earth oxyhahde compound.
- this invention is a novel process comprising the catalytic dehydrochlorination of a chlorinated alkane so as to form an alkene or a chlorinated alkene.
- the novel process comprises contacting a chlorinated alkane having three or more carbon atoms with a dehydro-chlo ⁇ nation catalyst under reaction conditions sufficient to prepare the corresponding alkene or chlorinated alkene, the dehydrochlorination catalyst being a rare earth halide or rare earth oxyhahde, more preferably, a rare earth chloride or rare earth oxychlo ⁇ de.
- the chlorinated alkane is 1 ,2-d ⁇ chloropropane or a mixture of chlorinated alkanes comprising predominantly 1 ,2-d ⁇ chloropropane, and the halogenated alkene comprises allyl chloride, 1 -chloropropene, or essentially a combination thereof.
- the chlorinated alkane is 1 ,2,3-trichloropropane. and the halogenated alkene is 1 ,3-dichloropropene
- the halogenated alkane which is used in the process of this invention, can be any halogenated alkane having three or more carbon atoms
- the halogenated alkane may also be an essentially pure halogenated alkane or a mixture of halogenated alkanes
- the halogenated alkane is a halogenated C ⁇ g alkane or mixture of halogenated C 3 8 alkanes. More preferably, the halogenated alkane is a halogenated C 4 alkane or a mixture of halogenated C 3 4 alkanes.
- the halogenated alkane will possess at least one halogen substituent Full saturation with halogen substituents is typically not preferred.
- At least one hydrogen atom is preferably present on at least one of the carbon atoms, because the dehydrohalogenation proceeds by eliminating hydrogen halide from the halogenated alkane.
- Each halogen substituent which is present, may be independently selected from chlorine, bromine, and iodine substituents
- the halogen substituent is selected from chlorine or bromine substituents
- Fluorine substituents may be present on the halogenated alkane, but typically fluorine remains inert and does not participate in dehydrofluo ⁇ nation (loss of HF)
- suitable halogenated alkanes include 1 ,2- dichloropropane, 1 ,2,3-trichloropropane, 1 ,2-dichlorobutane, 2.3-d ⁇ chlorobutane, 1 ,2,3- t ⁇ chlorobutane, 1 ,2-d ⁇ bromopropane, 1 ,2,3-t ⁇ bromopropane, 1 ,
- the halogenated alkane is 1 ,2-d ⁇ chloropropane or 1 ,2,3-trichloropropane.
- the halogenated alkane is a mixture of 1 ,2- dichloropropane with di- and tri-chlorinated C 3 alkanes and C 3 alkenes.
- These mixtures known in the art as “allyl propylene dichloride” (“allyl PDC”), may be obtained as byproduct streams in the chlorination of propylene to form allyl chloride.
- "Allyl PDC" compositions can vary with the specific conditions in the allyl chloride reactor and the particular purification steps employed.
- a typical "allyl PDC" composition comprises from 70 to 95 mole percent 1 ,2- dichloropropane, from 1 to 15 mole percent 2,3-dichloropropene, from 0.1 to 15 mole percent 3,3-dichloropropene, from 0.1 to 10 mole percent 1 ,3-dichloropropene isomers, from 0 to 3 mole percent 1 , 1-dichloropropene, and may contain other chlorinated alkanes and alkenes as well as non-chlorinated compounds.
- the feed to the dehydrohalogenation process comprising the halogenated alkane can be diluted with a diluent or carrier gas, which may be any gas that does not substantially interfere with the dehydrohalogenation process.
- the diluent may assist in removing products and heat from the reactor and in reducing the number of undesirable side-reactions.
- suitable diluents include nitrogen, argon, helium, carbon monoxide, carbon dioxide, steam, condensable halogenated hydrocarbons, and mixtures thereof.
- condensable halogenated hydrocarbons will include any halogenated hydrocarbon which is substantially inert with respect to the dehydrohalogenation process of this invention and which is readily separated from the dehydrohalogenation product effluent by fractional distillation or cooling.
- Fully perhalogenated alkenes such as perchloroethylene and perfluoroethylene, may be suitably employed as the condensable halogenated hydrocarbon.
- the quantity of diluent employed typically ranges from greater than 10 mole percent, and preferably, greater than 20 mole percent, to typically, less than 90 mole percent, and preferably, less than 70 mole percent, based on the total moles of starting halogenated alkane and optional diluent.
- One catalyst which is employed in the novel dehydrohalogenation process of this invention comprises a rare earth halide.
- the rare earths are a group of 17 elements consisting of scandium (atomic number 21 ), yttrium (atomic number 39) and the lanthanides (atomic numbers 57-71) [James B. Hedrick, U.S. Geological Survey - Minerals Information - 1997, "Rare-Earth Metals"].
- the term is taken to mean an element selected from lanthanum, cerium, neodymium, praseodymium, dysprosium, samarium, yttrium, gadolinium, erbium, ytterbium, hoimium, terbium, europium, thulium, lutetium, and mixtures thereof.
- Preferred rare earth elements for use in the aforementioned dehydrohalogenation process are those which are typically considered as being single valency metals Catalytic performance of multi-valency metals appears to be less desirable than those that are single valency.
- the rare earth element for this invention is even more preferably selected from lanthanum, neodymium, praseodymium, and mixtures thereof. Most preferably, the rare earth element used in the catalyst is lanthanum or a mixture of lanthanum with other rare earth elements
- the rare earth halide is represented by the formula MXi wherein M is at least one rare earth element selected from the group consisting of lanthanum, cerium, neodymium, praseodymium, dysprosium, samarium, yttrium, gadolinium, erbium, ytterbium, hoimium, terbium, europium, thulium, lutetium, and mixtures thereof; and wherein X is chloride, bromide, or iodide More preferably, X is chloride, and the more preferred rare earth halide is represented by the formula MC1 , wherein M is defined hereinbefore. Most preferably, X is chloride and M is lanthanum, and the rare earth halide is lanthanum chloride, which optionally can be mixed with other rare earth chlorides
- the rare earth halide catalyst is porous, which means that the catalyst contains void spaces, such as channels, pores, and/or cavities, within its crystallographic structure. This porosity creates surface area throughout the compound.
- the porous rare earth halide has a BET surface area greater than 5 ⁇ r/g, as determined by the BET (Brunauer-Emmet-Teller) method of measuring surface area, described by S Brunauer, P. H. Emmett, and E. Teller, Journal of the American Chemical Society, 60, 309 ( 1938).
- the porous rare earth halide has a BET surface area greater than 10 ⁇ r/g, more preferably, greater than 15 m7g, even more preferably, greater than 20 m " /g, and most preferably, greater than 30 m7g.
- the nitrogen adsorption isotherm is measured at 77K, and the surface area is calculated from the isotherm data utilizing the BET method
- the catalyst of this novel dehydrohalogenation process comp ⁇ ses a rare earth oxyhahde, the rare earths being identified hereinbefore
- this form of the catalyst is represented by the formula MOX, wherein M is at least one rare earth element selected from the group consisting of lanthanum, cerium, neodymium, praseodymium, dysprosium, samarium, yttrium, gadolinium, erbium, ytterbium, hoimium, terbium, europium, thulium, lutetium, and mixtures thereof, and wherein X is selected from the group consisting of chloride, bromide, and iodide
- the rare earth oxyhahde is a rare earth oxychlo ⁇ de, represented by the formula MOC1, wherein M is defined hereinbefore
- the rare earth oxychlo ⁇ de is lanthanum oxychlo ⁇ de, LaOCl, optionally
- the rare earth oxyhahde is porous, as defined hereinbefore in connection with the rare earth halide
- the porous rare earth oxyhahde has a BET surface area of greater than 12 m7g, preferably, greater than 15 m7g, more preferably, greater than 20 m7g, and most preferably, greater than 30 m7g
- the BET surface area is less than 200 m7g
- the MOC1 phases possess characteristic powder X-Ray Diffraction (XRD) patterns that are distinct from the MCL phases
- preferable elemental additives include alkali and alkaline earths, boron, phosphorous, sulfur, germanium, titanium, zirconium, hafnium, the noble metals, and combinations thereof
- the noble metals include ruthenium, rhodium, palladium, osmium, indium, platinum, silver, and gold
- the total concentration of elemental additives in the catalyst is typically greater than 0 01 weight percent and typically less than 20 weight percent, based on the total weight of the catalyst In the discussion hereinabove, the catalysts are not bound to a support or carrier.
