CN1216938A - 用于选择性芳构化的催化剂 - Google Patents
用于选择性芳构化的催化剂 Download PDFInfo
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- CN1216938A CN1216938A CN97194129A CN97194129A CN1216938A CN 1216938 A CN1216938 A CN 1216938A CN 97194129 A CN97194129 A CN 97194129A CN 97194129 A CN97194129 A CN 97194129A CN 1216938 A CN1216938 A CN 1216938A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 66
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- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 12
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 11
- 229910052718 tin Inorganic materials 0.000 claims abstract description 11
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 9
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 5
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- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims abstract description 4
- 230000000737 periodic effect Effects 0.000 claims abstract description 4
- 229910052714 tellurium Inorganic materials 0.000 claims abstract description 4
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000005864 Sulphur Substances 0.000 claims abstract description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 3
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- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 3
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- XINQFOMFQFGGCQ-UHFFFAOYSA-L (2-dodecoxy-2-oxoethyl)-[6-[(2-dodecoxy-2-oxoethyl)-dimethylazaniumyl]hexyl]-dimethylazanium;dichloride Chemical compound [Cl-].[Cl-].CCCCCCCCCCCCOC(=O)C[N+](C)(C)CCCCCC[N+](C)(C)CC(=O)OCCCCCCCCCCCC XINQFOMFQFGGCQ-UHFFFAOYSA-L 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
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- YKIAZARODMJWBV-UHFFFAOYSA-N formic acid;lanthanum Chemical compound [La].OC=O YKIAZARODMJWBV-UHFFFAOYSA-N 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical group [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
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- OXHNIMPTBAKYRS-UHFFFAOYSA-H lanthanum(3+);oxalate Chemical compound [La+3].[La+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O OXHNIMPTBAKYRS-UHFFFAOYSA-H 0.000 description 1
