CN105032448A - 催化剂及其制备和用途 - Google Patents
催化剂及其制备和用途 Download PDFInfo
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- CN105032448A CN105032448A CN201510361962.4A CN201510361962A CN105032448A CN 105032448 A CN105032448 A CN 105032448A CN 201510361962 A CN201510361962 A CN 201510361962A CN 105032448 A CN105032448 A CN 105032448A
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- catalyst
- compound
- ferriferous oxide
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- 239000003054 catalyst Substances 0.000 title claims abstract description 132
- 238000002360 preparation method Methods 0.000 title description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 63
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910052709 silver Inorganic materials 0.000 claims abstract description 37
- 239000004332 silver Substances 0.000 claims abstract description 36
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 31
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 20
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 32
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 11
- 150000002602 lanthanoids Chemical class 0.000 claims description 11
- 239000011148 porous material Substances 0.000 claims description 11
- 229910052684 Cerium Inorganic materials 0.000 claims description 9
- 229910052791 calcium Inorganic materials 0.000 claims description 8
- 239000011575 calcium Substances 0.000 claims description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- 239000011591 potassium Substances 0.000 claims description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 6
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 6
- 239000011733 molybdenum Substances 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 4
- -1 iron halide Chemical class 0.000 claims description 4
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 3
- 238000007906 compression Methods 0.000 claims description 2
- 230000006835 compression Effects 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- 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 1
- 238000000034 method Methods 0.000 abstract description 43
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 38
- 229930195733 hydrocarbon Natural products 0.000 abstract description 38
