CN1391548A - 使用稀土卤化物或卤氧化物催化剂进行卤代烷烃的脱氢卤化作用 - Google Patents
使用稀土卤化物或卤氧化物催化剂进行卤代烷烃的脱氢卤化作用 Download PDFInfo
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- CN1391548A CN1391548A CN00816025A CN00816025A CN1391548A CN 1391548 A CN1391548 A CN 1391548A CN 00816025 A CN00816025 A CN 00816025A CN 00816025 A CN00816025 A CN 00816025A CN 1391548 A CN1391548 A CN 1391548A
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- Prior art keywords
- rare earth
- lanthanum
- catalyzer
- porous
- earth halide
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 88
- -1 rare earth halide Chemical class 0.000 title claims abstract description 54
- 150000001335 aliphatic alkanes Chemical class 0.000 title claims abstract description 49
- 238000006704 dehydrohalogenation reaction Methods 0.000 title claims abstract description 34
- 239000003054 catalyst Substances 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 92
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 34
- UOORRWUZONOOLO-OWOJBTEDSA-N (E)-1,3-dichloropropene Chemical compound ClC\C=C\Cl UOORRWUZONOOLO-OWOJBTEDSA-N 0.000 claims abstract description 33
- 150000001336 alkenes Chemical class 0.000 claims abstract description 29
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 14
- 239000006227 byproduct Substances 0.000 claims abstract description 13
- KNKRKFALVUDBJE-UHFFFAOYSA-N 1,2-dichloropropane Chemical compound CC(Cl)CCl KNKRKFALVUDBJE-UHFFFAOYSA-N 0.000 claims abstract description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims description 49
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical group ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 claims description 38
- 239000000047 product Substances 0.000 claims description 29
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 27
- 150000001875 compounds Chemical class 0.000 claims description 22
- 230000000694 effects Effects 0.000 claims description 21
- 230000008929 regeneration Effects 0.000 claims description 21
- 238000011069 regeneration method Methods 0.000 claims description 21
- 229910052746 lanthanum Inorganic materials 0.000 claims description 20
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 20
- 239000007789 gas Substances 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 229910052799 carbon Inorganic materials 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- OWXJKYNZGFSVRC-UHFFFAOYSA-N 1-chloroprop-1-ene Chemical compound CC=CCl OWXJKYNZGFSVRC-UHFFFAOYSA-N 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 239000001307 helium Substances 0.000 claims description 12
- 229910052734 helium Inorganic materials 0.000 claims description 12