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Classifications
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/373—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen with simultaneous isomerisation
- C07C5/393—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen with simultaneous isomerisation with cyclisation to an aromatic six-membered ring, e.g. dehydrogenation of n-hexane to benzene
- C07C5/41—Catalytic processes
- C07C5/415—Catalytic processes with metals
- C07C5/417—Catalytic processes with metals of the platinum group
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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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/58—Platinum group metals with alkali- or alkaline earth metals
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
- B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
- B01J23/626—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with tin
-
- 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
- B01J37/0201—Impregnation
- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
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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
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Abstract
一种催化剂,特别是用于由含C6-C12直链的、支链的和/或环状的烷基-或亚烷基的烃类物流制备芳烃的催化剂,该催化剂含有至少一种选自元素周期表第八族元素和/或铼和/或锡,如果需要,还含有碱金属-或碱土金属的化合物、第三主族或副族元素的化合物或锌或至少一种选自硫、碲、砷、锑或硒的化合物,它们负载在元素周期表第ⅣB过滤金属的氧化物上,催化剂可用于由C6-C12烃类制备芳烃,例如乙苯或二甲苯。
Description
本发明涉及一种负载在陶瓷载体上的含贵金属催化剂,它用于由链烷属/环烷属烃类物流选择性制备芳烃,所述的烃类物流含有C6-C12直链的、支链的和/或环状的烷基或亚烷基链。本发明尤其涉及制备C8芳烃。
工业上重要的C6-C8芳烃例如苯、二甲苯或乙苯的最重要来源是催化重整工艺。在催化重整工艺中,正构烷烃转化成支链烷烃、脂族-芳族烃和芳烃。一方面,这一工艺用于提高四冲程发动机燃料的抗爆性能,也即得到的反应混合物通常就这样使用;另一方面,例如用蒸馏的方法将制得的芳族化合物分离,例如用于生产合成橡胶和合成纤维的中间体和合成原料。例如为了生产苯乙烯和聚苯乙烯,需要从C8馏分得到乙苯。
重整工艺涉及各种反应,例如异构化、芳构化(脱氢)和环化。该工艺在450-550℃、15-70巴下进行,它通常用铂/载体催化剂来控制。
除铂以外,还含有其他金属的催化剂也是已知的,例如Pt-Re/Al2O3·SiO2或Pt/Sn/Al2O3·SiO2(称为双金属催化剂);例如,基于Pt/Sn/Al2O3的催化剂在分子催化作用,88(1994)359-376中描述。载体材料通常为硅铝酸盐或沸石。Pt/L沸石催化剂(参见能源进展7,(1987),215-222)具有高的芳烃选择性,这一点归因于载体的形状选择性,但是它的空-时产率较低。相反,多组分催化剂,例如Pt/Co/Nd(US-A-4 136 130)或Pt/Co/Re/Ge(US-A 4 136017)在(非沸石的)氯化的Al2O3载体上的催化剂有更高的活性,但倾向于生成裂化产物,因此有较低的芳烃选择性,特别是就生成的C8芳烃(乙苯、苯乙烯、二甲苯)而言。