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 38
- 239000000203 mixture Substances 0.000 abstract description 31
- 238000001354 calcination Methods 0.000 abstract description 18
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 34
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 19
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 14
- 229910052799 carbon Inorganic materials 0.000 description 12
- 239000000463 material Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
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- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
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- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 5
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 5
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 5
- 239000008188 pellet Substances 0.000 description 5
- 229940072033 potash Drugs 0.000 description 5
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 5
- 235000015320 potassium carbonate Nutrition 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
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- 239000000126 substance Substances 0.000 description 4
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 4
- 229910000859 α-Fe Inorganic materials 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- 238000007605 air drying Methods 0.000 description 3
- 150000001339 alkali metal compounds Chemical class 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 150000007942 carboxylates Chemical class 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
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- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 3
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- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 229910052741 iridium Inorganic materials 0.000 description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 3
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- 238000004519 manufacturing process Methods 0.000 description 3
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- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 3
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
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- 239000007921 spray Substances 0.000 description 3
- 125000002769 thiazolinyl group Chemical group 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
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- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical class C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
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- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
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- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
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- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- WTFXARWRTYJXII-UHFFFAOYSA-N iron(2+);iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Fe+2].[Fe+3].[Fe+3] WTFXARWRTYJXII-UHFFFAOYSA-N 0.000 description 1
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- 230000001404 mediated effect Effects 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
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- 235000021313 oleic acid Nutrition 0.000 description 1
- OTCVAHKKMMUFAY-UHFFFAOYSA-N oxosilver Chemical group [Ag]=O OTCVAHKKMMUFAY-UHFFFAOYSA-N 0.000 description 1
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- 229910052698 phosphorus Inorganic materials 0.000 description 1
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- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Chemical class COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 description 1
- 229910001958 silver carbonate Inorganic materials 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- XNGYKPINNDWGGF-UHFFFAOYSA-L silver oxalate Chemical compound [Ag+].[Ag+].[O-]C(=O)C([O-])=O XNGYKPINNDWGGF-UHFFFAOYSA-L 0.000 description 1
- ONVGIJBNBDUBCM-UHFFFAOYSA-N silver;silver Chemical compound [Ag].[Ag+] ONVGIJBNBDUBCM-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 239000003826 tablet Substances 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
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Abstract
描述了一种脱氢催化剂,其包含铁氧化物、碱金属或它的化合物以及银或它的化合物。另外描述了用于制备脱氢催化剂的方法,所述方法包括:制备铁氧化物、碱金属或它的化合物以及银或它的化合物的混合物,和煅烧所述混合物。还描述了用于使可脱氢烃脱氢的方法和用于使脱氢烃聚合的方法。
Description
本申请为分案申请,其母案申请的申请号为200880017659.0,申请日为2008年5月1日,和发明名称为“催化剂及其制备和用途”。技术领域
本发明涉及催化剂、制备催化剂的方法和使可脱氢烃脱氢的方法。
背景技术
脱氢催化剂和这些催化剂的制备是本领域中已知的。铁氧化物基催化剂通常用于可脱氢烃的脱氢中,以获得相应的脱氢烃等化合物。在使可脱氢烃催化脱氢成脱氢烃的这个领域中,正在努力开发具有改进性能的脱氢催化剂。
