CN105579136B - Euo类型沸石的改性及其在芳族c8化合物的异构化中的用途 - Google Patents
Euo类型沸石的改性及其在芳族c8化合物的异构化中的用途 Download PDFInfo
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- CN105579136B CN105579136B CN201480043728.0A CN201480043728A CN105579136B CN 105579136 B CN105579136 B CN 105579136B CN 201480043728 A CN201480043728 A CN 201480043728A CN 105579136 B CN105579136 B CN 105579136B
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- 239000010457 zeolite Substances 0.000 title claims abstract description 137
- 238000006317 isomerization reaction Methods 0.000 title claims abstract description 18
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- 230000004048 modification Effects 0.000 title description 9
- 238000012986 modification Methods 0.000 title description 9
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 98
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 92
- 239000003054 catalyst Substances 0.000 claims abstract description 89
- 229910052751 metal Inorganic materials 0.000 claims abstract description 70
- 239000002184 metal Substances 0.000 claims abstract description 70
- 238000000034 method Methods 0.000 claims abstract description 52
- 239000011159 matrix material Substances 0.000 claims abstract description 18
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 13
- 125000003118 aryl group Chemical group 0.000 claims abstract description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 35
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- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 31
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 30
- 150000002739 metals Chemical class 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 229910052697 platinum Inorganic materials 0.000 claims description 16
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
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- 238000001354 calcination Methods 0.000 claims description 11
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 10
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- 150000001768 cations Chemical group 0.000 claims description 6
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- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
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- 229910052741 iridium Inorganic materials 0.000 claims description 2
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- 239000000395 magnesium oxide Substances 0.000 claims description 2