本发明的一个目的是提供一种没有上述缺点或上述缺点相当不明显的催化剂,该催化剂将C6-C12烃类物流高产率地较化成芳烃。一个特别的目的是,找到一种具有特别高乙苯选择性的催化剂,乙苯在C8芳烃中具有最高的附加价值。
我们已发现,这一目的可用这样一种催化剂来达到,该催化剂含有一种选自元素周期表第八族元素的贵金属,特别是钯、铂或铑和/或铼和/或锡,并负载在一种或多种第四副族(4B族)元素的金属陶瓷氧化物上、特别是ZrO2和TiO2。
除了上述元素外,使用其他元素也是可能的,特别是铼和/或锡作为添加物加到第八族元素中。此外,本发明一个重要的组成部分是加入或掺杂入第三主族或副族(3A或3B族)的化合物,或加入或掺杂入碱性化合物例如碱金属氧化物、碱土金属氧化物,或稀土元素氧化物,或可在400℃以上转化成相应氧化物的这些元素的化合物。同时用上述多种元素或其化合物掺杂是可能的。例如,钾和镧的化合物是很适用的。此外,催化剂还可与含硫、碲、砷、锑或硒的化合物混合,它们常常通过部分“中毒”(温和化剂)起提高选择性的作用。
与现有技术的已知催化剂相比,本发明的催化剂的优点是,有更高的芳烃总选择性,特别是C8芳烃选择性。此外,本发明的催化剂使更高的转化率成为可能,这与本发明的催化剂比现有技术的催化剂有更高的芳烃产率有关。
本发明的催化剂可用两性陶瓷氧化物、特别是锆和钛的氧化物或其混合物来制备;可通过焙烧转化成这些氧化物的相应化合物也是适用的。它们可用已知的方法来制备,例如溶胶-凝胶法、盐淀淀法、相应酸的脱水法、干混法、浆化法或喷雾干燥法。
适用的载体都是氧化锆和氧化钛的改性产物。但是,对于制备基于ZrO2的催化剂来说,已发现用X射线衍射法测定为单斜ZrO2的比例大于90%是有利的,在X射线衍射图中,单斜ZrO2的特征是,在约28.2和31.5的2θ值处有两个强峰。
在制备过程中可进行碱性化合物的掺杂,例如通过共沉淀进行掺杂,或者随后用碱金属化合物或碱土金属化合物或第三副族元素的化合物或稀土金属化合物浸渍陶瓷氧化物。
碱金属或碱土金属、第三主族或副族金属、稀土金属或锌的含量通常至多为20%(重量)、优选0.1-15%(重量)、特别优选0.5-10%(重量)。作为碱金属和碱土金属加入的化合物,通常使用通过焙烧可转化成相应氧化物的那些化合物。适合的化合物例如为碱金属和碱土金属的氢氧化物、碳酸盐、草酸盐、乙酸盐、硝酸盐或混合羟基碳酸盐。
如果陶瓷载体还用或单独用第三主族或副族金属掺杂,那么在这种情况下,用作原料的化合物也应为通过焙烧可转化成相应氧化物的那些化合物,如果使用镧,适合化合物的例子是碳酸氧化镧、La(OH)3、La2(CO3)3、La(NO3)3或含有有机阴离子的镧化合物,例如乙酸镧、甲酸镧或草酸镧。
可用各种方法加入贵金属组分。例如,用贵金属或铼或锡的适宜化合物的溶液浸渍或喷雾载体。适合制备这些溶液的金属盐例如是贵金属的硝酸盐、卤化物、甲酸盐、草酸盐或乙酸盐。也可使用络合物阴离子或这些络合物阴离子的酸,例如H2PtCl6。特别适用于制备本发明催化剂的化合物是PdCl2、Pd(OAc)2、Pd(NO3)2和Pt(NO3)2。
本发明的催化剂也可用含有一种或多种组分的贵金属溶胶来制备,其中活性组分完全或部分以还原态存在。
如果使用贵金属溶胶,它们预先用常规的方法制备,例如先将一种金属盐或多种金属盐的混合物在稳定剂例如聚乙烯基吡咯烷酮存在下还原,然后用浸渍或喷雾的方法涂布到载体上。这一制备方法在未在先公开的德国专利申请书19500366.7中详描。
第八族元素或铼或锡在催化剂中的含量例如可为0.005-5%(重量)、优选0.01-2%(重量)、特别优选0.1-1.5%(重量)。如果还使用铼或锡,它们对贵金属组分的比例如可为0.1∶1至20∶1、优选1∶1至10∶1。
作为温和化添加剂(按现在的概念,为催化剂部分中毒),如果需要,有可能使用含硫、碲、砷或硒的化合物。在催化剂使用过程中,一氧化碳的加入也是可能的。硫的使用是特别适用的,优选以硫化铵(NH4)2S的形式使用。贵金属组分与催化剂毒物的摩尔比可在1∶0至1∶10、优选1∶1至1∶0.05范围内变化。
催化剂在反应器中可以固定床形式使用,或以流化床形式使用,它可有一种适合的物理结构。适合的形状例如为颗粒、小条、整体物、球形物或挤条物(挤出的棒状物或小丸、车轮状物、环状物)。
催化剂制品的BET表面积至多500米2/克,通常为10-300米2/克、特别优选20-300米2/克。孔体积一般为0.1-1毫升/克、优选0.15-0.6毫升/克、特别优选0.2-0.4毫升/克。可用压汞法测定的中孔平均孔径通常为8-60纳米、优选10-40纳米。孔径大于20纳米的孔的比例在0-60%之间变化;发现使用大孔(即孔径大于20纳米)大于10%的载体是有利的。