EP1027928公开了基于铁氧化物的脱氢催化剂,所述催化剂通过喷雾焙烧铁盐溶液和添加选自以下的附加催化剂组分制得:Be、Mg、Ca、Sr、Ba、Sc、Ti、Zr、Hf、V、Ta、Mo、W、Mn、Tc、Re、Ru、Os、Co、Rh、Ir、Ni、Pd、Pt、Cu、Ag、Au、Zn、Cd、Hg、Al、Ga、In、Tl、Na、Cs、La、Li、Ge、Sn、Pb、Bi、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb和Lu。这些催化剂通常含有一种或多种钾化合物。
发明内容
本发明提供一种脱氢催化剂,其包含铁氧化物、碱金属或它的化合物以及银或它的化合物。
在优选实施方案中,本发明提供一种脱氢催化剂,其包含铁氧化物、碱金属或它的化合物以及银或它的化合物,其中银或它的化合物的存在量为每摩尔以Fe2O3计算的铁氧化物至少约0.01毫摩尔的银。
在另一个优选实施方案中,本发明提供一种脱氢催化剂,其包含铁氧化物、碱金属或它的化合物、银以及银铁氧体。
在另一个优选实施方案中,本发明提供一种脱氢催化剂,其包含铁氧化物、钾或它的化合物、铈或它的化合物、钙或它的化合物、钼或它的化合物以及银。
本发明另外提供制备脱氢催化剂的方法,其包括:制备包含铁氧化物、碱金属或它的化合物以及银或它的化合物的混合物,其中银或它的化合物的存在量为每摩尔以Fe2O3计算的铁氧化物至少约0.01毫摩尔的银,和煅烧所述混合物。
本发明提供制备脱氢催化剂的方法,其包括:制备铁氧化物、钾或它的化合物、铈或它的化合物、钙或它的化合物、钼或它的化合物以及银的混合物,和煅烧所述混合物。
本发明还提供使可脱氢烃脱氢的方法,其包括:使包含可脱氢烃的进料与催化剂接触,所述催化剂包含铁氧化物、碱金属或它的化合物以及银或它的化合物,其中银的存在量为每摩尔以Fe2O3计算的铁氧化物至少约0.01毫摩尔的银。
本发明另外提供使可脱氢烃脱氢的方法,其包括:使包含可脱氢烃的进料与催化剂接触,所述催化剂包含铁氧化物、钾或它的化合物、铈或它的化合物、钙或它的化合物、钼或它的化合物以及银。
本发明还提供使用脱氢烃制备聚合物或共聚物的方法,其包括:使脱氢烃聚合以形成包含源自脱氢烃的单体单元的聚合物或共聚物,其中所述脱氢烃在如上所述用于使可脱氢烃脱氢的方法中制得。
具体实施方式
本发明提供满足对改进的脱氢催化剂的需求的催化剂。所述催化剂包含铁氧化物、碱金属或它的化合物以及银或它的化合物。与不含银的相似催化剂相比,包含银的催化剂更具活性和/或更具选择性。另外,在使乙基苯脱氢成苯乙烯中使用该催化剂,可以导致产物物流中减少量的α-甲基苯乙烯。
脱氢催化剂是铁氧化物基催化剂。此外,铁可以以钾铁氧体或作为与任意其它催化剂组分(包括银)的化合物形式存在。催化剂包含10-90wt%的以Fe2O3计算的铁氧化物。催化剂优选包含40-85wt%的铁氧化物,和更优选包含60-80wt%的铁氧化物。
铁氧化物可以通过本领域技术人员已知的任意方法形成或处理。此外,催化剂可以含有一种或多种类型的铁氧化物。铁氧化物可以如美国专利申请公开2003/0144566中描述的通过使铁卤化物热分解形成铁氧化物(下文中称其为再生铁氧化物)而形成。再生铁氧化物可以任选进行处理,以将铁氧化物中的残留卤化物含量降低至至多2000ppm或优选至多1500ppm。铁氧化物可以在第6族金属或可水解金属氯化物存在下,通过喷雾焙烧铁氯化物形成。作为替代,铁氧化物可以通过沉淀法形成。在催化剂中使用铁氧化物之前,可以通过US5,668,075和US5,962,757中描述的方法,通过在重构剂存在下加热而使铁氧化物重构。如US5,401,485中所述,在该催化剂中使用铁氧化物之前,可以对铁氧化物进行处理、洗涤或热调节。铁氧化物可以是红、黄或黑铁氧化物。黄铁氧化物是通常描述为Fe2O3·H2O或α-FeOOH的水合铁氧化物。当加入黄铁氧化物时,以Fe2O3计算,催化剂中总铁氧化物的至少5wt%或优选至少10wt%可以是黄铁氧化物,和总铁氧化物的至多50wt%可以是黄铁氧化物。红铁氧化物的一个实例可以通过煅烧由Penniman法生产的黄铁氧化物而制得。可以在催化剂中存在的提供铁氧化物的化合物包括针铁矿、赤铁矿、磁铁矿、磁赤铁矿和纤铁矿。
催化剂还可以含有选自碱金属组(包括锂、钠、钾、铷、铯和钫)的碱金属,和所述碱金属优选钾。可以使用这些金属中的一种或多种。碱金属可以作为碱金属化合物存在于催化剂中。碱金属通常存在的总量为每摩尔以Fe2O3计算的铁氧化物至少0.2摩尔、优选至少0.25摩尔、更优选至少0.45摩尔和最优选至少0.55摩尔。碱金属通常存在的量为每摩尔铁氧化物至多5摩尔或优选至多1摩尔。碱金属化合物可以包括:氢氧化物;碳酸盐;碳酸氢盐;羧酸盐,例如甲酸盐、乙酸盐、草酸盐和柠檬酸盐;硝酸盐;和氧化物。优选的碱金属化合物是碳酸钾。
催化剂还包含银,所述银可以作为银的任意化合物(例如氧化银和银铁氧体)存在,或者它可以作为银金属存在。银可以作为银铁氧体、碳酸银、硝酸银、氧化银、铬酸银、草酸银、银粉末、银纳米颗粒或银金属添加。此外,在催化剂形成期间,银化合物可能转化成银铁氧体或其它银化合物。银通常存在的总量为每摩尔以Fe2O3计算的铁氧化物至少0.5毫摩尔、优选至少1毫摩尔和更优选至少2.5毫摩尔、和最优选至少10毫摩尔。银通常存在的总量为每摩尔铁氧化物至多1摩尔和优选至多0.5摩尔。