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- 229910052762 osmium Inorganic materials 0.000 claims description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
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- JUWGUJSXVOBPHP-UHFFFAOYSA-B titanium(4+);tetraphosphate Chemical compound [Ti+4].[Ti+4].[Ti+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JUWGUJSXVOBPHP-UHFFFAOYSA-B 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims description 2
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 claims description 2
- YAIQCYZCSGLAAN-UHFFFAOYSA-N [Si+4].[O-2].[Al+3] Chemical compound [Si+4].[O-2].[Al+3] YAIQCYZCSGLAAN-UHFFFAOYSA-N 0.000 claims 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 239000003513 alkali Substances 0.000 description 14
- 230000008569 process Effects 0.000 description 13
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 8
- 239000002243 precursor Substances 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 7
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 6
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- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
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Abstract
描述了用于制备包含至少一种具有改性EUO结构类型的沸石、至少一种基体和至少一种来自元素周期分类表的第VIII族的金属的催化剂的方法。所述催化剂被用在用于包含至少一种每分子含有8个碳原子的化合物的芳族进料的异构化方法中。
Description
本发明涉及用于制备包含具有改性EUO结构类型的沸石、至少一种基体和至少一种来自元素周期分类表的第VIII族的金属的催化剂的方法。本发明还涉及根据本发明制备的所述催化剂在用于包含至少一种每分子含有8个碳原子的芳族化合物的芳族馏分的异构化以生产对二甲苯的方法中的用途。这种馏分通常被称为“芳族C8馏分”。
现有技术
用于进行含有8个碳原子的芳族化合物的异构化的方法的催化剂通常是沸石催化剂。单独或作为与其它沸石(例如丝光沸石)的混合物使用的ZSM-5被包括在用于芳族C8馏分的异构化的沸石中。这些催化剂已经特别被描述在专利US A 4 467 129、US A 4 482773和EP B 0 013 617中。现有技术的催化剂,特别是基于丝光沸石的催化剂,具有平庸的催化性能,因为它们会引起不可忽略的副反应。可以举出的这样的次级反应的实例包括环烷烃开环,接着或者以其它方式裂化(转变为链烷烃),或甚至是含8个碳原子的芳族化合物的歧化和烷基转移反应(转变为不希望的芳族化合物),或甚至是芳族化合物的氢化(转变为环烷烃)。基于ZSM-5沸石的催化剂(单独或作为与其它沸石(例如丝光沸石)的混合物)已经被使用,并且还没有达到用于将乙苯转化成二甲苯的最佳的催化性能。
专利申请EP 0 923 987 A1和WO 2005/065380分别提出了基于具有EUO结构类型和具有MTW结构类型的沸石的催化剂。尽管这些沸石催化剂提供了引人关注的针对二甲苯的选择率,但是它们的二甲苯收率太低。
因此,仍然需要研发用于将芳族C8馏分异构化成为二甲苯,在选择率和活性方面有改进的性能的催化剂。
已知通过在所使用的沸石的微晶中和/或之间产生中孔(晶体内和/或晶体外的中孔率)来改进催化剂的活性。沸石在碱性介质中的脱硅构成可用于产生中孔率的技术之一。然而,尽管该处理对于本领域技术人员是已知,但是待使用的操作条件对每种沸石的具体特征(结构类型、尺寸和微晶的形态、Si/Al比等等)是特定的。在公开文献中,已描述了具有MFI、MTW、MOR、BEA、AST、FER、MWW、IFR、STF、CHA、FAU和TON结构类型的沸石在碱性介质中进行脱硅(D. Verboekend,J. Perez-Ramirez,Catalysis Science and Technology,2011,1,897-890),但是在该文献中没有文件描述具有EUO结构类型的沸石的碱处理。
本申请人的研究已经引起了用于制备新型催化剂的新方法的发展,所述新型催化剂包含通过特定的碱处理改性的具有EUO结构类型的沸石,更特别是EU-1沸石。已经令人惊奇地发现,包含至少一种基体、至少一种来自元素周期分类表的第VIII族的金属和至少一种EUO沸石,更特别是EU-1沸石(其已经在本发明所描述的条件下经过碱处理)的珠粒或挤出物形式的催化剂在所述催化剂被用在包含至少一种每分子含有8个碳原子的芳族化合物的芳族馏分的异构化方法中时产生对于芳族进料的异构化改进的催化性能。这种类型的催化剂比包含未经过本发明的碱处理或在不同于本发明中所描述的那些的条件下经过碱处理的EUO沸石的催化剂更有活性且更有选择性。当在本发明的催化剂存在下进行异构化过程时,这导致二甲苯收率的增加。