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- JEROREPODAPBAY-UHFFFAOYSA-N [La].ClOCl Chemical compound [La].ClOCl JEROREPODAPBAY-UHFFFAOYSA-N 0.000 claims description 11
- 125000003976 glyceryl group Chemical group [H]C([*])([H])C(O[H])([H])C(O[H])([H])[H] 0.000 claims description 11
- 229910052779 Neodymium Inorganic materials 0.000 claims description 8
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 8
- 125000005843 halogen group Chemical group 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
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 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
- 150000005826 halohydrocarbons Chemical class 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
- 229910052689 Holmium 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
- 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 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
- 230000026030 halogenation Effects 0.000 claims description 5
- 238000005658 halogenation reaction Methods 0.000 claims description 5
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 claims description 5
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 5
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims description 5
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 claims description 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 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 compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- 235000011089 carbon dioxide Nutrition 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- 208000006278 hypochromic anemia Diseases 0.000 claims description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 2
- 238000009418 renovation Methods 0.000 claims 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 abstract description 13
- CFXQEHVMCRXUSD-UHFFFAOYSA-N 1,2,3-Trichloropropane Chemical compound ClCC(Cl)CCl CFXQEHVMCRXUSD-UHFFFAOYSA-N 0.000 abstract description 11
- 239000006283 soil fumigant Substances 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- OWXJKYNZGFSVRC-NSCUHMNNSA-N (e)-1-chloroprop-1-ene Chemical compound C\C=C\Cl OWXJKYNZGFSVRC-NSCUHMNNSA-N 0.000 abstract description 2
- PNLQPWWBHXMFCA-UHFFFAOYSA-N 2-chloroprop-1-ene Chemical compound CC(Cl)=C PNLQPWWBHXMFCA-UHFFFAOYSA-N 0.000 abstract 1
- UOORRWUZONOOLO-UHFFFAOYSA-N telone II Natural products ClCC=CCl UOORRWUZONOOLO-UHFFFAOYSA-N 0.000 abstract 1
- 239000000460 chlorine Substances 0.000 description 18
- 229910052801 chlorine Inorganic materials 0.000 description 18
- 230000015572 biosynthetic process Effects 0.000 description 10
- 238000001556 precipitation Methods 0.000 description 10