催化剂可以还包含镧系元素。镧系元素选自原子序数为57-66(包括端值)的镧系元素。镧系元素优选铈。镧系元素可以作为镧系元素化合物存在。镧系元素通常存在的总量为每摩尔以Fe2O3计算的铁氧化物至少0.02摩尔、优选至少0.05摩尔、更优选至少0.06摩尔。镧系元素通常存在的总量为每摩尔铁氧化物至多0.2摩尔、优选至多0.15摩尔、更优选至多0.14摩尔。镧系元素化合物可以包括:氢氧化物;碳酸盐;碳酸氢盐;羧酸盐,例如甲酸盐、乙酸盐、草酸盐和柠檬酸盐;硝酸盐;和氧化物。优选镧系元素化合物是碳酸铈。
催化剂可以还包含碱土金属或它的化合物。碱土金属可以是钙或镁,和优选是钙。碱土金属化合物通常存在的量为每摩尔以Fe2O3计算的铁氧化物至少0.01摩尔和优选至少0.02摩尔。碱土金属化合物通常存在的量为每摩尔铁氧化物至多1摩尔和优选至多0.2摩尔。
催化剂可以还包含第6族金属或它的化合物。第6族金属可以是钼或钨,和优选是钼。第6族金属通常存在的量为每摩尔以Fe2O3计算的铁氧化物至少0.01摩尔,优选至少0.02摩尔。第6族金属通常存在的量为每摩尔铁氧化物至多0.5摩尔,优选至多0.1摩尔。
可以与铁氧化物组合的附加催化剂组分包括选自以下的金属及其化合物:Sc、Y、Ti、Zr、Hf、V、Nb、Ta、Cr、Mn、Tc、Re、Ru、Os、Co、Rh、Ir、Ni、Pd、Pt、Cu、Au、Zn、Cd、Hg、Al、Ga、In、Tl、Si、Ge、Sn、Pb、P、As、Sb、Bi、S、Se和Te。这些组分可以通过本领域技术人员已知的任意方法添加。附加催化剂组分可以包括:氢氧化物;碳酸氢盐;碳酸盐;羧酸盐,例如甲酸盐、乙酸盐、草酸盐和柠檬酸盐;硝酸盐;和氧化物。钯、铂、钌、铑、铱、铜和铬是优选的附加催化剂组分。
催化剂可以通过本领域技术人员已知的任意方法制备。例如,可以形成包含铁氧化物、碱金属或它的化合物、银或它的化合物和任意附加催化剂组分的糊剂。可以对这些催化剂组分的混合物进行研磨和/或捏合,或可以在铁氧化物上浸渍这些组分中的任一种的均相或非均相溶液。各组分的足够量可以根据待制备的催化剂的组成进行计算。可应用方法的实例可以在US5,668,075、US5,962,757、US5,689,023、US5,171,914、US5,190,906、US6,191,065和EP1027928中找到,上述文献经此引用并入本文。
在形成催化剂中,可以使包含铁氧化物、碱金属或它的化合物、银或它的化合物和任意附加催化剂组分的混合物成型为任意形式的粒料,例如片剂、小球、丸剂、鞍状料、三叶草、扭曲三叶草、四叶草、环形料、星形料、中空和实心柱状料、以及不对称叶状颗粒,如美国专利申请公开2005/0232853中所述。添加适合量的水,例如以混合物重量计算至多30wt%、通常是2-20wt%可以促进成型为粒料。如果加入了水,则在煅烧前可以至少部分脱除水。适合的成型方法是造粒、挤出和压制。作为造粒、挤出或压制的替代,混合物可以喷雾或喷雾干燥形成催化剂。必要时,喷雾干燥可以扩展为包括造粒和煅烧。
可以使附加化合物与所述混合物组合,所述附加化合物作为成型和/或挤出催化剂过程的助剂,所述附加化合物例如饱和或不饱和脂肪酸(例如软脂酸、硬脂酸或油酸)或它的盐、多醣衍生酸或它的盐、或石墨、淀粉、或纤维素。可以应用脂肪酸或多醣衍生酸的任意盐,例如铵盐或前文提及的任意金属的盐。脂肪酸的分子结构中可以含有6-30个碳原子(包括端值),优选10-25个碳原子(包括端值)。当使用脂肪酸或多醣衍生酸时,它可以与制备催化剂中应用的金属盐组合,以形成脂肪酸或多醣衍生酸的盐。附加化合物的适合量为例如混合物重量的至多1wt%、特别是0.001-0.5wt%。
在成形后,可以干燥和煅烧催化剂混合物。干燥通常包括在约30-500℃、优选约100-300℃的温度下加热催化剂。干燥时间通常是约2分钟-5小时,优选约5分钟-1小时。煅烧通常包括在惰性气体(例如氮或氦)或氧化气氛(例如含氧气体、空气、富氧空气)或氧气/惰性气体混合物中加热催化剂。煅烧温度通常是至少约600℃、或优选至少约700℃、更优选至少825℃和最优选至少880℃。煅烧温度通常是至多约1600℃或优选至多约1300℃。通常,煅烧时长为5分钟-12小时,更通常为10分钟-6小时。
根据本发明形成的催化剂可以表现出宽范围的物理性质。可以在宽范围内选择催化剂的表面结构,通常从孔体积、中值孔径和表面积角度进行。催化剂的表面结构可以通过煅烧温度和时间的选择以及通过应用挤出助剂而影响,
适合地,催化剂的孔体积为至少0.01ml/g,更适合地为至少0.05ml/g。适合地,催化剂的孔体积为至多0.5、优选至多0.4ml/g、更优选至多0.3ml/g和最优选至多0.2ml/g。适合地,催化剂的中值孔径为至少特别是至少适合地,催化剂的中值孔径为至多特别是至多在优选实施方案中,中值孔径为如本文所用,孔体积和中值孔径利用MicromereticsAutopore9420型根据ASTMD4282-92至6000psia的绝对压力(4.2×107Pa)通过压汞法测量(130°接触角,汞的表面张力为0.473N/m)。如本文所用,中值孔径定义为达到50%的压汞法体积时的孔径。
催化剂的表面积优选是0.01-20m2/g,更优选0.1-10m2/g。
催化剂的抗压强度适合地为至少10N/mm,和更适合地为20-100N/mm,例如约55或60N/mm。
在另一方面中,本发明提供通过使可脱氢烃和蒸汽与根据本发明制备的铁氧化物基催化剂接触使可脱氢烃脱氢以生产相应的脱氢烃的方法。