具体的反应在以下条件下进行:温度300-800℃、优选400-600℃、特别优选400-550℃,压力为100毫巴至100巴、优选1-40巴,LHSV为0.01-100小时-1、优选0.1-20小时-1。除了要脱氢的烃类混合物外,还可有稀释剂例如CO2、N2、稀有气体或水蒸汽存在。同样,如果需要,还可加入氢气,氢与烃类(气体)的体积比可为0.1-100、优选1-20。加入的氢可用于除去随着反应时间增加在催化剂表面上积累的碳。
除了连续加入用于防止在反应过程中碳的沉积的气体外,还可不时地将氢气或空气通过催化剂来再生催化剂。再生可在300-900℃、优选400-800℃,使用游离氧化剂、优选使用空气,或在还原气氛中、优选使用氢气来进行。再生可在常压下、减压下或加压下进行。适合的压力例如为500毫巴至100巴。
催化剂制备
实施例1、2
将6.38克Pd(OAc)2溶于500毫升水中,加入5克聚乙烯基吡咯烷酮。将500毫升0.34M的柠檬酸钠溶液加到该溶液中,并将混合物回流4小时。得到透明的Pd溶胶。
分析结果:0.3%Pd
用双流体喷嘴将钯溶胶喷雾到加热旋转板上的200克ZrO2小条(5×3毫米小条)上。随后将小条在120℃下干燥72小时,并根据其吸水量(23.5毫升/100克),用2.96克K2CO3于47毫升水中的溶液浸渍1小时。在浸渍过程中,将它们摇动数次,然后在120℃下干燥18小时。
用水将1.1克40%(重量)硫化铵((NH4)2S)溶液稀释到47毫升,再用它浸渍上述预处理的小条,并在120℃下干燥16小时。
分析结果:1.3%Pd、0.96%K、0.17%S
实施例3、4、5
将5.6克草酸溶于55毫升水中。将4.27克Pd(OAc)2加到该溶液中,并通过缓和加热到50℃并剧烈搅拌使之溶解。
所用的二氧化锆为挤条状物,其BET表面积为92米2/克、孔体积为0.25毫升/克(压汞孔隙率计)和大约30%孔径大于0.02微米的孔。在每一情况下,用水吸附量(27.2克水/100克)计算的浓缩钯溶液浸渍200克ZrO2,一直到液体完全被吸收(约30分钟)。然后在旋转蒸发器上、在80℃下干燥挤条状物。随后在120℃下干燥16小时。
钯涂布后,将挤条状物浆化在3.61克K2CO3于55毫升水中的溶液中,约30分钟后再次在旋转蒸发器上、在80℃下干燥。然后将挤条状物在120℃下干燥28小时。
用55毫升水将1.1克40%(重量)硫化铵溶液稀释,然后用它浸渍预处理过的挤条状物,在旋转蒸发器上、在80℃下干燥,然后在120℃下干燥65小时。
分析结果:0.97%Pd、0.98%K、0.13%S、其余为ZrO2。
实施例6、7、8
将5.6克草酸溶于60毫升水中。将4.27克Pd(OAc)2加到该溶液中,通过剧烈搅拌和缓和加热到55℃使它溶解。用水吸附量(30.6克水/100克)计算的钯溶液量浸渍200克ZrO2挤条状物,其BET表面积为70米2/克,孔体积为0.28毫升/度,大于20纳米的孔约30%。约30分钟后,将挤条状物在旋转蒸发器上、在80℃下干燥。然后在120℃下干燥24小时。
钯涂布后,将挤条状物浆化在3.61克K2CO3于60毫升水中的溶液中,大约30分钟后再次在旋转蒸发器上、在80℃下干燥。然后将挤条状物在120℃下干燥28小时。
用55毫升水稀释1.1克40%(重量)硫化铵溶液。用稀释的溶液浸渍预处理的挤条状物,然后在旋转蒸发器上、在80℃下干燥。随后将挤条状物在120℃下干燥70小时。
分析结果:0.98%Pd、0.94%K、0.11%S。
实施例9、10
将5.6克草酸溶于52毫升水中。将4.27克Pd(OAc)2加到该溶液中,并通过剧烈搅拌和缓和加热到50℃使它溶解。
所用的二氧化锆为挤条状,其BET表面积为46米2/克,孔体积为0.23毫升/克(压汞孔隙率计)和约15%的孔大于0.02微米。用水吸附量(26克水/100克)计算的钯溶液量浸渍200克挤条状物。约30分钟后,将挤条状物在旋转蒸发器上、在80℃下干燥。随后将挤条状物在120℃下干燥14小时。
涂布钯后,将挤条状物浆化在3.61克K2CO3于52毫升水中的溶液中,约30分钟后,再次在旋转蒸发器上、在80℃下干燥。然后将挤条状物在120℃下干燥20小时。
用52毫升水稀释1.1克40%(重量)硫化铵溶液,用它浸渍预处理的挤条状物,然后在旋转蒸发器上干燥,先在80℃下干燥,然后在120℃下干燥65小时。
分析结果:0.92%Pd、0.89%K、0.11%S。
实施例11
将溶于2.7毫升水中的0.181克Pt(NO3)2(由Heraeus得到的商业产品#006438)和溶于2.6毫升水中的0.100克Sn(OAc)2在间隔1小时下依次涂布到10克二氧化锆挤条状物上(由Norton得到的商业产品#93163335;BET表面积为40米2/克,水吸附量为26克/100克),再涂布1小时后,将挤条状物在120℃下干燥16小时,然后在650℃下焙烧。制得的催化剂含在1%Pt和0.5%Sn。
实施例12