- the rare earth halide or rare earth oxyhahde catalyst may be bound to, extruded with, or deposited onto a catalyst support or carrier.
- suitable carriers include alumina, silica, silica-alumina, porous aluminosilicate (zeolite), silica-magnesia, bauxite, magnesia, silicon carbide, titanium oxide, zirconium oxide, zirconium silicate, or combinations thereof.
- the support is used in a quantity greater than 1 weight percent, and preferably, greater than 10 weight percent, based on the total weight of the catalyst and support.
- the support is used in a quantity less than 90 weight percent, preferably, less than 80 weight percent, and more preferably, less than 70 weight percent, based on the total weight of the catalyst and support.
- the rare earth halide and rare earth oxyhahde catalysts may be obtained from commercial suppliers.
- the porous rare earth halide and porous rare earth oxyhahde catalysts may be synthesized as described hereinafter, as the porous embodiments of the catalyst are not known to be commercially available at the current time.
- a method currently felt to be preferable for forming the composition comprising the porous rare earth oxyhahde comprises the following steps: (a) preparing a solution of a halide salt of the rare earth element or elements in a solvent comprising either water, an alcohol, or mixtures thereof; (b) adding a base to cause the formation of a precipitate; and (c) collecting and calcining the precipitate in order to form the MOX.
- the halide salt is a rare earth chloride salt, for example, any of such salts which are commercially available.
- a nitrogen-containing base is employed selected from ammonium hydroxide, alkyl amines, aryl amines, arylalkyl amines, alkyl ammonium hydroxides, aryl ammonium hydroxides, arylalkyl ammonium hydroxides, and mixtures thereof.
- the nitrogen-containing base may also be provided as a mixture of a nitrogen-containing base with other bases that do not contain nitrogen.
- the nitrogen-containing base is ammonium hydroxide or tetra(alkyl)ammonium hydroxide, more preferably, tetra(C ⁇ _ 0 alkyl)ammonium hydroxide.
- the solvent in Step (a) is preferably water.
- Porous rare earth oxychlorides may also be produced by appropriate use of alkali or alkaline earth hydroxides, preferably, with the buffering action of a nitrogen-containing base.
- the precipitation is conducted at a temperature greater than 0°C
- the precipitation is conducted at a temperature less than 200°C, preferably, less than 100°C
- the precipitation is conducted generally at ambient atmospheric pressure, although higher pressures may be used, as necessary, to maintain liquid phase at the precipitation temperature employed
- the calcination is typically conducted at a temperature greater than 200°C, preferably, greater than 300°C, but less than 800°C, and preferably, less than 600°C
- Mixtures of carboxylic acid and rare earth chloride salts also can yield rare earth oxychlorides upon appropriate decomposition
- a method currently felt to be preferable for forming the catalyst composition comprising the porous rare earth halide (MX ) comprises the following steps (a) preparing a solution of a halide salt of the rare earth element or elements in a solvent comprising either water, an alcohol, or mixtures thereof, (b) adding a base to cause the formation of a precipitate, (c) collecting and calcining the precipitate, and (d) contacting the calcined precipitate with a halogen source
- the rare earth halide is a rare earth chloride salt, such as any commercially available rare earth chloride
- the solvent is water
- the base is any of those bases noted hereinbefore in connection with the preparation of MOX
- the precipitation is generally conducted at a temperature greater than 0°C and less than 200°C, preferably less than 100°C, at ambient atmospheric pressure or a higher pressure so as to maintain liquid phase
- the calcination is typically conducted at a temperature greater than 200°C, preferably, greater than 300°C
- any process conditions for example, molar ratios of feed components, temperature, pressure, gas hourly space velocity
- the process temperature is greater than 100°C, preferably, greater than 150°C, and more preferably, greater than 180°C.
- the process temperature is less than 500°C, preferably, less than 300°C, and more preferably, less than 250°C. It is further within the scope of this invention to preheat the reactant feed comprising the halogenated alkane plus optional diluent.
- the preheat temperature is greater than 50°C, preferably, greater than 100°C, but typically equal to or less than the process temperature.
- the preheat temperature is less than 500°C, and preferably, less than 300°C.
- the process will be conducted at atmospheric pressure or a higher pressure.
- the pressure will be equal to or greater than 14 psia (96 kPa), but typically less than 1 ,000 psia (6,895 kPa), preferably, less than 600 psia (4, 137 kPa), and more preferably, less than 300 psig (2,068 kPa).
- the total gas hourly space velocity (GHSV) of the feed (halogenated alkane plus optional diluent) will be greater than 10 ml total feed per ml catalyst per hour (h “ 1 ), preferably, greater than 100 h " 1 , more preferably, greater than 400 h " .
- the total gas hourly space velocity of the feed will be less than 30,000 h " 1 , preferably, less than 20,000 h " 1 , and more preferably, less than 10,000 h0
- the alkene or halogenated alkene formed in the dehydrohalogenation cracking process of this invention may be any alkene or halogenated alkene.
- the product alkene contains the same number of carbon atoms as the reactant alkane.
- the alkene or halogenated alkene will be a C . 8 , more preferably, a C 3 . 4 alkene or halogenated alkene.
- the halogenated alkene will contain one or more halogen substituents, preferably, selected from chlorine, bromine, and iodine. More preferably, the halogen substituent is chlorine.
- Non-limiting examples of product alkenes include propylene and butenes, and higher homologues thereof.
- Non-limiting examples of halogenated alkenes include chloropropenes, dichloropropenes, chlorobutenes, dichlorobutenes, trichlorobutenes, bromopropenes, dibromopropenes, bromobutenes, dibromobutenes.
- the alkene is propylene or butene.
- the halogenated alkene is selected from the group consisting of allyl chloride, 1 -chloropropene, 1 ,3-dichloropropene, and mixtures thereof.
- 1 ,2-Dichloropropane which is produced as a substantial by-product in the manufacture of allyl chloride, can be advantageously dehydrohalogenated via the process of this invention selectively to mixtures of allyl chloride and 1 -chloropropene, with very low levels of unwanted 2-chloropropene being formed.
- the conversion of 1 ,2-dichloropropane is greater than 50 mole percent, and preferably, greater than 60 mole percent at temperatures less than 240°C.
- conversion is defined as the mole percentage of halogenated alkane feed, such as 1 ,2-dichloropropane feed, reacted in the dehydrohalogenation process.
- the total selectivity to allyl chloride and 1 -chloropropene exceeds 90 mole percent.
- selectivity to unwanted 2-chloropropene is less than 2 mole percent, and preferably, less than 1 mole percent.
- selectivity is defined as the mole percentage of reacted halogenated alkane which forms the specified product.
- the 1 -chloropropene which is produced during dehydrohalogenation of 1,2- dichloropropane, can be advantageously recycled to an allyl chloride reactor, where propylene is chlorinated to allyl chloride.
- 1 - chloropropene is converted to 1 ,3-dichloropropene, a component of soil fumigants.
- 1 ,2,3-trichloropropane produced in the chlorination of allyl chloride, can be selectively dehydrochlorinated by the process of this invention to a mixture comprising predominantly cis and trans- 1 ,3-dichloropropenes.
- a combined selectivity of greater than 55 mole percent of cis and trans- 1 ,3-dichloro-propenes is typically achieved.
- a combined selectivity of greater than 70 mole percent cis and trans- 1 ,3-dichloropropenes is achieved.
- the process of this invention cracks hydrogen halide, preferably, hydrogen chloride, from the halogenated alkane feed.