- 150000001721 carbon Chemical group 0.000 description 9
- 230000009466 transformation Effects 0.000 description 9
- 239000003513 alkali Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 229910052736 halogen Inorganic materials 0.000 description 8
- 150000002367 halogens Chemical class 0.000 description 8
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 7
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 239000004411 aluminium Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
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- 239000000908 ammonium hydroxide Substances 0.000 description 5
- 238000005336 cracking Methods 0.000 description 5
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 5
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- 239000002585 base Substances 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 229910000039 hydrogen halide Inorganic materials 0.000 description 4
- 239000012433 hydrogen halide Substances 0.000 description 4
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
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- 238000009835 boiling Methods 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 description 3
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- ZLRANBHTTCVNCE-UHFFFAOYSA-N 2-phenyl-3-(trifluoromethyl)pyridine Chemical compound FC(F)(F)C1=CC=CN=C1C1=CC=CC=C1 ZLRANBHTTCVNCE-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
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- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
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- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
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- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
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- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000013079 quasicrystal Substances 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
- 239000010458 rotten stone Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 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
- 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
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- 238000001577 simple distillation Methods 0.000 description 1
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- 238000005987 sulfurization reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
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Abstract
一种用于将卤代烷烃进行脱氢卤代作用的方法,该方法涉及将具有3个或更多个碳原子的卤代烷烃与稀土卤代物或稀土卤氧代物催化剂在足以产生烯烃或卤带烯烃的反应条件下进行接触。本方法将低价值的工业氯化工艺的副产品卤代烷烃转化成为高价值的烯烃和卤代烯烃。例如,1,2-二氯丙烷可以被脱氢氯化主要转化成为烯丙基氯和1-氯丙烯,而产生的低价值的2-氯丙烯很少。1,2,3-三氯丙烷可以被脱氢氯化主要转化成为用于土壤熏剂的1,3-二氯丙烯。