通过脱氢过程形成的脱氢烃是具有以下通式的化合物:R1R2C=CH2,其中R1和R2独立地表示烷基、烯基或苯基或氢原子。
可脱氢烃是具有以下通式的化合物:R1R2HC-CH3,其中R1和R2独立地表示烷基、烯基或苯基或氢原子。
适合的苯基可以含有一个或多个甲基作为取代基。适合的烷基通常每分子含有2-20个碳原子,和优选3-8个碳原子,例如正丁烷和2-甲基丁烷的情况。适合的烷基取代基是丙基(-CH2-CH2-CH3)、2-丙基(即1-甲基乙基,-CH(-CH3)2)、丁基(-CH2-CH2-CH2-CH3)、2-甲基-丙基(-CH2-CH(-CH3)2)、和己基(-CH2-CH2-CH2-CH2-CH2-CH3),特别是乙基(-CH2-CH3)。适合的烯基通常每分子含有约4-20个碳原子、和优选4-8个碳原子。
可脱氢烃可以是烷基取代苯,虽然还可以应用其它芳族化合物,例如烷基取代萘、蒽或吡啶。适合的可脱氢烃是丁基-苯、己基苯、(2-甲基丙基)苯、(1-甲基乙基)苯(即枯烯)、1-乙基-2-甲基-苯、1,4-二乙基苯、乙基苯、1-丁烯、2-甲基丁烷和3-甲基-1-丁烯。利用本方法,可以通过1-丁烯将正丁烷转化成1,3-丁二烯,和通过叔戊烯将2-甲基丁烷转化成异戊二烯。
可以通过本方法生产的脱氢烃实例是丁二烯、α-甲基苯乙烯、二乙烯基苯、异戊二烯和苯乙烯。
脱氢过程通常是气相法,其中使包含反应物的气态进料与固体催化剂接触。催化剂可以作为催化剂颗粒的流化床形式或填充床形式存在。所述方法可以作为间歇法或作为连续法进行。氢可以是脱氢过程的另外产物,和正在讨论的脱氢可以是非氧化脱氢。可用于脱氢过程的方法的实例可以在US5,689,023、US5,171,914、US5,190,906、US6,191,065和EP1027928中找到,上述文献经此引用并入本文。
将水作为进料的附加组分应用是有利的,所述水可以是蒸汽形式。在脱氢过程期间,水的存在将降低催化剂上焦炭的沉积速率。通常进料中水与可脱氢烃的摩尔比为1-50,更通常为3-30,例如5-10。
脱氢过程通常在500-700℃、更通常550-650℃(例如600℃或630℃)的温度下进行。在一个实施方案中,脱氢过程是等温进行的。在其它实施方案中,脱氢过程以绝热方式进行,其中提及的温度是反应器入口温度,和随着脱氢进行,所述温度可以通常下降至多150℃、更通常下降10-120℃。绝对压力通常是10-300kPa,更通常是20-200kPa,例如50kPa或120kPa。
必要时,可以应用1个、2个或更多个反应器,例如3个或4个。反应器可以串连或并联操作。它们可以是或可以不是互相独立操作,和各反应器可以在相同条件下或在不同条件下操作。
当利用填充床反应器作为气相法操作脱氢过程时,LHSV可以优选为0.01-10h-1,更优选为0.1-2h-1。如本文所用,术语“LHSV”表示液体小时空速,其定义为在标准条件(即0℃和1bar绝压)下测量的烃进料的液体体积流量除以催化剂床层的体积或除以催化剂床层的总体积(如果存在两个或更多个催化剂床层)。
可以选择脱氢过程的条件,使得可脱氢烃的转化率为20-100摩尔%,优选30-80摩尔%或更优选35-75摩尔%。
催化剂的活性(T70)定义为在给定操作条件下脱氢过程中可脱氢烃的转化率为70摩尔%时的温度。因此,活性更高的催化剂的T70低于活性较低的催化剂。相应的选择性(S70)定义为在转化率为70摩尔%时的温度下所需产物的选择性。
可以通过任意已知的装置,从脱氢过程的产物中回收脱氢烃。例如,脱氢过程可以包括分馏或反应蒸馏。必要时,脱氢过程可以包括加氢步骤,其中使至少一部分产物经历加氢,通过所述加氢步骤使脱氢期间形成的任意副产物的至少一部分转化成脱氢烃。经历加氢的部分产物可以是富含副产物的产物的一部分。该加氢为本领域中已知。例如,从US5,504,268、US5,156,816、和US4,822,936已知的方法可以容易用于本发明,上述文献经此引用并入本文。
脱氢过程的一个优选实施方案是使乙基苯非氧化脱氢形成苯乙烯。该实施方案通常包括在约500-700℃的温度下,将包含乙基苯和蒸汽的进料加入包含催化剂的反应区。蒸汽通常在蒸汽与烃的摩尔比为约7-15下存在于进料中。作为替代,该过程可以在约1-7、优选约2-6的更低蒸汽与烃的摩尔比下进行。除了苯乙烯之外,该过程通常生产少量的副产物,例如苯基乙炔和α-甲基苯乙烯。α-甲基苯乙烯是不希望的副产物,因为当在苯乙烯的后续聚合时,它作为链终止剂。
脱氢过程的另一个优选实施方案是使乙基苯氧化脱氢形成苯乙烯。该实施方案通常包括在约500-800℃的温度下,将乙基苯和氧化剂加入包含催化剂的反应区,所述氧化剂例如氧、碘化物、硫、二氧化硫或二氧化碳。氧化脱氢反应是放热的,所以所述反应可以在更低的温度和/或更低的蒸汽与油的比下进行。
脱氢过程的另一个优选实施方案是使异戊烯脱氢形成异戊二烯。该实施方案通常包括在约525-675℃的温度下,将包含2-甲基-1-丁烯、2-甲基-2-丁烯和3-甲基-1-丁烯的混合异戊烯进料加入包含催化剂的反应区中。所述过程通常在大气压力下进行。蒸汽通常以约13.5-31的蒸汽与烃的摩尔比加入进料中。
脱氢过程的另一个优选实施方案是使丁烯脱氢形成丁二烯。该实施方案通常包括在约500-700℃的温度下,将包含1-丁烯和2-丁烯(顺式和/或反式异构体)的混合丁烯进料加入包含催化剂的反应区。