- the hydrogen halide, which is formed may be recycled to an oxidative halogenation process, preferably an oxidative chlorination process, wherein a hydrocarbon or halogenated hydrocarbon (the starting hydrocarbon) can be reacted with oxygen and the recycle hydrogen halide in the presence of an oxidative halogenation catalyst, for example, a copper-based catalyst, to produce a halogenated hydrocarbon having a greater number of halogenated substituents than the starting hydrocarbon.
- an oxidative halogenation catalyst for example, a copper-based catalyst
- a preferred method of regeneration involves contacting the partially or fully deactivated catalyst with steam at a temperature sufficient to regenerate, at least in part, the catalytic activity
- the steam is provided in a regeneration gas mixture containing an inert diluent, such as nitrogen, helium, or argon.
- the quantity of steam in the mixture may vary from greater than 0.005 mole percent to less than 50 mole percent, based on the total moles of regeneration gas.
- oxygen may be added to the regeneration gas to aid in the removal of coke.
- Oxygen-containing mixtures can contain from greater than 1 mole percent to less than 50 mole percent oxygen, as desired, but preferably, the oxygen content of the regeneration gas mixture is greater than 2 mole percent and less than 20 mole percent, based on the total moles of regeneration gas mixture
- the regeneration is usually conducted at a temperature greater than 200°C, preferably, greater than 300°C.
- the regeneration is usually conducted at a temperature less than 700°C, and preferably, less than 600°C.
- the duration of the regeneration can range from greater than 30 minutes to less than 12 hours, and preferably from greater than 30 minutes to less than 5 hours.
- a porous lanthanum oxychlo ⁇ de catalyst was prepared as follows. Lanthanum chloride (LaCl 7 H O, 15.0 g) was dissolved in deio zed water ( 150 ml). Ammonium hydroxide (6 M, 20 ml) was added to the lanthanum chloride solution quickly with stirring, resulting in a white precipitate. The mixture was cent ⁇ fuged and the excess liquid decanted yielding a lanthanum-containing gel. The precipitate was calcined at 400°C for 4 hours yielding a porous lanthanum oxychlo ⁇ de catalyst. X-ray diffraction data indicated the presence of a quasi-crystalline form of lanthanum oxychlo ⁇ de. The surface area of the catalyst was 25.8 m7g, as measured by the BET method.
- the catalyst was dried at 130°C under flowing helium for 1 h and further heated to 230°C under flowing helium.
- 1 ,2-Dichloropropane (PDC) was pumped via a Gilson Model 305 pump at a rate of 7.68 cm /h and mixed with helium at a flow rate of 33 cm /min to form a PDC/He feed.
- the feed was preheated to 170°C and fed to the reactor operating at 230°C and atmospheric pressure.
- the feed gas hourly space velocity was 682 h ' .
- Table 1 The composition of the exit feed is shown in Table 1.
- the catalyst was regenerated by passing a stream of steam at a rate of 1.2 cm /h and a stream of oxygen and helium ( 15 percent oxygen in helium) at a rate of 200 cm /min over the catalyst for 2 h at a temperature of 400°C After regeneration, the dehydrochlorination process was restarted at the same operating conditions as noted hereinbefore Start-up conversion of PDC was found to be 40 percent.
- a stock solution of lanthanum chloride was prepared by dissolving lanthanum chloride (30 16 g) into deionized and distilled water ( 18.50 g). The stock solution was used to impregnate alumina (Norton alumina) to incipient wetness at ambient temperature After drying the impregnated alumina overnight in air at ambient temperature, the alumina-supported lanthanum chloride catalyst was further dried in air at 120°C.
- the catalyst ( 10.46 g) was loaded into a reactor and tested in the dehydrochlorination of 1 ,2-d ⁇ chloropropane in the manner described in Example 1 Process conditions and results are shown in Table 1 , where it is seen that the alumina-supported lanthanum chloride catalyst was capable of dehydrochlo ⁇ nating 1 ,2-d ⁇ chloropropane predominantly to allyl chloride and cis- 1- chloropropene. both valuable products, in a combined selectivity of over 90 percent. Only a small amount of trans- 1 -chloropropene was formed. The least valuable product, 2- chloropropene, was formed in an advantageously small quantity (0 40 percent of the exit stream).
- the catalyst was regenerated by passing a stream of steam at a rate of 1.2 cm /h and a stream of oxygen ( 15 percent in helium) at a rate of 200 cm 3 /m ⁇ n over the catalyst for 6 h at a temperature of 450°C. After regeneration, the dehydrochlorination process was restarted at the same operating conditions as noted hereinbefore. The catalyst was found to have regained full activity towards dehydrochlorination.
- the alumina-supported lanthanum chloride catalyst of Example 2 was tested in the dehydrochlorination of "allyl PDC," which is a mixture of halogenated C 3 alkanes and C 3 alkenes obtained as an intermediate cut from an allyl chloride process. More specifically, the "allyl PDC" feed comprises 87.44 percent 1 ,2-dichloropropane, 7.55 percent 2,3- dichloropropene, 2.02 percent 1 ,3-dichloropropene, 1.01 percent 3,3-dichloropropene, 0.37 percent allyl chloride, the balance of 1.6 percent being other chlorinated alkanes and alkenes, all percentages given in mole percent. Dehydrochlorination conditions were similar to those used in Example 2. Results are set forth in Table 2 hereinbelow.
- Allyl PDC comprises, as mole percentages, 87.44 percent 1,2- dichloropropane, 7.55 percent 2,3-dichloropropene, 2.02 percent 1,3- dichloropropene, 1.01 percent 3,3-dichloropropene, 0.37 percent allyl chloride, the balance of 1.6 percent being other chlorinated alkanes and alkenes. Conversion and product selectivities (Sel.) are given as mole percentages.
- the lanthanum chloride catalyst is capable of dehydrochlorinating "Allyl PDC" to a mixture of cis- 1 -chloropropene and allyl chloride, both valuable products, in a combined selectivity of greater than 90 percent. A small amount of trans- 1 -chloropropene is formed. 2-Chloropropene, which is the least desirable product, is advantageously formed in a selectivity of less than 1 percent
- the catalyst was regenerated by passing a stream of steam at a rate of 1.2 cm /h and a stream containing oxygen and helium ( 15 percent oxygen in helium) at a rate of 200 cm /min over the catalyst for 2 h at a temperature of 400°C. After regeneration, the dehydrochlorination process was restarted at the same operating conditions as noted hereinbefore. Start-up conversion of PDC was found to be 55 percent.
- Example 2 The alumina-supported lanthanum chloride catalyst of Example 2 was evaluated in the dehydrochlorination of 1 ,2,3-trichloropropane. Process conditions were similar to those used in Example 2, with the results set forth in Table 3.
- the lanthanum chloride catalyst is capable of dehydrochlo ⁇ nating 1 ,2,3-trichloropropane predominantly to cis- and trans- 1 ,3- dichloropropenes, which are valuable products, in a combined selectivity of 72.2 percent.
- the TCP conversion had decreased to 1.3 percent.
- the catalyst was regenerated by passing a stream of steam at a rate of 1.2 cm /h and a stream containing oxygen and helium (15 mole percent oxygen in helium) at a rate of 200 cm 3 /m ⁇ n over the catalyst for 2 h at a temperature of 400°C. After regeneration, the dehydrochlorination process was restarted at the same operating conditions as noted hereinbefore. Start-up conversion of TCP was found to be 6.0 percent.
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Abstract
A process for the dehydrohalogenation of halogenated alkanes involving contacting a halogenated alkane having three or more carbon atoms with a rare earth halide or rare earth oxyhalide catalyst under process conditions sufficient to prepare an alkene or halogenated alkene. The process converts low valued halogenated alkanes, which are by-products of industrial chlorination processes, into higher valued alkenes and halogenated alkenes. 1,2-Dichloropropane, for example, can be dehydrochlorinated predominantly to allyl chrloride and 1-chloropropene with little production of low value 2-chloropropene. 1,2,3-Trichloropropane can be dehydrochlorinated predominantly to 1,3-dichloropropene which is useful in soil fumigants.