Description
本申请要求1999年11月22日提出的美国临时申请60/166.897的权利。
本发明涉及对卤代烷烃例如1,2-二氯丙烷或1,2,3-三氯丙烷分别产生烯丙基氯或1,3-二氯丙烯进行催化脱氢卤化作用产生烯烃或卤代烯烃的方法。
发现烯烃,例如丙烯,在聚烯烃多聚物和合成橡胶的生产中作为单体有着广阔的用途。发现卤代烯烃在多种碱性化学制品和特制化学制品中有用。例如,烯丙基氯在制备表氯醇中是一种有用的原料,从它可以制备环氧聚合物。发现1,3-二氯丙烯和其他氯化烯烃可以用作杀线虫剂、土壤熏剂、杀虫剂的成分和生产塑料、树脂和化学中间体的单体。
烯丙基氯的生产涉及高温下丙烯和氯的快速接触,例如美国专利4,319,062所述。使用蒸馏法去除含有烯丙基氯的低沸点成分和主要含有顺式-和反式-1,3-二氯丙烯的高沸点成分后,得到的由中沸点物质构成的副产品流包含多种氯化丙烷和丙烯,例如1,2-二氯丙烷、3,3-二氯丙烯、2,3-二氯丙烯、2,2-二氯丙烷和其他相关的氯化三碳系化合物。通常,1,2-二氯丙烷是主要成分,摩尔含量在副产品流中常常达到约70%一95%,一般情况下为75%-90%。通常,3,3-二氯丙烯在副产品流中的摩尔含量范围是0.1%-15%。3,3-二氯丙烯一般异构化产生上面提到的1,3-二氯丙烯,例如美国专利5,072,063和5,510,546所述。1,2-二氯丙烷本身没有用处,也必须升级成具有较高价值的产品。
一般情况下,通过热脱氢卤化作用将1,2-二氯丙烷升级成为烯丙基氯。热脱氢卤化作用的副产品包括顺式-和反式-1-氯丙烯,该副产品可以回收进入上述烯丙基氯的生产过程中,其中丙烯被氯化成为烯丙基氯。此处对顺式-和反式-1-氯丙烯的氯化作用产生了如前指明的使用于土壤熏剂配方的有用化合物,1,3-二氯丙烯。将1,2-二氯丙烷进行热脱氢卤化作用的另外一个不太受欢迎的副产品是2-氯丙稀,该副产品难以使用并且难以升级成为具有较高价值的产品。所以期望找到一种脱氢卤化的方法,其主要将1,2-二氯丙烷转化成为烯丙基氯和1-氯丙烯,并且基本上没有、或者最多也只有很少的低使用价值的2-氯丙稀形成。
作为另外一个例子,烯丙基氯产物本身可被氯化形成具有非常有限价值和用途的副产品,1,2,3-三氯丙烷;但是,1,2,3-三氯丙烷可以被脱氢卤化形成1,3-二氯丙烯,该化合物在土壤熏剂中由用途。但是,传统的脱氢卤化方法一般产生不受欢迎的产物2,3-二氯丙烯,该化合物通过简单蒸馏法难以分离。所以期望找到一种脱氢卤化法,该方法可以将1,2,3-三氯丙烷转化成更加令人期望的顺式-和反式-1,3-二氯丙烯,并且减少了2,3-二氯丙烯的形成。
本发明是一种将卤代烷烃通过脱氢卤化作用形成烯烃或卤代烯烃的新方法。本发明所述的新方法包括在反应条件下,将含有三个或更多个碳原子的卤代烷烃与一种脱氢卤化催化剂充分接触,产生烯烃或卤代烯烃。在本发明的新方法中,脱氢卤化催化剂包括一种稀土卤化物或卤氧化物。
本发明的新方法在稀土卤化物或卤氧化物催化剂存在的条件下,通过脱氢卤化作用(裂解)简单而有效地将卤代烷烃转变成为烯烃或卤代烯烃。本发明所述方法也可以有益地用于将低价值卤代烷烃升级成为适合商业用途的高价值烯烃或卤代烯烃。例如,在丙烯氯化形成烯丙基氯的过程中产生的1,2-二氯丙烷可以通过本发明所述方法有益地进行脱氢卤化高产形成烯丙基氯和1-氯丙烯。1,2-二氯丙烷脱氢卤化的不受欢迎的副产物,2-氯丙烯在本发明所述方法中产量低。在此处1,2-二氯丙烷的裂解过程中产生的1-氯丙烯可被有益地循环到烯丙基氯反应器中,氯化为在土壤熏剂中有用的1,3-二氯丙烯。本发明所述方法的另外一个例子是1,2,3-三氯丙烷可被有益地脱氢卤化产生以1,3-二氯丙烯为主的产物,其在土壤熏剂中有前述的用途。本发明的另外一个优点在于,一般地,该脱氢卤化作用发生的温度低于已有脱氢卤化方法所要求的温度。相应地,本发明所述方法比已有方法消耗的能量低,提供了在较低的操作温度下进行高效转化的可能性。还有另外一个优点,本发明所用的稀土卤化物催化剂是水溶性的。相应地,如果加工设备,例如过滤器、运输线、阀门和反应器的复杂小部件或弧形部件,塞上了催化剂颗粒,则堵塞部分只需要用水冲洗就可以使其恢复正常运转状态。
就其广义而言,本发明是一个包括将卤代烷烃转变成为烯烃或卤代烯烃的催化型脱氢卤化作用的新方法。本发明所述的新方法包括在反应条件下,将含有三个或更多碳原子的卤代烷烃与一种脱氢卤化催化剂充分接触,以便产生烯烃或卤代烯烃。在本发明所述新方法中所用的脱氢卤化催化剂包括一种稀土卤化物或卤氧化物化合物。
在一个优选实施方案中,本发明是一个包括将氯代烷烃进行催化脱氢卤化以便形成烯烃或氯代烯烃的新方法。在本优选实施方案中,新方法包括在反应条件下,将含有三个或更多碳原子的氯代烷烃与一种脱氢氯化催化剂充分接触,以便产生相应的烯烃或氯代烯烃,其中该脱氢氯化催化剂是一种稀土卤化物或卤氧化物,更优选地是一种稀土氯化物或氯氧化物。在一个更优选的实施方案中,该氯代烷烃是1,2-二氯丙烷或一种主要包括1,2-二氯丙烷的氯代烷烃混合物,而氯代烯烃包括烯丙基氯、1-氯丙烯或主要是它们的混合物。在另外一个更优选的实施方案中,氯代烷烃是1,2,3-三氯丙烷,而氯代烯烃是1,3-二氯丙烯。
本发明所述方法中使用的卤代烷烃可以是任何一种含有三个或更多碳原子的卤代烷烃。该卤代烷烃也可以是基本上纯化的卤代烷烃或卤代烷烃混合物。优选地,卤代烷烃是一种卤化的含有3-8个碳原子的烷烃或卤化的含有3-8个碳原子的烷烃的混合物。更优选地,卤代烷烃是一种卤化的含有3-4个碳原子的烷烃或卤化的含有3-4个碳原子的烷烃的混合物。该卤代烷烃至少具有一个卤素取代基。一般不选卤素取代饱和的烷烃。优选地,至少一个碳原子上存在至少一个卤素原子,这是因为通过从卤代烷烃上去除卤化氢而进行脱氢卤化作用。所存在的每个卤素取代基可以独立地选自氯、溴和碘取代基。优选地,卤素取代基选自氯或溴取代基。氟取代基可以出现在卤代烷烃上;但是,一般地,氟是惰性的,不参与脱氢氟化作用(即失去HF)。不受限制的合适卤代烷烃实例包括1,2-二氯丙烷、1,2,3-三氯丙烷、1,2-二氯丁烷、2,3-二氯丁烷、1,2,3-三氯丁烷、1,2-二溴丙烷、1,2,3-三溴丙烷、1,2-二溴丁烷、1,2,3-三溴丁烷、上述卤代烷烃的异构物和更高的同族体以及上述化合物的任意混合物。卤代烷烃也可以以含有卤代烷烃的混合物提供。最优选地,卤代烷烃是1,2-二氯丙烷或1,2,3-三氯丙烷。