将溶于3.06毫升的0.181克Pt(NO3)2(如实施例11中的商业产品)和溶于3.06毫升水的0.100克Sn(OAc)2在间隔1小时下依次涂布到10克二氧化锆挤条状物上(由Norton得到的商业产品#93163321;BET表面积为49米2/克,水吸附量为30.6克/100克),再涂布1小时后,将挤条状物在120℃下干燥16小时,然后在650℃下焙烧。制得的催化剂含有1%Pt和0.5%Sn。
实施例13
将溶于21.4毫升水中的0.65克Pt(NO3)2(如实施例11中的商业产品)、3.27克硝酸钯(Ⅱ)溶液(11%(重量)水溶液)和溶于21.4毫升水中的1.42克Sn(OAc)2在间隔1小时下依次涂布到70克二氧化锆挤条状物上(如上述由Norton得到的商业产品#93163321),再涂布1小时后,将挤条状物在120℃下干燥16小时,然后在650℃下焙烧。制得的催化剂含1%Pt和0.5%Sn。
实施例14
将溶于21.4毫升水中的0.65克Pt(NO3)2(如实施例11中的商业产品)、3.27克硝酸钯(Ⅱ)溶液(11%(重量)水溶液)和溶于21.4毫升水中的1.42克Sn(OAc)2在间隔1小时下依次涂布到10克二氧化锆挤条状物上(如上由Norton得到的商业产品#93163321);再涂布1小时后,将挤条状物在120℃下干燥16小时,然后在650℃下焙烧。制得的催化剂含1%Pt和0.5%Sn。
实施例15
将溶于12毫升水中的0.182克Pt(NO3)2(上述商业产品)涂布到10克二氧化钛粉末上(由Kemira得到的商业产品Finnti S 140#71077);BET表面积277米2/克,水吸附量120克/100克),然后将它在120℃下干燥,在500℃下焙烧。制得的催化剂含1.15%Pt。
实施例16
将溶于12毫升水中的0.182克Pt(NO3)2(上述的商业产品)涂布到10克二氧化钛粉末上(BET表面积90米2/克,水吸附量94克/100克),在120℃干燥,在500℃下焙烧。得到的催化剂含1.1%铂。
实施例17
将溶于3.06毫升水中的0.066克Pt(NO3)2(上述的商业产品)和0.087克Pd(NO3)2涂布到10克挤条状物的氧化锆上,其孔体积0.28毫升/克;30%的孔为直径小于20纳米;晶相为单斜晶的;水吸附量为30.6克/100克);然后在120℃干燥,在500℃焙烧。得到的催化剂各含有0.5%的铂和钯。
在脉冲反应器中的实验
正辛烷(实施例1-16)或正壬烷(实施例17)物流的芳构化在微型固定床脉冲反应器中进行。称重约0.6克催化剂加到反应器中,并用上述烃类物流脉冲进料(常压,不加入氢)处理。在两次相继的脉冲之间(约1.5分钟),将氦气载气流过反应器。载气流速为约21.5毫升/分钟。一次脉冲含有约100μg正辛烷或正壬烷。用在线的GC-MS定量测量每一脉冲的反应产物。
得到约结果列入表1和2。所示的选择性基于每一情况下的最大转化率期间的结果。已知组成的商业重整催化剂用于比较。
表1
实施例 | 类型 | T | Ua) | 选择性[%] | ||||
序号 | [℃] | [%] | EB | o-Xl | Xlb) | ∑Arc) | ∑C8 d) | |
1 | Pd/K/ZrO2 | 450 | 62.27 | 11.1 | 6.7 | 5.4 | 86.6 | 23.2 |
2 | Pd/K/ZrO2 | 500 | 62.25 | 3.28 | 9.4 | 12.3 | 89.3 | 24.9 |
3 | Pd/K/ZrO2 | 450 | 75.1 | 21.8 | 32.1 | - | 74.6 | 53.9 |
4 | Pd/K/ZrO2 | 500 | 67.3 | 5.0 | 24.3 | 1.23 | 91.1 | 30.5 |
5 | Pd/K/ZrO2 | 450 | 66.0 | 16.5 | 37.1 | 2.1 | 90.8 | 55.7 |
6 | Pd/K/ZrO2 | 450 | 82.3 | 20.4 | 21.2 | 3.73 | 88.0 | 45.3 |
7 | Pd/K/ZrO2 | 450 | 76.3 | 14.4 | 14.0 | 6.2 | 86.1 | 34.6 |
8 | Pd/K/ZrO2 | 500 | 97.5 | 4.0 | 11.2 | 5.0 | 97.5 | 20.2 |
9 | Pd/K/ZrO2 | 450 | 51.4 | 8.3 | 11.7 | 13.6 | 80.6 | 33.6 |
10 | Pd/K/ZrO2 | 500 | 32.3 | 4.7 | 8.8 | 7.4 | 85.8 | 20.9 |
11 | Pt/Sn/ZrO2 | 500 | 97.8 | 33.4 | 52.9 | 2.8 | 96.9 | 89.1 |
12 | Pt/Sn/ZrO2 | 500 | 99.7 | 29.4 | 51.3 | 4.0 | 85.4 | 85.4 |