Description
DEHYDROHA OGENATION OF HALOGENATED ALKANES USING RARE EARTH HALIDE OR OXYHALIDE CATALYST
This application claims the benefit of U.S. Provisional Application No. 60/166,897, filed November 22, 1999.
This invention pertains to a process of catalytically dehydrohalogenating a halogenated alkane, such as 1 ,2-dιchloropropane or 1 ,2,3-tπchloropropane, to produce an alkene or a halogenated alkene, such as allyl chloride or 1 ,3-dichloropropene, respectively
Alkenes, such as propylene. find wide utility as monomers in the manufacture of polyolefin polymers and synthetic rubbers. Halogenated alkenes find utility in a variety of basic and specialty chemicals. Allyl chloride, for example, is a valuable starting material in the preparation of epichlorohydrm. from which epoxy polymers are manufactured. 1 ,3- Dichloropropene and other chlorinated alkenes find utility as components in nematocides, soil fumigants, insecticides, and as monomers in the production of plastics, resins, and chemical intermediates.
The manufacture of allyl chloride involves contacting propylene and chlorine rapidly at elevated temperatures, as described, for example, in U S. 4,319,062. The by-product stream that is obtained as material of intermediate boiling point, after removing the lower boiling fractions containing the allyl chloride and the higher boiling fractions containing mostly cis- and trans- 1 ,3-dιchloropropenes by distillation, contains a variety of chlorinated propanes and propenes including 1 ,2-dιchloropropane, 3,3-dιchloropropene, 2,3- dichloropropene, 2.2-dιchloropropane, and other related chlorinated C3 species. Usually, 1 ,2-dιchloropropane is present as a major component, often amounting to approximately 70 to 95 mole percent, and typically 75 to 90 mole percent, of the by-product stream. Usually 3,3-dιchloropropene is present in an amount ranging from 0.1 to 15 mole percent of the by- product stream. 3,3-Dichloropropene is typically isomeπzed to yield the above-mentioned 1 ,3-dichloropropene, as described, for example, in US 5,072,063 and 5,510,546. 1 ,2- Dichloropropane is not useful per se and must also be up-graded to a product of higher value.
Typically, 1,2-dιchloropropane has been up-graded via thermal dehydrochloπnation to allyl chloride By-products of the thermal dehydrochloπnation include cis- and trans- 1 - chloropropene, which can be recycled to the aforementioned allyl chloride manufacturing process, wherein propylene is chlorinated to allyl chloride. The chlorination therein of cis and trans- 1 -chloropropene produces 1.3-dιchloropropene, a valuable chemical used in fumigant formulations, as indicated previously A less favorable by-product of the thermal dehydrochloπnation of 1 ,2-dιchloropropane is 2-chloropropene, which cannot be readily used or up-graded to a product of higher value It would be highly desirable to discover a dehydrohalogenation process which converts 1 ,2-dιchloropropane principally to allyl chloride and 1 -chloropropenes with essentially no formation, or at best a lower formation, of the less valuable 2-chloropropene
As another example, allyl chloride product can itself be chlorinated to form 1 ,2,3- trichloropropane, a by-product of very limited value and utility, but 1 ,2,3-tπchloropropane can be dehydrohalogenated to form 1 ,3-dιchloropropene, which has utility in fumigants Conventional dehydrohalogenation processes, however, typically produce unfavorable yields of 2,3-dιchloropropene, which may be difficult to separate by simple distillation It would be desirable to discover a dehydrohalogenation process that converts 1 ,2,3- trichloropropane to the more desirable cis and trans- 1 ,3-dιchloropropene products with reduced levels of 2,3-dιchloropropene
This invention is a novel process of dehydrohalogenating a halogenated alkane to form an alkene or a halogenated alkene The novel process of this invention comprises contacting a halogenated alkane having three or more carbon atoms with a dehydrohalogenation catalyst under reaction conditions sufficient to produce the alkene or halogenated alkene In the novel process of this invention, the dehydrohalogenation catalyst comprises a rare earth halide or rare earth oxyha de compound
The novel process of this invention simply and efficiently converts a halogenated alkane via dehydrohalogenation (cracking) in the presence of a rare earth halide or rare earth oxyhahde catalyst to an alkene or a halogenated alkene The process of this invention can
be advantageously used to up-grade lower valued halogenated alkanes to higher valued alkenes or halogenated alkenes suitable for commercial use. As an example, 1 ,2- dichloropropane, produced in the chlorination of propylene to allyl chloride, can be advantageously dehydrohalogenated by the process of this invention to allyl chloride and 1- chloropropene in high yield. 2-Chloropropene, an undesirable by-product of the dehydrohalogenation of 1 ,2-dichloropropane, is produced at an advantageously low level in the process of this invention. 1 -Chloropropene, produced in the cracking process herein of 1 ,2-dichloropropane, can be beneficially recycled to the allyl chloride reactor and chlorinated to 1 ,3-dichloropropene, which is useful in fumigants. As another example of the process of this invention, 1 ,2,3-trichloropropane can be beneficially dehydrohalogenated to produce predominantly 1 ,3-dichloropropene, having the aforementioned utility in fumigants. As a further advantage of this invention, typically the dehydrohalogenation occurs at a temperature that is lower than the temperatures required of prior art dehydrohalogenation processes. Accordingly, the process of this invention consumes less energy than prior art processes and provides the opportunity for higher conversion at lower operating temperatures. As yet another advantage, the rare earth halide catalyst of this invention is soluble in water. Accordingly, should process equipment, such as filters, transport lines, valves, and intricate small or curved parts of the reactor, become plugged with catalyst particles, the plugged parts need only be washed with water to restore the parts to working order.
In its broadest concept, this invention is a novel process comprising the catalytic dehydrohalogenation of a halogenated alkane to form an alkene or a halogenated alkene. The novel process of this invention comprises contacting a halogenated alkane having three or more carbon atoms with a dehydrohalogenation catalyst under reaction conditions sufficient to prepare the alkene or halogenated alkene. The dehydrohalogenation catalyst used in the novel process of this invention comprises a rare earth halide or rare earth oxyhahde compound.
In a preferred embodiment, this invention is a novel process comprising the catalytic dehydrochlorination of a chlorinated alkane so as to form an alkene or a chlorinated alkene. In this preferred embodiment, the novel process comprises contacting a chlorinated
alkane having three or more carbon atoms with a dehydro-chloπnation catalyst under reaction conditions sufficient to prepare the corresponding alkene or chlorinated alkene, the dehydrochlorination catalyst being a rare earth halide or rare earth oxyhahde, more preferably, a rare earth chloride or rare earth oxychloπde. In another more preferred embodiment, the chlorinated alkane is 1 ,2-dιchloropropane or a mixture of chlorinated alkanes comprising predominantly 1 ,2-dιchloropropane, and the halogenated alkene comprises allyl chloride, 1 -chloropropene, or essentially a combination thereof. In another more preferred embodiment, the chlorinated alkane is 1 ,2,3-trichloropropane. and the halogenated alkene is 1 ,3-dichloropropene
The halogenated alkane, which is used in the process of this invention, can be any halogenated alkane having three or more carbon atoms The halogenated alkane may also be an essentially pure halogenated alkane or a mixture of halogenated alkanes Preferably, the halogenated alkane is a halogenated C^ g alkane or mixture of halogenated C3 8 alkanes. More preferably, the halogenated alkane is a halogenated C 4 alkane or a mixture of halogenated C3 4 alkanes. The halogenated alkane will possess at least one halogen substituent Full saturation with halogen substituents is typically not preferred. At least one hydrogen atom is preferably present on at least one of the carbon atoms, because the dehydrohalogenation proceeds by eliminating hydrogen halide from the halogenated alkane. Each halogen substituent, which is present, may be independently selected from chlorine, bromine, and iodine substituents Preferably, the halogen substituent is selected from chlorine or bromine substituents Fluorine substituents may be present on the halogenated alkane, but typically fluorine remains inert and does not participate in dehydrofluoπnation (loss of HF) Non-limiting examples of suitable halogenated alkanes include 1 ,2- dichloropropane, 1 ,2,3-trichloropropane, 1 ,2-dichlorobutane, 2.3-dιchlorobutane, 1 ,2,3- tπchlorobutane, 1 ,2-dιbromopropane, 1 ,2,3-tπbromopropane, 1 ,2-dιbromobutane, 1 ,2,3- tπbromobutane, as well as isomers and higher homologues of the aforementioned halogenated alkanes, and mixtures of any of the aforementioned compounds The halogenated alkanes may be provided in mixtures which also contain halogenated alkenes. Most preferably, the halogenated alkane is 1 ,2-dιchloropropane or 1 ,2,3-trichloropropane.