在另外一个最优选的实施方案中,卤代烷烃由1,2-二氯丙烷与二氯代和三氯代含有三个碳原子的烷烃和含有三个碳原子的烯烃形成的混合物。该混合物,在本技术领域称为“烯丙基丙烯二氯化物”(“烯丙基PDC”),可以在丙烯氯化形成烯丙基氯的过程中作为副产物流而产生。“烯丙基PDC”的组成可能随着烯丙基氯反应器中的特定条件和所用的特定纯化步骤而变化。纯化步骤可以包括蒸馏、异构化、选择反应和本技术领域的技术人员所知的其他分离操作。典型“烯丙基PDC”组成以摩尔百分含量来说,包括:70-95%的1,2-二氯丙烷、1-15%的2,3-二氯丙烯、0.1-15%的3,3-二氯丙烯、0.1-10%的1,3-二氯丙烯异构体、0-3%的1,1-二氯丙烯,可能包含其他的氯代烷烃和烯烃以及非氯代化合物。
非强制性地,如果愿意,含有卤代烷烃的、用于脱氢卤化作用工艺的原料可以用稀释气体或载体气体进行稀释,该气体可以是任何基本上不干扰脱氢卤化作用工艺的气体。稀释剂可能有助于从反应器去除产物和热量,并有助于减少令人生厌的副反应数量。不加限制的合适稀释剂的实例包括氮气、氩气、氦气、一氧化碳、二氧化碳、蒸汽、可冷凝的卤代烃和它们的混合物。根据本发明的用途,术语“可冷凝的卤代烃”将包括任何相对于本发明所述的脱氢卤化作用工艺而言基本上是惰性的、并且容易通过分馏或冷却进行分离的卤代烃。全卤代烯烃,例如全氯代乙烯、全氟代乙烯,适于用作可冷凝的卤代烃。一般来说,所用稀释剂的量是从摩尔百分数高于10%,优选地高于20%,到达低于90%,优选地低于70%,该摩尔百分数是以起始的卤代烷烃和任意稀释剂的总摩尔数为基础计算的。
使用于本发明所述新脱氢卤化作用工艺的一种催化剂包括一种稀土卤化物。稀土包括17种元素,即钪(原子序数为21)、钇(原子序数为39)和镧系元素(原子序数为57至71)[James B.Hedrick,美国地理概况-矿产信息-1997,“稀土金属”]。在此所用,优选地,本术语是指一种选自镧、铈、钕、镨、镝、钐、钇、钆、铒、镱、钬、铽、铕、铥、镥及其混合物。用于上述脱氢卤化作用工艺的优选稀土元素是那些一般被认为是单价金属的稀土元素。用于本发明的稀土元素更优选自镧、钕、镨及其混合物。最优选地,用作催化剂的稀土元素是镧或镧与其它稀土元素的混合物。
优选地,稀土卤化物是用分子式MX3表示,其中M是指至少一种稀土元素,选自镧、铈、钕、镨、镝、钐、钇、钆、铒、镱、钬、铽、铕、铥、镥及其混合物;并且,其中X是指氯化物、溴化物或碘化物。更优选地,X是指氯化物,并且更优选的稀土卤化物是用分子式MCl3表示,其中M如前定义。最优选地,X是指氯化物并且M是指镧,稀土卤化物是能够与其他稀土氯化物任意混合的氯化镧。在另一个实施方案中,稀土卤化物催化剂是多孔的,其意味着催化剂在其结晶结构中包含空隙空间,例如通道、孔和/或空穴。这种多孔性在整个化合物中产生了表面。一般地,用S.Brunauer,P.H.Emmett,和E.Teller,美国化学协会杂志,60,309(1938)所述的测量表面积的博纳-埃默特-特勒法(BET方法)确定该多孔稀土卤化物具有的BET表面积大于5平方米/克。优选地,多孔稀土卤化物具有的BET表面积大于10平方米/克,更优选地,表面积大于15平方米/克,甚至更优选地,表面积大于20平方米/克,最优选地,表面积大于30平方米/克。对于上面的这些测量数据,氮气吸收等温线是在77K,并且表面积用BET方法从等温数据中计算出来的。
另一方面,新脱氢卤化作用工艺的催化剂包括稀土卤氧化物,该稀土在上文已经说明。优选地,这种形式的催化剂是用分子式MOX表示的,其中M是指至少一种稀土元素,选自镧、铈、钕、镨、镝、钐、钇、钆、铒、镱、钬、铽、铕、铥、镥及其混合物;而且其中X选自氯化物、溴化物或碘化物。更优选地,稀土卤氧化物是一种用分子式MOCl表示的稀土卤氧化物,其中M在上文中已经定义。最优选地,稀土卤氧化物是与其它稀土氯氧化物任意混合的镧氯氧化物LaOCl。
在另一个实施方案中,稀土卤氧化物是多孔的,这在上文中已经和稀土卤化物一起定义。一般地,多孔稀土卤氧化物具有的BET表面积大于12平方米/克,优选地,大于15平方米/克,更优选地,大于20平方米/克,最优选地,大于30平方米/克。总的来说,BET表面积低于200平方米/克。另外,注意到MOCl相位具有典型的粉状物X射线衍射图形,这不同于MCl3相位所具有的。
在催化剂中包含其它的元素也是有益的。例如,优选的元素添加剂包括碱和碱土金属、硼、磷、硫、锗、钛、锆、铪、贵金属及其混合物。贵金属包括钌、铑、钯、锇、铱、铂、银和金。这些元素可以用来改变这种组合物的催化性能,或者提高材料的机械性能(例如抗磨损性)。一般地,依催化剂的总重量而言,催化剂中元素添加剂的浓度的重量百分比大于0.01%,小于20%。
在上面的讨论中,催化剂不与支持物或载体结合。在另一个实施方案中,稀土卤化物或稀土卤氧化物催化剂可以结合,突出或沉淀在催化剂的支持物或载体上。不限制的合适载体实例包括氧化铝、硅土、硅土-氧化铝、多孔铝矽酸盐(沸石)、硅土-氧化镁、矾土、氧化镁、碳化硅、氧化钛、氧化锆、锆硅酸盐及其混合物。在使用支持物的实施方案中,依催化剂和支持物的总重量而言,支持物的重量百分比大于1%,优选地,大于10%。在使用支持物的实施方案中,依催化剂和支持物的总重量而言,支持物的重量百分比小于90%,优选地,小于80%,更优选地,小于70%。
稀土卤化物或稀土卤氧化物催化剂可以从商业供应者得到。由于催化剂的多孔型实施方案当前并不知晓有商业化产品,所以,多孔稀土卤化物或稀土卤氧化物催化剂可以如后所述进行合成。