13 | Pt/Pd/Sn/ZrO2 | 500 | 100 | 28.5 | 50.5 | 5.6 | 94.4 | 86.4 |
14 | Pt/Sn/ZrO2 | 500 | 99.6 | 32.1 | 59.4 | 1.6 | 98.4 | 94.8 |
15 | Pt/TiO2 | 500 | 100 | 37.1 | 48.7 | 5.4 | 96.3 | 91.3 |
16 | Pt/TiO2 | 500 | 100 | 37.8 | 50.0 | 2.3 | 97.5 | 90.9 |
对比例 | Pt/Sn/Al2O3 | 500 | 75.1 | 3.0 | 37.6 | 10.9 | 72.0 | 51.5 |
a)转化率基于正辛烷(气相色谱的面积百分数)
b)间-和对-二甲苯的总和
c)所有测定的芳烃的总和
d)所有C8芳烃(乙苯+二甲苯)的总和
在相同温度下,本发明的催化剂与对比催化剂相比,对于总的芳烃产率有更高的选择性。显著的效果是有高的乙苯含量,乙苯有最高的附加价值。
表2
实施例 | 类型 | T | Ua) | 选择性(%) | ||||
[℃] | [%] | EB | ∑二甲苯 | 甲苯 | ∑C8 b) | ∑C9 c) | ||
17 | Pt/Pd/ZrO2 | 500 | 95 | 9.6 | 6.2 | 21.7 | 15.8 | 31 |
Claims (15)
1.一种催化剂,特别是用于由含有C6-C12直链的、支链的和/或环状的烷基或亚烷基链的烃类物流选择性地制备芳烃的催化剂,该催化剂含有至少一种选自元素周期表第八族元素中的元素和/或铼和/或锡,它们负载在第4B族过渡金属的氧化物上。
2.根据权利要求1的催化剂,其中它含有TiO2和/或ZrO2作为过渡金属氧化物。
3.根据权利要求2的催化剂,其中它含有绝大多数为锐钛矿的TiO2。
4.根据权利要求2的催化剂,其中含有绝大多数为单斜晶改进体的TiO2。
5.根据权利要求1的催化剂,其中含有0.005-5%(重量)钯、铂、铑和/或铼。
6.根据权利要求1的催化剂,其中还含有一种碱金属-或碱土金属的化合物、一种第三主族或副族元素的化合物和/或锌。
7.根据权利要求6的催化剂,其中碱金属为钠或钾。
8.根据权利要求6的催化剂,其中第三主族或副族元素的化合物为镧、钇、镓、铟或铊的化合物。
9.根据权利要求1的催化剂,其中含有至少一种选自硫、碲、砷、锑和/或硒中的化合物。
10.一种权利要求1的催化剂,其中BET表面积为10-500米2/克。
11.根据权利要求1的催化剂,其孔径为8-60纳米,其中至少10%的孔的孔径宽度大于20纳米,且比孔体积为0.1-1毫升/克。
12.一种制备权利要求1的催化剂的方法,该方法包括,将钯、铂、铑和/或铼的溶胶涂布到载体上。
13.权利要求1的催化剂的应用,用于由含有C6-C12直链的、支链的和/或环状的烷基-或亚烷基链的烃类制备芳烃。
14.权利要求1的催化剂的应用,用于制备乙苯和/或二甲苯。
15.权利要求1的催化剂的应用,用于制备C9芳烃。
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Cited By (6)
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CN101234349B (zh) * | 2007-01-31 | 2010-09-22 | 中国石油化工股份有限公司 | 一种烷烃和/或环烷烃芳构化催化剂及芳构化方法 |
CN102441412A (zh) * | 2010-10-12 | 2012-05-09 | 中国石油化工股份有限公司 | 一种芳构化催化剂及其在高选择性制备对二甲苯中的应用 |
CN106423255A (zh) * | 2015-08-12 | 2017-02-22 | 中国石油化工股份有限公司 | 乙苯催化剂及其制备方法 |
CN107282089A (zh) * | 2016-04-12 | 2017-10-24 | 中国石油化工股份有限公司 | 苯与乙烷烷基化的催化剂 |
CN107952476A (zh) * | 2017-12-13 | 2018-04-24 | 中石化炼化工程(集团)股份有限公司 | 用于醇石脑油耦合制备汽油调和组分的催化剂、制备方法及其应用 |
CN115518679A (zh) * | 2021-06-24 | 2022-12-27 | 中国石油化工股份有限公司 | 一种芳构化催化剂及其制备方法和应用和丁烷芳构化方法 |
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FR2770775B1 (fr) * | 1997-11-07 | 1999-12-24 | Oreal | Composition pour la teinture d'oxydation des fibres keratiniques comprenant un 3,4-diamino pyrazole 5-substitue et un meta-aminophenol halogene, et procede de teinture |