In another most preferred embodiment, the halogenated alkane is a mixture of 1 ,2- dichloropropane with di- and tri-chlorinated C3 alkanes and C3 alkenes. These mixtures, known in the art as "allyl propylene dichloride" ("allyl PDC"), may be obtained as byproduct streams in the chlorination of propylene to form allyl chloride. "Allyl PDC" compositions can vary with the specific conditions in the allyl chloride reactor and the particular purification steps employed. Purification steps can include distillation, isomerization, selective reaction, and other separation operations known to those skilled in the art. A typical "allyl PDC" composition comprises from 70 to 95 mole percent 1 ,2- dichloropropane, from 1 to 15 mole percent 2,3-dichloropropene, from 0.1 to 15 mole percent 3,3-dichloropropene, from 0.1 to 10 mole percent 1 ,3-dichloropropene isomers, from 0 to 3 mole percent 1 , 1-dichloropropene, and may contain other chlorinated alkanes and alkenes as well as non-chlorinated compounds.
Optionally, if desired, the feed to the dehydrohalogenation process comprising the halogenated alkane can be diluted with a diluent or carrier gas, which may be any gas that does not substantially interfere with the dehydrohalogenation process. The diluent may assist in removing products and heat from the reactor and in reducing the number of undesirable side-reactions. Non-limiting examples of suitable diluents include nitrogen, argon, helium, carbon monoxide, carbon dioxide, steam, condensable halogenated hydrocarbons, and mixtures thereof. For the purposes of this invention, the term
"condensable halogenated hydrocarbons" will include any halogenated hydrocarbon which is substantially inert with respect to the dehydrohalogenation process of this invention and which is readily separated from the dehydrohalogenation product effluent by fractional distillation or cooling. Fully perhalogenated alkenes, such as perchloroethylene and perfluoroethylene, may be suitably employed as the condensable halogenated hydrocarbon. The quantity of diluent employed typically ranges from greater than 10 mole percent, and preferably, greater than 20 mole percent, to typically, less than 90 mole percent, and preferably, less than 70 mole percent, based on the total moles of starting halogenated alkane and optional diluent.
One catalyst which is employed in the novel dehydrohalogenation process of this invention comprises a rare earth halide. The rare earths are a group of 17 elements
consisting of scandium (atomic number 21 ), yttrium (atomic number 39) and the lanthanides (atomic numbers 57-71) [James B. Hedrick, U.S. Geological Survey - Minerals Information - 1997, "Rare-Earth Metals"]. Preferably, herein, the term is taken to mean an element selected from lanthanum, cerium, neodymium, praseodymium, dysprosium, samarium, yttrium, gadolinium, erbium, ytterbium, hoimium, terbium, europium, thulium, lutetium, and mixtures thereof. Preferred rare earth elements for use in the aforementioned dehydrohalogenation process are those which are typically considered as being single valency metals Catalytic performance of multi-valency metals appears to be less desirable than those that are single valency. The rare earth element for this invention is even more preferably selected from lanthanum, neodymium, praseodymium, and mixtures thereof. Most preferably, the rare earth element used in the catalyst is lanthanum or a mixture of lanthanum with other rare earth elements
Preferably, the rare earth halide is represented by the formula MXi wherein M is at least one rare earth element selected from the group consisting of lanthanum, cerium, neodymium, praseodymium, dysprosium, samarium, yttrium, gadolinium, erbium, ytterbium, hoimium, terbium, europium, thulium, lutetium, and mixtures thereof; and wherein X is chloride, bromide, or iodide More preferably, X is chloride, and the more preferred rare earth halide is represented by the formula MC1 , wherein M is defined hereinbefore. Most preferably, X is chloride and M is lanthanum, and the rare earth halide is lanthanum chloride, which optionally can be mixed with other rare earth chlorides
In an alternative embodiment, the rare earth halide catalyst is porous, which means that the catalyst contains void spaces, such as channels, pores, and/or cavities, within its crystallographic structure. This porosity creates surface area throughout the compound. Typically, the porous rare earth halide has a BET surface area greater than 5 πr/g, as determined by the BET (Brunauer-Emmet-Teller) method of measuring surface area, described by S Brunauer, P. H. Emmett, and E. Teller, Journal of the American Chemical Society, 60, 309 ( 1938). Preferably, the porous rare earth halide has a BET surface area greater than 10 πr/g, more preferably, greater than 15 m7g, even more preferably, greater than 20 m"/g, and most preferably, greater than 30 m7g. For these above measurements, the
nitrogen adsorption isotherm is measured at 77K, and the surface area is calculated from the isotherm data utilizing the BET method
In another aspect, the catalyst of this novel dehydrohalogenation process compπses a rare earth oxyhahde, the rare earths being identified hereinbefore Preferably, this form of the catalyst is represented by the formula MOX, wherein M is at least one rare earth element selected from the group consisting of lanthanum, cerium, neodymium, praseodymium, dysprosium, samarium, yttrium, gadolinium, erbium, ytterbium, hoimium, terbium, europium, thulium, lutetium, and mixtures thereof, and wherein X is selected from the group consisting of chloride, bromide, and iodide More preferably, the rare earth oxyhahde is a rare earth oxychloπde, represented by the formula MOC1, wherein M is defined hereinbefore Most preferably, the rare earth oxychloπde is lanthanum oxychloπde, LaOCl, optionally mixed with other rare earth oxychloπdes
In an alternative embodiment, the rare earth oxyhahde is porous, as defined hereinbefore in connection with the rare earth halide Typically, the porous rare earth oxyhahde has a BET surface area of greater than 12 m7g, preferably, greater than 15 m7g, more preferably, greater than 20 m7g, and most preferably, greater than 30 m7g Generally, the BET surface area is less than 200 m7g In addition, it is noted that the MOC1 phases possess characteristic powder X-Ray Diffraction (XRD) patterns that are distinct from the MCL phases
It may also be advantageous to include other elements within the catalyst For example, preferable elemental additives include alkali and alkaline earths, boron, phosphorous, sulfur, germanium, titanium, zirconium, hafnium, the noble metals, and combinations thereof The noble metals include ruthenium, rhodium, palladium, osmium, indium, platinum, silver, and gold These elements can be present to alter the catalytic performance of the composition or to improve the mechanical properties (for example, attrition-resistance) of the material The total concentration of elemental additives in the catalyst is typically greater than 0 01 weight percent and typically less than 20 weight percent, based on the total weight of the catalyst
In the discussion hereinabove, the catalysts are not bound to a support or carrier. In an alternative embodiment, the rare earth halide or rare earth oxyhahde catalyst may be bound to, extruded with, or deposited onto a catalyst support or carrier. Non-limiting examples of suitable carriers include alumina, silica, silica-alumina, porous aluminosilicate (zeolite), silica-magnesia, bauxite, magnesia, silicon carbide, titanium oxide, zirconium oxide, zirconium silicate, or combinations thereof. In this supported embodiment, the support is used in a quantity greater than 1 weight percent, and preferably, greater than 10 weight percent, based on the total weight of the catalyst and support. In this supported embodiment, the support is used in a quantity less than 90 weight percent, preferably, less than 80 weight percent, and more preferably, less than 70 weight percent, based on the total weight of the catalyst and support.