由于大多数这些脱氢过程的吸热属性,通常期望附加的热量输入以维持所需的温度,从而维持转化率和选择性。热量可以在反应区之前、反应区之间(当存在两个或更多个区时)或直接加入反应区。
适合加热方法的优选实施方案是使用常规换热器。可以在进入第一或任意后续反应器之前加热过程物流。优选的热源包括蒸汽和其它加热的过程物流。
适合加热方法的另一优选实施方案是使用US7,025,940中描述的无火焰分布式燃烧加热器系统,上述文献经此引用并入本文。
适合加热方法的另一优选实施方案是催化或非催化氧化再热。这类加热方法的实施方案描述于US4,914,249、US4,812,597、和US4,717,779中,上述文献经此引用并入本文。
通过脱氢过程生产的脱氢烃可以用作聚合过程和共聚过程中的单体。例如,获得的苯乙烯可以用于生产聚苯乙烯和苯乙烯/二烯橡胶中。通过本发明使用较低成本催化剂获得的改进催化剂性能导致用于生产脱氢烃的更具吸引力的方法,和因此包括生产脱氢烃以及随后在生产包含脱氢烃的单体单元的聚合物和共聚物的制备中使用脱氢烃的更具吸引力的方法。对于可应用的聚合催化剂、聚合过程、聚合物处理方法和所得聚合物的用途,参考H.F.Marks等人编辑的“EncyclopediaofPolymerScienceandEngineering”,第2版,纽约,第16卷,第1-246页,以及其中引用的参考文献。
提供下列实施例以描述本发明,但是这些实施例不应被理解为限定本发明的范围。
实施例1(对比)
通过组合900g含有0.08wt%的Cl和表面积为3.2m2/g的铁氧化物(Fe2O3)(通过铁氯化物热分解制得)和100g黄铁氧化物(FeOOH)以及足够的碳酸钾、碳酸铈(作为含52wt%Ce的水合Ce2(CO3)3)、三氧化钼、和碳酸钙制备催化剂,从而获得含有每摩尔铁氧化物18mmolMo和其它组分如表1中所示的催化剂。加入水(约为干燥混合物重量的10wt%),以形成糊剂,和挤出糊剂以形成3mm直径的柱状料,随后将所述柱状料切成6mm长度。将粒料在170℃下、于空气中干燥15分钟和随后在888℃下、于空气中煅烧1小时。表1中以每摩尔以Fe2O3计算的铁氧化物的毫摩尔数显示了煅烧后催化剂的组成。
将100cm3催化剂样品用于在设计用于连续操作的反应器中,在等温测试条件下从乙基苯制备苯乙烯。条件如下:绝对压力76kPa,蒸汽与乙基苯的摩尔比为10,和LHSV为0.65h-1。在该测试中,将温度初始保持在595℃下约5-10天。之后调节温度,使得达到70摩尔%的乙基苯转化率(T70)。测量在选定温度下的苯乙烯选择性(S70)。
实施例2-17
催化剂根据本发明制备。使用实施例1中描述的成分。一些实施例使用了不同量的这些成分,如表1中的催化剂组成所示。另外,煅烧温度如表1中所示,因为一些催化剂在不同温度下煅烧。实施例2-17的催化剂含有以氧化银形式添加的不同量的银。催化剂在与实施例1的催化剂相同的条件下测试,和催化剂性能示于表1中。
表1
从实施例1-4中可以看出,对于含有相同成分和在相同温度下煅烧的催化剂,如果它含有银,则活性更高和选择性更高。实施例5-12显示了改变催化剂的铈量和煅烧温度的效果。实施例13和14显示了在不同温度下煅烧的催化剂,实施例13的催化剂在740℃下煅烧,和实施例14的催化剂在1035℃下煅烧。实施例15-17证明了改变催化剂中钙和钾的量对催化剂性能的影响。
实施例18(对比)和19
实施例18-19证实了当使用的铁氧化物与实施例1-17中使用的铁氧化物不同时观测到的催化剂性能。在实施例18中,催化剂利用通过热处理沉淀黄铁氧化物生产的红铁氧化物制备。红铁氧化物的表面积是5.1m2/g和红铁氧化物含有小于10ppmw的氯化物。黄铁氧化物从铁硫酸盐的氧化制得。组合以下成分:1000g上文描述的铁氧化物,足量的碳酸钾、碳酸铈(作为含52wt%Ce的水合Ce2(CO3)3)、三氧化钼、和碳酸钙,从而获得表2中所示的组合物。加入水(约为干燥混合物重量的10wt%),以形成糊剂,和挤出糊剂以形成3mm直径的柱状料,随后将所述柱状料切成6mm长度。将粒料在170℃下、于空气中干燥15分钟和随后在875℃下、于空气中煅烧1小时。实施例19的催化剂以与实施例18相同的方式制备,只是加入了氧化银,从而获得表2中所示的组合物。实施例18和19的催化剂的催化剂性能利用实施例1-17中相同的方法测试,只是温度初始保持在600℃下。结果示于表2中。
实施例20(对比)和21
实施例20-21证实了当如实施例1-17中一样使用通过热分解制备的再生铁氧化物、但在如上所述于催化剂中使用之前对所述再生铁氧化物进行了重构时观测到的催化剂性能。在实施例20中,通过在995℃下煅烧1000g再生铁氧化物与足量的三氧化钼制备混合物,以生产含有每摩尔以Fe2O3计算的铁氧化物19.5毫摩尔钼的重构铁氧化物组合物。重构铁氧化物组合物与足量的碳酸钾、碳酸铈(作为含52wt%Ce的水合Ce2(CO3)3)和碳酸钙组合,从而获得表2中所示的组合物。加入水(约为干燥混合物重量的5wt%),以形成糊剂,和挤出糊剂以形成3mm直径的柱状料,随后将所述柱状料切成6mm长度。将粒料在170℃下、于空气中干燥15分钟和随后在775℃下、于空气中煅烧1小时。表2中显示了煅烧后催化剂的组成。实施例21的催化剂以与实施例20相同的方式制备,只是与碳酸钾、碳酸铈和碳酸钙一起加入了氧化银,以获得表2中所示的组合物。实施例20和21的催化剂利用实施例1-17中相同的方法测试,只是温度初始保持在600℃下。结果示于表2中。