DE19937106A1 (de) * | 1999-08-06 | 2001-02-08 | Basf Ag | Multikomponenten-Katalysatoren |
WO2002051543A1 (de) * | 2000-12-22 | 2002-07-04 | Basf Aktiengesellschaft | Multikomponenten-katalysatoren |
DE102005053230A1 (de) * | 2005-11-06 | 2007-05-10 | Basf Ag | Verfahren zur Aromatisierung von Nichtaromaten und anschließende Dealkylierung von Alkyl-substituierten aromatischen Kohlenwasserstoffen mit Wasserdampf |
SG10201402458SA (en) * | 2009-05-20 | 2014-07-30 | Basf Se | Monolith catalyst and use thereof |
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US4136130A (en) * | 1977-01-12 | 1979-01-23 | Uop Inc. | Dehydrocyclization with an acidic multimetallic catalytic composite |
US4246095A (en) * | 1979-06-04 | 1981-01-20 | Uop Inc. | Hydrocarbon conversion with a sulfided superactive multimetallic catalytic composite |
GB8303574D0 (en) * | 1983-02-09 | 1983-03-16 | Ici Plc | Hydrocarbon conversion processes |
EP0614692A1 (en) * | 1990-05-03 | 1994-09-14 | Sakai Chemical Industry Co., Ltd., | Catalysts and methods for denitrization |
DE4109502A1 (de) * | 1991-03-22 | 1992-09-24 | Degussa | Katalysator zur haertung von fettsaeuren und verfahren zu seiner herstellung |
US5221464A (en) * | 1991-08-12 | 1993-06-22 | Sun Company, Inc. (R&M) | Process for catalytically reforming a hydrocarbon feed in the gasoline boiling range |
PL175047B1 (pl) * | 1993-04-22 | 1998-10-30 | Kti Group Bv | Sposób wytwarzania katalizatora do procesu wytwarzania gazu syntezowego |
DE4422046A1 (de) * | 1994-06-27 | 1996-01-04 | Basf Ag | Verfahren zur Herstellung von 1,2-Butylenoxid |
DE4445142A1 (de) * | 1994-12-17 | 1996-06-20 | Basf Ag | Katalysatoren oder Träger die im wesentlichen aus monoklinem Zirconiumdioxid bestehen |
DE19516318A1 (de) * | 1995-04-28 | 1996-10-31 | Inst Angewandte Chemie Berlin | Selektiver Aromatisierungskatalysator, Verfahren zur Herstellung und Verwendung |
-
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JP2000512539A (ja) | 2000-09-26 |
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