The rare earth halide and rare earth oxyhahde catalysts may be obtained from commercial suppliers. The porous rare earth halide and porous rare earth oxyhahde catalysts may be synthesized as described hereinafter, as the porous embodiments of the catalyst are not known to be commercially available at the current time.
A method currently felt to be preferable for forming the composition comprising the porous rare earth oxyhahde (MOX) comprises the following steps: (a) preparing a solution of a halide salt of the rare earth element or elements in a solvent comprising either water, an alcohol, or mixtures thereof; (b) adding a base to cause the formation of a precipitate; and (c) collecting and calcining the precipitate in order to form the MOX. Preferably, the halide salt is a rare earth chloride salt, for example, any of such salts which are commercially available. Typically, a nitrogen-containing base is employed selected from ammonium hydroxide, alkyl amines, aryl amines, arylalkyl amines, alkyl ammonium hydroxides, aryl ammonium hydroxides, arylalkyl ammonium hydroxides, and mixtures thereof. The nitrogen-containing base may also be provided as a mixture of a nitrogen-containing base with other bases that do not contain nitrogen. Preferably, the nitrogen-containing base is ammonium hydroxide or tetra(alkyl)ammonium hydroxide, more preferably, tetra(Cι_ 0 alkyl)ammonium hydroxide. The solvent in Step (a) is preferably water. Porous rare earth oxychlorides may also be produced by appropriate use of alkali or alkaline earth hydroxides, preferably, with the buffering action of a nitrogen-containing base. Generally, the
precipitation is conducted at a temperature greater than 0°C Generally, the precipitation is conducted at a temperature less than 200°C, preferably, less than 100°C The precipitation is conducted generally at ambient atmospheric pressure, although higher pressures may be used, as necessary, to maintain liquid phase at the precipitation temperature employed The calcination is typically conducted at a temperature greater than 200°C, preferably, greater than 300°C, but less than 800°C, and preferably, less than 600°C Mixtures of carboxylic acid and rare earth chloride salts also can yield rare earth oxychlorides upon appropriate decomposition
A method currently felt to be preferable for forming the catalyst composition comprising the porous rare earth halide (MX ) comprises the following steps (a) preparing a solution of a halide salt of the rare earth element or elements in a solvent comprising either water, an alcohol, or mixtures thereof, (b) adding a base to cause the formation of a precipitate, (c) collecting and calcining the precipitate, and (d) contacting the calcined precipitate with a halogen source Preferably, the rare earth halide is a rare earth chloride salt, such as any commercially available rare earth chloride Preferably, the solvent is water, and the base is any of those bases noted hereinbefore in connection with the preparation of MOX Likewise, the precipitation is generally conducted at a temperature greater than 0°C and less than 200°C, preferably less than 100°C, at ambient atmospheric pressure or a higher pressure so as to maintain liquid phase The calcination is typically conducted at a temperature greater than 200°C, preferably, greater than 300°C, but less than 800°C, and preferably, less than 600°C Preferably, the halogen source is a halogen halide, such as hydrogen chloride, hydrogen bromide, or hydrogen iodide, or is a molecular halogen, such as molecular chlorine, bromine, or iodine More preferably, the halogen source is hydrogen chloride or molecular chlorine The contacting with the source of halogen is generally carried out at a temperature greater than 150°C, and preferably, greater than 200°C The contacting with the source of halogen is usually carried out at a temperature less than 450°C, and preferably, less than 250°C Typical pressures for the contacting with the source of halogen range from ambient atmospheric pressure to pressures less than 150 psia ( 1 ,034 kPa)
The dehydrohalogenation process of this invention can be conducted in a reactor of any conventional design suitable, preferably, for gas phase processes, including batch, fixed bed, fluidized bed. transport bed, continuous and intermittent flow reactors. Any process conditions (for example, molar ratios of feed components, temperature, pressure, gas hourly space velocity), can be employed, provided that the desired product alkene or halogenated alkene is selectively obtained. Typically, the process temperature is greater than 100°C, preferably, greater than 150°C, and more preferably, greater than 180°C. Typically, the process temperature is less than 500°C, preferably, less than 300°C, and more preferably, less than 250°C. It is further within the scope of this invention to preheat the reactant feed comprising the halogenated alkane plus optional diluent. Typically, the preheat temperature is greater than 50°C, preferably, greater than 100°C, but typically equal to or less than the process temperature. Preferably, the preheat temperature is less than 500°C, and preferably, less than 300°C. Ordinarily, the process will be conducted at atmospheric pressure or a higher pressure. Typically then, the pressure will be equal to or greater than 14 psia (96 kPa), but typically less than 1 ,000 psia (6,895 kPa), preferably, less than 600 psia (4, 137 kPa), and more preferably, less than 300 psig (2,068 kPa). Typically, the total gas hourly space velocity (GHSV) of the feed (halogenated alkane plus optional diluent) will be greater than 10 ml total feed per ml catalyst per hour (h" 1), preferably, greater than 100 h" 1, more preferably, greater than 400 h" . Typically, the total gas hourly space velocity of the feed will be less than 30,000 h" 1, preferably, less than 20,000 h" 1, and more preferably, less than 10,000 h0
The alkene or halogenated alkene formed in the dehydrohalogenation cracking process of this invention may be any alkene or halogenated alkene. Generally, the product alkene contains the same number of carbon atoms as the reactant alkane. Preferably, the alkene or halogenated alkene will be a C .8, more preferably, a C3.4 alkene or halogenated alkene. The halogenated alkene will contain one or more halogen substituents, preferably, selected from chlorine, bromine, and iodine. More preferably, the halogen substituent is chlorine. Non-limiting examples of product alkenes include propylene and butenes, and higher homologues thereof. Non-limiting examples of halogenated alkenes include chloropropenes, dichloropropenes, chlorobutenes, dichlorobutenes, trichlorobutenes, bromopropenes, dibromopropenes, bromobutenes, dibromobutenes. Most preferably, the
alkene is propylene or butene. Most preferably, the halogenated alkene is selected from the group consisting of allyl chloride, 1 -chloropropene, 1 ,3-dichloropropene, and mixtures thereof.
1 ,2-Dichloropropane, which is produced as a substantial by-product in the manufacture of allyl chloride, can be advantageously dehydrohalogenated via the process of this invention selectively to mixtures of allyl chloride and 1 -chloropropene, with very low levels of unwanted 2-chloropropene being formed. Generally, in the process of this invention, the conversion of 1 ,2-dichloropropane is greater than 50 mole percent, and preferably, greater than 60 mole percent at temperatures less than 240°C. For the purposes of this invention, "conversion" is defined as the mole percentage of halogenated alkane feed, such as 1 ,2-dichloropropane feed, reacted in the dehydrohalogenation process. Typically, the total selectivity to allyl chloride and 1 -chloropropene exceeds 90 mole percent. Typically, the selectivity to unwanted 2-chloropropene is less than 2 mole percent, and preferably, less than 1 mole percent. For the purposes of this invention, "selectivity" is defined as the mole percentage of reacted halogenated alkane which forms the specified product.
The 1 -chloropropene, which is produced during dehydrohalogenation of 1,2- dichloropropane, can be advantageously recycled to an allyl chloride reactor, where propylene is chlorinated to allyl chloride. In the reaction environment therein, 1 - chloropropene is converted to 1 ,3-dichloropropene, a component of soil fumigants. From another route, 1 ,2,3-trichloropropane, produced in the chlorination of allyl chloride, can be selectively dehydrochlorinated by the process of this invention to a mixture comprising predominantly cis and trans- 1 ,3-dichloropropenes. A combined selectivity of greater than 55 mole percent of cis and trans- 1 ,3-dichloro-propenes is typically achieved. Preferably, a combined selectivity of greater than 70 mole percent cis and trans- 1 ,3-dichloropropenes is achieved.