表2
从实施例18-19可以看出,含有银的非再生铁氧化物基催化剂的选择性高于不含银的相似催化剂。从实施例20-21可以看出,含有银的重构铁氧化物基催化剂的活性和选择性高于不含银的相似催化剂。
实施例22(对比)和23-27
催化剂根据实施例1-17的方法制备。成分以不同的量使用,和表3中显示了煅烧后的催化剂组成。实施例22-27的催化剂根据上述实施例的相同方法进行测试。测量产物中α-甲基苯乙烯(AMS)的量,和作为相对于来自脱氢反应器的冷凝产物物流重量的ppmw示于表3中。在T70温度下,通过气相色谱测试α-甲基苯乙烯水平。实施例22描述了具有相同组成的三种催化剂的平均结果。
表3
从实施例22-27可以看出,含有银的铁氧化物基脱氢催化剂可以导致乙基苯脱氢过程中产生减少量的α-甲基苯乙烯杂质。
本领域技术人员可以改变上文显示的多个变量以及其它变量,以获得对于特定应用最有效的脱氢催化剂。还可以加入附加催化剂组分以影响催化剂的性质和性能。可以针对变量如干燥时间和温度、煅烧时间和温度、以及处理速度改变催化剂制备方法,以影响催化剂的性质和性能。
Claims (15)
1.一种脱氢催化剂,其包含铁氧化物、碱金属或它的化合物、第6族金属或它的化合物以及银或它的化合物,其中铁氧化物的存在量以Fe2O3计算为10-90wt%,碱金属或它的化合物的存在量为每摩尔以Fe2O3计算的铁氧化物0.2-5摩尔,第6族金属或它的化合物的存在量为每摩尔以Fe2O3计算的铁氧化物10-500毫摩尔,和银或它的化合物的存在量为每摩尔以Fe2O3计算的铁氧化物0.5-1000毫摩尔。
2.权利要求1的催化剂,其中所述催化剂的孔体积为0.05-0.2ml/g,所述催化剂的表面积为0.1-10m2/g,和所述催化剂的抗压强度为20-100N/mm。
3.权利要求1的催化剂,其中铁氧化物包括通过铁卤化物热分解形成的再生铁氧化物,其中由于热分解使所述铁氧化物中残余卤化物的含量降至至多1500ppm。
4.权利要求1的催化剂,其中催化剂还包含镧系元素,镧系元素的存在量为每摩尔以Fe2O3计算的铁氧化物20-200毫摩尔。
5.权利要求4的催化剂,其中镧系元素的存在量为每摩尔以Fe2O3计算的铁氧化物60-140毫摩尔。
6.权利要求1的催化剂,其中催化剂还包含碱土金属,碱土金属的存在量为每摩尔以Fe2O3计算的铁氧化物10-1000毫摩尔。
7.权利要求6的催化剂,其中碱土金属的存在量为每摩尔以Fe2O3计算的铁氧化物20-200毫摩尔。
8.权利要求1的催化剂,其中铁氧化物的存在量以Fe2O3计算为60-80wt%。
9.权利要求1的催化剂,其中碱金属或它的化合物的存在量为每摩尔以Fe2O3计算的铁氧化物0.55-1摩尔。
10.权利要求1的催化剂,其中第6族金属或它的化合物的存在量为每摩尔以Fe2O3计算的铁氧化物20-100毫摩尔。
11.权利要求1的催化剂,其中银或它的化合物的存在量为每摩尔以Fe2O3计算的铁氧化物10-500毫摩尔。
12.权利要求1的催化剂,其中碱金属或它的化合物包括钾。
13.权利要求4的催化剂,其中镧系元素或它的化合物包括铈。
14.权利要求6的催化剂,其中碱土金属或它的化合物包括钙。
15.权利要求1的催化剂,其中第6族金属或它的化合物包括钼。
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN113880684A (zh) * | 2020-07-01 | 2022-01-04 | 中国石油化工股份有限公司 | 混合二乙烯基苯及其生产方法 |
CN113880684B (zh) * | 2020-07-01 | 2023-10-31 | 中国石油化工股份有限公司 | 混合二乙烯基苯及其生产方法 |
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JP5313233B2 (ja) | 2013-10-09 |
TW200911365A (en) | 2009-03-16 |
BRPI0810802A2 (pt) | 2014-10-29 |
KR20100017489A (ko) | 2010-02-16 |
EP2152412A2 (en) | 2010-02-17 |
US20090062588A1 (en) | 2009-03-05 |
US8119559B2 (en) | 2012-02-21 |
WO2008137583A2 (en) | 2008-11-13 |
JP2013240789A (ja) | 2013-12-05 |
JP2016117057A (ja) | 2016-06-30 |
CN101678334A (zh) | 2010-03-24 |
CA2685692A1 (en) | 2008-11-13 |
JP2010525941A (ja) | 2010-07-29 |
RU2009144774A (ru) | 2011-06-10 |
WO2008137583A3 (en) | 2009-11-05 |
AR066417A1 (es) | 2009-08-19 |
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