目前优选使用的、用于形成含有多孔的稀土卤氧化物(MOX)成分的方法包括如下步骤:(a)准备一种稀土元素或几种稀土元素的卤酸盐的溶液,其溶剂包括水,酒精或它们的混合物;(b)加碱形成沉淀;(c)收集煅烧沉淀以便形成MOX。优选地,卤酸盐是一种稀土氯酸盐,例如任何可以商业性获得的稀土氯酸盐。一般地,所用含氮碱选自氢氧化铵、烷基胺、芳基胺、芳基烷基胺、氢氧化烷基铵、氢氧化芳基铵、氢氧化芳基烷基铵及其混合物。含氮碱也可以以与其他不含氮的碱的混合物形式提供。优选地,该含氮碱是氢氧化铵或氢氧化四铵(氢氧化烷基铵),更优选地,氢氧化四铵(为含有碳原子1-20的烷基)。步骤(a)所述溶剂优选水。多孔的稀土氯氧化物也可以通过适当使用碱或碱土金属氢氧化物,优选地,结合含氮碱的缓冲行为。通常,沉淀是在0℃以上进行的。通常,沉淀是在200℃以下进行,优选地,低于100℃。通常,沉淀是在环境大气压下进行,虽然可以使用高大气压可能对在所用沉淀温度下保持液体相是必要的。虑过一般在大于200℃的条件下进行,优选地,大于300℃,但是低于800℃,优选地,低于600℃。在合适的分解过程中,羧酸和稀土氯化物盐的混合物也可以产生稀土氯氧化物。
目前优选使用的、用于形成含有多孔的稀土卤化物(MX3)催化剂组合物的方法包括如下步骤:(a)准备一种稀土元素或几种稀土元素的卤酸盐的溶液,其溶剂包括水,酒精或它们的混合物;(b)加碱形成沉淀;(c)收集煅烧沉淀;和(d)使煅烧物与卤素源接触。优选地,稀土卤化物是一种稀土氯酸盐,例如任何可以商业性的获得的稀土氯酸盐。优选地,该溶剂是水,该碱是与前面记录的与MOX制备有关的任何一种碱。同样地,沉淀通常是在大于0℃而小于200℃的温度条件下形成,优选地低于100℃,在环境大气压或更高的压力的条件下,以便保持液体相。一般地,煅烧在大于200℃,优选地,大于300℃,但是低于800℃,优选地,低于600℃。优选地,卤素源是卤素卤化物,例如氯化氢,溴化氢,碘化氢或卤素分子,例如氯分子,溴分子或碘分子。更优选地,卤素源是氯化氢或氯分子。与卤素源的接触通常是在高于150的条件下进行,优选地高于200。通常与卤素源的接触通常是在低于450的条件下进行,优选地低于250。一般而言与卤素源的接触的压强通常是从环境大气压到低于150psia的压强(1,034kPa)。
本发明的脱氢卤化作用可以在任何传统设计适合,优选适合气相工艺的反应器,包括间歇式,固定床,硫化床,传输床,连续和间隙流反应器。任何工艺条件(例如,进料成分的摩尔比,温度,压强,气体时空速率)可以使用,只要选择性得到了期望的产品烯烃或卤代烯烃。一般地,工艺温度是大于100,优选地,大于150,更优选地,大于180。一般地,工艺温度是小于500,优选地,小于300,更优选地,小于250。预热包括卤代烷烃和任意稀释剂的反应物进料也包括在本发明的范围中。一般地,预热温度大于50,优选地,大于100,但是,一般等于或者低于工艺温度。优选地,预热温度低于500,优选地,低于300。通常,该工艺是在大气压或更高地压强下进行。那么,一般而言,压强将等于或大于14psia(96kPa),但是一般低于1000,优选地,低于600,更优选地,低于300。一般地,进料(卤代烷烃和任意稀释剂)的总气体时空速率(GHSV)将超过每小时每毫升催化剂的总进料超过10毫升,优选地大于100,更优选地大于400。一般地,进料的总气体时空速率(GHSV)将小于30000,优选地,小于20000,更优选地,小于10000。
在本发明所述的脱氢卤化裂解工艺中形成的烯烃或卤代烯烃可以是任何烯烃或卤代烯烃。通常来说,烯烃产物含有的碳原子数目和反应物烷烃与一样。优选地,烯烃或卤代烯烃将是含有3-8个的碳原子,优选地,含有3-4个的碳原子的烯烃或卤代烯烃。该卤代烯烃将包括一个或几个卤素取代基,优选地,选自氯、溴、碘。更优选地,卤素取代基是氯。不限制的烯烃产物的实例包括丙烯和丁烯,和它们的高级类似物。不限制的卤代烯烃产物的实例包括氯丙烯、二氯丙烯、氯丁烯、二氯丁烯、三氯丁烯、溴丙烯、二溴丙烯、溴丁烯、二溴丁烯。最优选地,该烯烃是丙烯或丁烯。最优选地,卤代烯烃选自烯丙基氯、1-氯丙烯,1,3-二氯丙烯及其混合物。
在生产烯丙基氯的过程中作为重要副产物的1,2-二氯丙烷,在非常低的不需要2-氯丙烯形成水平下,可以被通过本发明所述的过程选择性的脱氢卤化作用,形成烯丙基氯和1-氯丙烯混合物。通常,本发明所述的过程在温度低于240℃地条件下,1,2-二氯丙烷的摩尔转化率大于50%,优选地大于60%。在本发明中,“转化”被定义为卤代烷烃进料地摩尔百分比,例如在脱氢卤化过程中反应的1,2-二氯丙烷进料。一般地,对烯丙基氯和1-氯丙烯总的选择率的摩尔百分比超过90%。一般地,对不需要的2-氯丙烯的选择率的摩尔百分比小于2%,优选地,小于1%。在本发明中,“选择性”被定义为参加反应的形成特定产物的卤代烷烃的摩尔百分比。
在1,2-二氯丙烷的脱氢卤化过程中产生的1-氯丙烯可以有益的循环进烯丙基氯反应器,在反应器中丙烯被氯代为烯丙基氯。在这里所述的反应条件下,1-氯丙烯被转化为土壤熏剂成分1,3-二氯丙烯。从另一途径,在烯丙基氯氯代的过程中产生的1,2,3-三氯丙烷可以用本发明所述的过程选择性地被脱氢氯代为主要包括顺式和反式-1,3-二氯丙烷的混合物。在一般条件下就可以达到总摩尔百分比选择率大于55%的顺式和反式-1,3-二氯丙烷地。优选地,可以达到总摩尔百分比选择率大于70%的顺式和反式-1,3-二氯丙烷地。
本领域的技术人员可以认识到本发明所述的方法可以用卤代烷烃进料来裂解卤化氢,优选地可以裂解氯化氢。所形成的卤化氢可以被循环到氧化卤代过程中,优选地可以被循环到氧化氯代过程中,其中烃或者卤代烃(原料烃)可以在有氧化卤代催化剂,例如以铜为基础的催化剂的条件下与氧和循环的卤化氢反应,产生比原料烃更多的卤代基团的。乙烯与氯化氢和氧的氧氯代形成乙烯二氯化合物是循环氯化氢流的此种用途的一个实例。
当本发明过程的脱氢卤代催化剂部分或者完全失去活性,催化剂可以容易的再生。再生的优选方法涉及将部分或者完全失去活性的催化剂与水蒸气在合适温度下充分接触进行再生,至少部分再生催化活性。通常,水蒸气是以再生气体混合物形式提供,该混合物种包括惰性稀释剂,例如氮气、氦气或氩气。以再生气体的总摩尔数为基础,混合物中水蒸气的摩尔百分比数量可在大于0.005%到小于50%的范围内变化。氧气可以被任意加入到再生气体中以帮助去除焦炭。根据个人喜好,含氧的混合物中含氧量的摩尔百分比从大于1%到小于50%;但是优选地,以再生气体的总摩尔数为基础,再生气体混合物中含氧量的摩尔百分比大于2%到小于20%。再生通常是在高于200℃的情况下进行的,优选地,高于300℃。再生通常是在低于700℃,优选地低于600℃的情况下进行的。再生时间在大于30分钟到小于12小时的范围内变化,优选地是大于30分钟到小于5小时。