One skilled in the art may recognize that the process of this invention cracks hydrogen halide, preferably, hydrogen chloride, from the halogenated alkane feed. The hydrogen halide, which is formed, may be recycled to an oxidative halogenation process,
preferably an oxidative chlorination process, wherein a hydrocarbon or halogenated hydrocarbon (the starting hydrocarbon) can be reacted with oxygen and the recycle hydrogen halide in the presence of an oxidative halogenation catalyst, for example, a copper-based catalyst, to produce a halogenated hydrocarbon having a greater number of halogenated substituents than the starting hydrocarbon. The oxychlonnation of ethylene with hydrogen chloride and oxygen to form ethylene dichloπde is an example of one such use of the recycle hydrogen chloride stream.
When the dehydrohalogenation catalyst of this process invention is partially or fully deactivated, the catalyst may be easily regenerated A preferred method of regeneration involves contacting the partially or fully deactivated catalyst with steam at a temperature sufficient to regenerate, at least in part, the catalytic activity Generally, the steam is provided in a regeneration gas mixture containing an inert diluent, such as nitrogen, helium, or argon. The quantity of steam in the mixture may vary from greater than 0.005 mole percent to less than 50 mole percent, based on the total moles of regeneration gas.
Optionally, oxygen may be added to the regeneration gas to aid in the removal of coke. Oxygen-containing mixtures can contain from greater than 1 mole percent to less than 50 mole percent oxygen, as desired, but preferably, the oxygen content of the regeneration gas mixture is greater than 2 mole percent and less than 20 mole percent, based on the total moles of regeneration gas mixture The regeneration is usually conducted at a temperature greater than 200°C, preferably, greater than 300°C. The regeneration is usually conducted at a temperature less than 700°C, and preferably, less than 600°C. The duration of the regeneration can range from greater than 30 minutes to less than 12 hours, and preferably from greater than 30 minutes to less than 5 hours.
The following examples are provided as an illustration of the process of this invention. These examples should not be construed as limiting the invention in any manner. In light of the disclosure herein, those of skill in the art will recognize alternative embodiments, for example of reactants, process conditions, and catalyst species, which all fall within the scope of this invention Unless otherwise noted, percentages are given in units of mole percent.
Example 1
A porous lanthanum oxychloπde catalyst was prepared as follows. Lanthanum chloride (LaCl 7 H O, 15.0 g) was dissolved in deio zed water ( 150 ml). Ammonium hydroxide (6 M, 20 ml) was added to the lanthanum chloride solution quickly with stirring, resulting in a white precipitate. The mixture was centπfuged and the excess liquid decanted yielding a lanthanum-containing gel. The precipitate was calcined at 400°C for 4 hours yielding a porous lanthanum oxychloπde catalyst. X-ray diffraction data indicated the presence of a quasi-crystalline form of lanthanum oxychloπde. The surface area of the catalyst was 25.8 m7g, as measured by the BET method.
The lanthanum oxychloπde (7 35 g, 5 cm ), prepared hereinabove, was charged into a tubular reactor [nickel base, 1/2 inch ( 1.25 cm) O.D. x 14 inches (35 cm) length] The catalyst was dried at 130°C under flowing helium for 1 h and further heated to 230°C under flowing helium. 1 ,2-Dichloropropane (PDC) was pumped via a Gilson Model 305 pump at a rate of 7.68 cm /h and mixed with helium at a flow rate of 33 cm /min to form a PDC/He feed. The feed was preheated to 170°C and fed to the reactor operating at 230°C and atmospheric pressure. The feed gas hourly space velocity was 682 h ' . The composition of the exit feed is shown in Table 1.
Table 1. Dehydrochlorination of 1 ,2-Dichloropropane (PDC)
a. PDC Conversion and product selectivities (Sel.) are given in mole percentages. b. Feed. PDC, 7.68 cm h, helium, 33 cm /min; 230°C, atmospheric pressure; feed GHSV, 682 h"1 ; feed residence time, 5.3 sec.
From Table 1 it is seen that a lanthanum oxychloπde catalyst is capable of dehydrochloπnating 1 ,2-dιchloropropane to cis- 1 -chloropropene and allyl chloride, both valuable products, in a combined selectivity of over 90 percent. A small amount of trans- 1- chloropropene is formed 2-Chloropropene, which is the least desirable product, is advantageously formed in a selectivity of less than 1 percent.
After 16 h of operation, the PDC conversion had decreased to 31 percent. The catalyst was regenerated by passing a stream of steam at a rate of 1.2 cm /h and a stream of oxygen and helium ( 15 percent oxygen in helium) at a rate of 200 cm /min over the catalyst for 2 h at a temperature of 400°C After regeneration, the dehydrochlorination process was restarted at the same operating conditions as noted hereinbefore Start-up conversion of PDC was found to be 40 percent.
Example 2
A stock solution of lanthanum chloride was prepared by dissolving lanthanum chloride (30 16 g) into deionized and distilled water ( 18.50 g). The stock solution was used to impregnate alumina (Norton alumina) to incipient wetness at ambient temperature After drying the impregnated alumina overnight in air at ambient temperature, the alumina- supported lanthanum chloride catalyst was further dried in air at 120°C. The catalyst ( 10.46 g) was loaded into a reactor and tested in the dehydrochlorination of 1 ,2-dιchloropropane in the manner described in Example 1 Process conditions and results are shown in Table 1 , where it is seen that the alumina-supported lanthanum chloride catalyst was capable of dehydrochloπnating 1 ,2-dιchloropropane predominantly to allyl chloride and cis- 1- chloropropene. both valuable products, in a combined selectivity of over 90 percent. Only a small amount of trans- 1 -chloropropene was formed. The least valuable product, 2- chloropropene, was formed in an advantageously small quantity (0 40 percent of the exit stream).
After 16 h of operation, the catalyst was regenerated by passing a stream of steam at a rate of 1.2 cm /h and a stream of oxygen ( 15 percent in helium) at a rate of 200 cm3/mιn over the catalyst for 6 h at a temperature of 450°C. After regeneration, the
dehydrochlorination process was restarted at the same operating conditions as noted hereinbefore. The catalyst was found to have regained full activity towards dehydrochlorination.
Example 3
The alumina-supported lanthanum chloride catalyst of Example 2 was tested in the dehydrochlorination of "allyl PDC," which is a mixture of halogenated C3 alkanes and C3 alkenes obtained as an intermediate cut from an allyl chloride process. More specifically, the "allyl PDC" feed comprises 87.44 percent 1 ,2-dichloropropane, 7.55 percent 2,3- dichloropropene, 2.02 percent 1 ,3-dichloropropene, 1.01 percent 3,3-dichloropropene, 0.37 percent allyl chloride, the balance of 1.6 percent being other chlorinated alkanes and alkenes, all percentages given in mole percent. Dehydrochlorination conditions were similar to those used in Example 2. Results are set forth in Table 2 hereinbelow.
Table 2. Dehydrochlorination of "Allyl PDC ι»a,b
a. "Allyl PDC" comprises, as mole percentages, 87.44 percent 1,2- dichloropropane, 7.55 percent 2,3-dichloropropene, 2.02 percent 1,3- dichloropropene, 1.01 percent 3,3-dichloropropene, 0.37 percent allyl chloride, the balance of 1.6 percent being other chlorinated alkanes and alkenes. Conversion and product selectivities (Sel.) are given as mole percentages. b. Feed: "Allyl PDC," 7.68 cmVh, helium, 33 cm /min; 230°C; atmospheric pressure; feed GHSV, 682 h"1; residence time, 5.3 sec.
From Table 2 it is seen that the lanthanum chloride catalyst is capable of dehydrochlorinating "Allyl PDC" to a mixture of cis- 1 -chloropropene and allyl chloride, both valuable products, in a combined selectivity of greater than 90 percent. A small
amount of trans- 1 -chloropropene is formed. 2-Chloropropene, which is the least desirable product, is advantageously formed in a selectivity of less than 1 percent
After 16 h of operation, the "Allyl PDC" conversion had decreased to 15 percent. The catalyst was regenerated by passing a stream of steam at a rate of 1.2 cm /h and a stream containing oxygen and helium ( 15 percent oxygen in helium) at a rate of 200 cm /min over the catalyst for 2 h at a temperature of 400°C. After regeneration, the dehydrochlorination process was restarted at the same operating conditions as noted hereinbefore. Start-up conversion of PDC was found to be 55 percent.