下面的实施例用来说明本发明方法。这些实施例不应该理解为以另一种方式限制本发明。按照此处的公开材料,本技术领域的技术人员将认识到另一种实施方案,例如反应物、工艺条件和催化剂种类,这些将被包含在本发明的范围之内。除了特殊说明,百分比是以摩尔百分比给出。
实施例1
多孔镧氯氧化物催化剂按如下方法制备。氯化镧(LaCl3 7H2O,15.0g)溶解在(150ml)去离子水中。很快将氢氧化铵(6M,20ml)边搅拌边加入氯化镧溶液中,产生白色沉淀。将混合物离心,去除多余液体,产生含镧凝胶。沉淀是在400℃经过4个小时煅烧产生多孔镧氯氧化物催化剂。X射线衍射资料表明存在镧氯氧化物的准晶体形式。正如用BET方法测量的,催化剂的表面积是25.8平方米/克。
如前所制备的镧氯氧化物(7.35g,5cm3)被转入管形反应器{碱性镍,1/2英寸(1.25cm)O.D.×14英寸(35cm)长}。催化剂在130℃通入氦气1小时进行干燥,然后再在通入氦气的条件下加热到230℃。在速率是7.68cm3/h时,将1,2-二氯丙烷(PDC)通过Gilson Model 305泵泵入,并入流速是33cm3/min的氦气混合,形成PDC/He进料。将进料预加热到170℃,然后加入到在230℃大气压条件下运行的反应器中。进料气体时空速率是682h-1。现有的进料成分如表1所述。
表1.1,2-二氯丙烷(PDC)的脱氢氯化作用
a.PDC转化率和产物选择性以摩尔百分比给出。b.进料:PDC7.68cm3/h,氦气33cm3/min;230℃;大气压;进料GHSV,682h-1;进料停留时间,5.3秒。
实例 | 1a.b | 2a.b |
PDC转化 | 50.22% | 65.66% |
选择性的2-氯丙烯 | 0.46% | 0.40% |
选择性的顺式-1-氯丙烯 | 54.1% | 51.5% |
选择性的反式-1-氯丙烯 | 4.03% | 4.47% |
选择性的烯丙基氯 | 37.0% | 41.0% |
从表1可以看出,镧氯氧化物催化剂能使1,2-二氯丙烷脱氢氯化为两种有用的产品顺式-1-氯丙稀和烯丙基氯,这两种产品的总选择率高于90%。形成了少量的反式-1-氯丙稀。最令人讨厌的产品2-氯丙稀形成的选择率低于1%。
在反应16小时之后,PDC转化率降到31%。催化剂通过速率为1.2cm3/h的蒸气流和速率为200cm3/min的氧气氦气流再生,这些气流在400℃温度下在催化剂上作用2小时。再生之后,脱氢氯化作用如前描述的反应条件下重新开始。PDC的起始转化率达到40%。
实施例2
通过将氯化镧(30.16g)溶入去离子的蒸馏水(18.50g)制备氯化镧的储存溶液。在合适的温度下,该储存溶液被用于让铝吸收初始湿度。在合适的温度下将吸收了湿度的铝在空气中干燥过夜后铝支持的镧氯氧化物催化剂,进一步在空气中120℃的条件下干燥。将催化剂(10.46g)加到反应器中,按照实施例1所述方式检验1,2-二氯丙烷的脱氢氯化作用。工艺条件和结果如表1所述,其中表明铝支持的镧氯氧化物催化剂能够把1,2-二氯丙烷脱氢氯化,主要产生两种有用的产品烯丙基氯和顺式-1-氯丙稀,这两种产品地总选择率高于90%。只有少量的反式-1-氯丙稀形成。最没有价值的产品2-氯丙稀的形成量很低(出料流的0.40%)。
在反应16小时之后,催化剂通过速率为1.2cm3/h的蒸气流和速率为200cm3/min的氧气流(占氦气的15%)再生,这些气流在450℃温度下在催化剂上作用6小时。再生之后,脱氢氯化作用如前描述的反应条件下重新开始。发现催化剂获得了进行脱氢氯化作用的完全活性。
实施例3
如实施例2所述的铝支持的镧氯氧化物催化剂在“烯丙基PDC”的脱氢氯化作用中测试,该“烯丙基PDC”是从烯丙基氯工艺过程中获得的中间体卤代三碳烷烃和三碳烯烃的混合物。更详细地说,该“烯丙基PDC”进料包括87.44%的1,2-二氯丙烯,7.55%的2,3-二氯丙烯,2.02%的1,3-二氯丙烯,1.01%的3,3-二氯丙烯,0.37%的烯丙基氯,1.6%的其它卤代烷烃和烯烃的平衡成分,所有百分比是摩尔百分比。脱氢卤代条件与实施例2中所用的相似。结果如下表2所述。
表2.“烯丙基PDC”a,b的脱氢氯化作用
a.该“烯丙基PDC”包括以摩尔百分比表示的87.44%的1,2-二氯丙烯, 7.55%的2,3-二氯丙烯,2.02%的1,3-二氯丙烯,1.01%的3,3-二氯丙烯,0.37%的烯丙基氯,1.6%的其它卤代烷烃和烯烃的平衡成分。转化率和产品产物选择性以摩尔百分比给出。b.进料:“烯丙基PDC”7.68cm3/h,氦气33cm3/min;230℃;大气压;进料GHSV,682h-1;进料停留时间,5.3秒。
实例 | 3 |
PDC转化 | 55.0% |
选择性的2-氯丙烯 | 0.45% |
选择性的顺式-1-氯丙烯 | 51.2% |
选择性的反式-1-氯丙烯 | 5.03% |
选择性的烯丙基氯 | 43.3% |
从表2可以看出镧氯氧化物催化剂可以脱氢氯化“烯丙基PDC”,产生两种有用的产物顺式-1-氯丙稀和烯丙基氯,这两种产品的总选择率高于90%。形成了少量的反式-1-氯丙稀。最令人讨厌的产品2-氯丙稀形成的选择率低于1%。
在反应16小时之后,“烯丙基PDC”转化率降至15%。催化剂通过速率为1.2cm3/h的蒸气流和速率为200cm3/min的氧气氦气流(氧在氦气中占15%)再生,这些气流在400℃温度下在催化剂上作用2小时。再生之后,脱氢氯化作用如前描述的反应条件下重新开始。PDC起始转化率是55%。
实施例4如实施例2所属的铝支持的镧氯氧化物催化剂用1,2,3-三氯丙烷的脱氢氯代作用评价。工艺条件与实施例2一样,结果如表3所述。
表3.1,2,3-三氯丙烷(TCP)a,b的脱氢氯代作用
a.TCP的转化率和产品选择性是用摩尔百分比表示的。b.进料:TCP7.68cm3/h,氦气33cm3/min;230℃;大气压;进料GHSV,682h-1;进料停留时间,5.3秒。
实例 | 4 |
TCP转化 | 6.1% |
选择性的顺式-1,3-二氯丙烯 | 46.7% |
选择性的反式-1,3-二氯丙烯 | 25.5% |
选择性的2,3-二氯丙烯 | 27.7% |
从表3可以看出镧氯氧化物催化剂可以脱氢氯化1,2,3-三氯丙烷,主要产生两种有用的产物顺式-1,3-二氯丙烯和反式-1,3-二氯丙烯,这两种产品的总选择率是72.2%。
在反应16小时之后,TCP转化率降至1.3%。催化剂通过速率为1.2cm3/h的蒸气流和速率为200cm3/min的氧气氦气流(氧在氦气中占15%)再生,这些气流在400℃温度下在催化剂上作用2小时。再生之后,脱氢氯化作用如前描述的反应条件下重新开始。TCP起始转化率是6.0%。
Claims (34)
1.一种将卤代烷烃进行脱氢卤化作用形成烯烃或卤代烯烃的方法,该方法包括在足以产生烯烃或卤代烯烃的反应条件下将含有三种或更多个碳原子的卤代烷烃与一种稀土卤化物或稀土卤氧化物催化剂接触。
2.如权利要求1所述的方法,其中卤代烷烃是一种氯代的含有3到4个碳原子的烷烃或氯代的含有3到4个碳原子的烷烃混合物。
3.如权利要求2所述的方法,其中卤代烷烃是1,2-二氯丙烷或1,2,3-三氯丙烷。
4.如权利要求1所述的方法,其中卤代烷烃是一种混合物,该混合物包括1,2-二氯丙烷,二氯代三碳烷烃和三碳烯烃,三氯代三碳烷烃和三碳烯烃。
5.如权利要求1所述的方法,其中所以稀释剂是氮气、氦气、氩气、一氧化碳、二氧化碳、水蒸气、可冷凝的卤代烃或上述一种或多种的混合物。
6.如权利要求1到5的任一项所述的方法,其中稀土卤化物用分子式MX3表示,其中M是指至少一种稀土元素,选自镧、铈、钕、镨、镝、钐、钇、钆、铒、镱、钬、铽、铕、铥和镥;其中X是指氯化物、溴化物或碘化物。
7.如权利要求6所述的方法,其中M是指镧,X是氯化物,并且稀土卤化物是氯化镧。
8.如权利要求6所述的方法,其中稀土卤化物是多孔的,具有的BET表面积大于5m2/g。
9.如权利要求8所述的方法,其中多孔稀土卤化物的BET表面积大于15m2/g。
10.如权利要求6所述的方法,其中催化剂是沉淀在、结合到或从催化剂载体上伸出。
11.如权利要求1到5的任一项所述的方法,其中稀土卤氧化物是用分子式MOX表示的,其中M是指至少一种稀土元素,选自镧、铈、钕、镨、镝、钐、钇、钆、铒、镱、钬、铽、铕、铥和镥;而且其中X选自氯化物、溴化物或碘化物。
12.如权利要求11所述的方法,其中M是镧,X是氯化物,稀土卤氧化物是镧氯氧化物。
13.如权利要求11所述的方法,其中稀土卤氧化物是多孔的,具有的BET表面积大于12m2/g。
14.如权利要求13所述的方法,其中多孔稀土卤氧化物具有的BET表面积大于20m2/g。
15.如权利要求11所述的方法,其中催化剂是沉淀在、结合到或从催化剂载体上伸出。
16.如权利要求1所述的方法,其中当催化剂部分或者完全失去活性时,可以通过一种方法再生,该再生方法包括将部分或者完全失去活性的催化剂与含有蒸气的再生气体接触,足以使至少部分再生催化活性。
17.如权利要求16所述的方法,其中再生气体进一步包括氧气。
18.一种将1,2-二氯丙烷转化成为烯丙基氯和1-氯丙烯的脱氢氯代作用方法,该方法包括在150℃以上500℃以下的温度范围内将1,2-二氯丙烷与稀土卤化物或稀土卤氧化物催化剂接触,以便形成烯丙基氯和1-氯丙烯。
19.如权利要求18所述的方法,其中催化剂是一种稀土卤化物或稀土卤氧化物,其中稀土是镧、钕、镨或它们的混合物。
20.如权利要求19所述的方法,其中稀土卤化物是卤化镧,稀土卤氧化物是氧卤化镧。
21.如权利要求18到20任一项所述的方法,其中稀土卤化物或稀土卤氧化物是多孔的。
22.如权利要求21所述的方法,其中多孔稀土卤化物的BET表面积大于5m2/g。
23.如权利要求21所述的方法,其中多孔稀土卤氧化物的BET表面积大于12m2/g。
24.如权利要求18所述的方法,其中对烯丙基氯和1-氯丙烯的总选择性的摩尔百分比大于90%。
25.如权利要求24所述的方法,其中2-氯丙烯作为副产品产生的选择性摩尔百分比小于2%。
26.如权利要求18所述的方法,其中1-氯丙烯循环到烯丙基氯反应器中被氯代,从而这种氯代产品被脱氢卤代为1,3-二氯丙烯。
27.如权利要求18所述的方法,其中当部分或全部失去活性的催化剂可以通过一种方法再生,该方法包括将部分或全部失去活性的催化剂与水蒸气和任意量氧气在温度高于200℃低于700℃的条件下接触。
28.一种将1,2,3-三氯丙烷转化成为1,3-二氯丙烯的脱氢氯代作用方法,该方法包括在100℃以上500℃以下的温度范围内将1,2,3-三氯丙烷与稀土卤化物或稀土卤氧化物催化剂接触,接触是在高于100℃低于500℃的条件下进行,以便形成1,3-二氯丙烯。
29.如权利要求28所述的方法,其中催化剂是一种稀土卤化物或稀土卤氧化物,其中稀土是镧、钕、镨或它们的混合物。
30.如权利要求29所述的方法,其中稀土卤化物是卤化镧而稀土卤氧化物是氧卤化镧。
31.如权利要求30所述的方法,其中稀土卤化物或稀土卤氧化物是多孔的。
32.如权利要求31所述的方法,其中多孔稀土卤化物的BET表面积大于5m2/g。
33.如权利要求31所述的方法,其中多孔稀土卤氧化物的BET表面积大于12m2/g。
34.如权利要求28所述的方法,其中当部分或全部失去活性的催化剂可以通过一种方法再生,该方法包括将部分或全部失去活性的催化剂与水蒸气和任意量氧气在温度高于200℃低于700℃的条件下接触。
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CN107759441A (zh) * | 2017-11-22 | 2018-03-06 | 中国科学院兰州化学物理研究所 | 一种1,2‑二氯丙烷催化脱氯化氢制备1‑氯丙烯的方法 |
CN107759441B (zh) * | 2017-11-22 | 2021-03-23 | 中国科学院兰州化学物理研究所 | 一种1,2-二氯丙烷催化脱氯化氢制备1-氯丙烯的方法 |
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