Example 4
The alumina-supported lanthanum chloride catalyst of Example 2 was evaluated in the dehydrochlorination of 1 ,2,3-trichloropropane. Process conditions were similar to those used in Example 2, with the results set forth in Table 3.
Table 3. Dehydrochlorination of
a. TCP conversion and product selectivities (Sel.) given in mole percentages. b Feed. TCP, 7.68 cm /h, helium, 33 cm /min; 230°C; atmospheric pressure; feed
GHSV, 682 h '; residence time, 5.3 sec.
From Table 3 it is seen that the lanthanum chloride catalyst is capable of dehydrochloπnating 1 ,2,3-trichloropropane predominantly to cis- and trans- 1 ,3- dichloropropenes, which are valuable products, in a combined selectivity of 72.2 percent.
After 16 h of operation, the TCP conversion had decreased to 1.3 percent. The catalyst was regenerated by passing a stream of steam at a rate of 1.2 cm /h and a stream containing oxygen and helium (15 mole percent oxygen in helium) at a rate of 200 cm3/mιn
over the catalyst for 2 h at a temperature of 400°C. After regeneration, the dehydrochlorination process was restarted at the same operating conditions as noted hereinbefore. Start-up conversion of TCP was found to be 6.0 percent.
Claims
1. A process of dehydrohalogenating a halogenated alkane to form an alkene or a halogenated alkene, comprising contacting a halogenated alkane having three or more carbon atoms with a rare earth halide or rare earth oxyhahde catalyst under reaction conditions sufficient to prepare the alkene or the halogenated alkene.
2. The process of Claim 1 wherein the halogenated alkane is a chlorinated C3. alkane or a mixture of chlorinated C3.4 alkanes.
3. The process of Claim 2, wherein the halogenated alkane is 1 ,2- dichloropropane or 1,2,3-trichloropropane.
4. The process of Claim 1 wherein the halogenated alkane is a mixture comprising 1 ,2-dichloropropane and di- and tri-chlorinated C alkanes and C3 alkenes.
5. The process of Claim 1, wherein a diluent is employed that is nitrogen, helium, argon, carbon monoxide, carbon dioxide, steam, condensable halogenated hydrocarbons or a mixture of one or more of these.
6. The process of any of Claims 1 through 5, wherein the rare earth halide is represented by the formula MX3, wherein M is at least one rare earth selected from lanthanum, cerium, neodymium, praseodymium, dysprosium, samarium, yttrium, gadolinium, erbium, ytterbium, hoimium, terbium, europium, thulium, and lutetium; and wherein X is chloride, bromide, or iodide.
7. The process of Claim 6 wherein M is lanthanum, X is chloride, and the rare earth halide is lanthanum chloride.
8. The process of Claim 6 wherein the rare earth halide is porous with a BET surface area greater than 5 m /g.
9. The process of Claim 8 wherein the porous rare earth hahde has a BET surface area greater than 15 m7g.
10. The process of Claim 6 wherein the catalyst is deposited on, bonded to, or extruded with a catalyst support or carrier.
1 1. The process of any of Claims 1 through 5, wherein the rare earth oxyhahde is represented by the formula MOX, wherein M is at least one rare earth lanthanum, cerium, neodymium, praseodymium, dysprosium, samarium, yttrium, gadolinium, erbium, ytterbium, hoimium, terbium, europium, thulium and lutetium; and wherein X is chloride, bromide, or iodide.
12. The process of Claim 1 1 wherein M is lanthanum, X is chloride, and the rare earth oxyhahde is lanthanum oxychloπde
13. The process of Claim 1 1 wherein the rare earth oxyhahde is porous and has a BET surface area greater than 12 m7g.
14. The process of Claim 13 wherein the porous rare earth oxyhahde has a BET surface area greater than 20 m7g.
15. The process of Claim 1 1 wherein the catalyst is deposited on, bonded to, or extruded with a catalyst support or carrier.
16 The process of Claim 1 wherein the catalyst, when partially or fully deactivated, is regenerated by a method comprising contacting the partially or fully deactivated catalyst with a regeneration gas comprising steam under conditions sufficient to regenerate, at least in part, catalytic activity.
17 The process of Claim 16 wherein the regeneration gas further comprises oxygen.
18. A process of dehydrochloπnating 1 ,2-dichloropropane to allyl chloride and 1 -chloropropene. the process comprising contacting 1 ,2-dichloropropane with a rare earth halide or rare earth oxyhahde catalyst, the contacting being conducted at a temperature greater than 150°C and less than 500°C, so as to form allyl chloride and 1 -chloropropene.
19. The process of Claim 18 wherein the catalyst is a rare earth chloride or rare earth oxychloπde. wherein the rare earth is lanthanum, neodymium, praseodymium, or mixtures thereof.
20. The process of Claim 19 wherein the rare earth hahde is lanthanum chloride or the rare earth oxyhahde is lanthanum oxychloπde.
21. The process of any of Claims 18 through 20 wherein the rare earth hahde or rare earth oxyhahde is porous.
22. The process of Claim 21 wherein the porous rare earth hahde has a BET surface area greater than 5 m7g.
23. The process of Claim 21 wherein the porous rare earth oxyhahde has a BET surface area greater than 12 m7g.
24 The process of Claim 18 wherein the total selectivity to allyl chloride and 1 - chloropropene is greater than 90 mole percent.
25. The process of Claim 24 wherein 2-chloropropene is produced as a byproduct in a selectivity less than 2 mole percent.
26. The process of Claim 18 wherein the 1 -chloropropene produced is recycled to an allyl chloride reactor wherein it is chlorinated, and thereafter the chlorinated product is dehydrohalogenated to 1 ,3-dichloropropene.
27. The process of Claim 18 wherein the catalyst, when partially or fully deactivated, is regenerated by a method comprising contacting the partially or fully deactivated catalyst with steam, and optionally oxygen, at a temperature greater than 200°C and less than 700°C.
28. A process of dehydrochlorinating 1,2,3-trichloropropane to form 1,3- dichloropropene, the process comprising contacting 1,2,3-trichloropropane with a rare earth halide or a rare earth oxyhahde catalyst, the contacting being conducted at a temperature greater than 100°C and less than 500°C, so as to form 1,3-dichloropropene.
29. The process of Claim 28 wherein the catalyst is a rare earth chloride or rare earth oxychloride, wherein the rare earth is lanthanum, neodymium, praseodymium, or mixtures thereof.
30. The process of Claim 29 wherein the rare earth halide is lanthanum chloride, and the rare earth oxyhahde is lanthanum oxychloride.
31. The process of Claim 30 wherein the rare earth halide or rare earth oxyhahde is porous.
32. The process of Claim 31 wherein the porous rare earth halide has a BET surface area greater than 5 m7g.
33. The process of Claim 31 wherein the porous rare earth oxyhahde has a BET surface area greater than 12 m7g.
34. The process of Claim 28 wherein the catalyst, when partially or fully deactivated, is regenerated by a method comprising contacting the partially or fully deactivated catalyst with steam, and optionally oxygen, at a temperature greater than 200°C and less than 700°C.
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PCT/US2000/031488 WO2001038275A1 (en) | 1999-11-22 | 2000-11-16 | Dehydrohalogenation of halogenated alkanes using rare earth halide or oxyhalide catalyst |
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EP00976557A Expired - Lifetime EP1235773B1 (en) | 1999-11-22 | 2000-10-06 | Process for vinyl chloride manufacture from ethane and ethylene with partial hcl recovery from reactor effluent |
EP00980431A Withdrawn EP1235774A1 (en) | 1999-11-22 | 2000-11-16 | Dehydrohalogenation of halogenated alkanes using rare earth halide or oxyhalide catalyst |
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