发明详述
本发明涉及用于制备用于包含至少一种每分子含有8个碳原子的芳族化合物的芳族馏分的异构化的催化剂的方法,所述催化剂包含至少一种已经过碱处理的改性的EUO沸石、至少一种基体和至少一种来自元素周期分类表的第VIII族的金属。
本发明的方法是用于由具有在5-100的范围内的总Si/Al原子比、具有EUO结构类型的初始沸石制备用于包含至少一种每分子含有8个碳原子的芳族化合物的芳族馏分的异构化的催化剂的方法,所述催化剂包含至少一种基体和至少一种来自第VIII族的金属,所述方法包括至少以下步骤:
i)通过悬浮在具有在0.1-3M的范围内的当量浓度的碱性溶液中,在100-1000rpm的范围内的搅拌速度下搅拌,并加热至在40℃-100℃的范围内的温度,保持在5分钟-24小时的范围内的时间段使所述具有EUO结构类型的初始沸石脱硅的步骤;
ii)用蒸馏水洗涤获自步骤i)的所述沸石的步骤;
iii)通过以使得所述沸石相对于载体的重量的重量百分数在1%-90%的范围内的方式采用基体使获自步骤ii)的所述经洗涤的EUO沸石成型来制备所述载体的步骤;
iv)至少一个以使得消除至少部分存在于所述沸石中的阳离子位置的碱性阳离子的方式使获自步骤ii)的所述经洗涤的沸石或获自步骤iii)的所述载体离子交换的步骤;
v)以使得所述金属相对于所述催化剂的重量的重量百分数为0.01%-4%的方式使至少一种来自元素周期分类表的第VIII族的金属沉积在获自步骤iv)的所述经交换的沸石或获自步骤iv)的所述经交换的载体上的步骤。
i)脱硅步骤
本发明中使用的具有初始EUO结构类型的初始沸石可选自EU-1沸石、TPZ-3沸石和ZSM-50沸石;优选地,所述沸石是EU-1沸石。
具有EUO结构类型的EU-1、TPZ-3和ZSM-50沸石在现有技术(Atlas of ZeoliteFramework Types,Ch. Baerlocher,W.M. Meier, D.H. Olson,第5版,2001)中是公知的。已知具有EUO结构类型的沸石,特别是EU-1沸石,具有孔直径为4.1×5.4 Å (1 Å = 1埃=10-10m)的一维微孔骨架。此外,在他们的综述Zeolites (1988, 8, 74)的文章中,N.ABriscoe等人公开了这些一维通道具有深度为8.1 Å且直径为6.8×5.8 Å的侧袋(pocket)。
本发明中使用的具有EUO结构类型的初始沸石具有在5-100的范围内,优选在10-50的范围内,且高度优选在10-35的范围内的总Si/Al原子比。所述沸石有利地由具有在5nm-1µm的范围内,优选在10nm-500nm的范围内,且更优选在20nm-100nm的范围内的尺寸的优选各向同性的微晶组成。本发明中使用的初始沸石可以是合成后原样的形式(具有有机模板(template))或经煅烧的形式;优选地,所述初始沸石是经煅烧的形式。
本发明的脱硅步骤在碱性溶液,优选含水碱性溶液中进行。所述碱性溶液有利地为基于氢氧化锂LiOH、氢氧化钠NaOH、氢氧化钾KOH或氢氧化铯CsOH的含水碱性溶液。所述碱性溶液具有在0.1-3M的范围内,优选在0.5-2M的范围内,更优选在0.7-1.5M的范围内,且还更优选在0.8-1.2M的范围内的当量浓度。
有利地,在脱硅步骤i)中使用的所述碱性溶液的体积(以mL表示)与待被脱硅的干沸石的质量(以g表示)之间的比在2-20的范围内,且优选在4-18的范围内。所述沸石和所述碱性溶液的混合物必须采用在100-1000rpm的范围内,优选在200-400rpm的范围内的搅拌速度进行搅拌,并加热至在40℃-100℃的范围内,优选在50℃-100℃的范围内,更优选在50℃-90℃的范围内,且还更优选在60℃-90℃的范围内的温度,保持在5分钟至24小时的范围内,优选在15分钟至10小时的范围内,更优选在15分钟至5小时的范围内,且还更优选在30分钟至3小时的范围内的时间段。
ii)洗涤步骤
在产生改性的沸石的所述脱硅步骤i)之后,在进行本发明的制备方法的洗涤步骤ii)之前将混合物有利地冷却至环境温度。
用蒸馏水将获自步骤i)的沸石有利地洗涤2-10次。所使用的蒸馏水的体积(mL)与沸石的质量(g)之间的比通常在2-20的范围内,优选在4-18的范围内。通过在2000-14000rpm的范围内,优选在5000-1000rpm的范围内的速度下的离心有利地将经洗涤的沸石分离。可以用蒸馏水进行连续洗涤直至在通过离心分离的水溶液中获得接近7的pH。将经洗涤的沸石任选地在60℃-130℃的范围内的温度下烘干1小时至24小时的范围内的时间段。然后任选干燥的沸石可以经过制备方法的步骤iv),即离子交换步骤。在本发明的方法的一个变体中,所述沸石首先经过采用基体成型的步骤iii),使得在进行离子交换步骤iv)之前,所述沸石相对于所述载体的重量的重量百分数在1%-90%的范围内。
酸处理
有利地,根据本发明,在离子交换步骤iv)之前,获自步骤ii)的所述经洗涤的EUO沸石或获自步骤iii)的载体的沸石通过悬浮在酸性溶液,优选含水酸性溶液中经过酸处理。
可以采用无机酸或有机酸,例如盐酸HCl、磷酸H3PO4、硝酸HNO3、柠檬酸C6H8O7、乙酸C2H4O2或甚至硫酸H2SO4的任何稀的水溶液进行所述酸处理,所述稀的水溶液具有在0.001-2M的范围内,优选在0.01至1.5M的范围内,更优选0.02-1M的范围内,且还更优选在0.05-0.8M的范围内的当量浓度。优选地,采用盐酸的稀的水溶液进行所述酸处理。用于进行所述酸处理的水溶液的体积(mL)与经洗涤且经干燥的沸石的质量或经干燥的载体(成型的沸石)的质量(g)之间的比在2-200的范围内,优选在5-150的范围内。在100-1000rpm的范围内,优选在200-400rpm的范围内的搅拌速度下搅拌所述混合物,并将其加热至在30℃-100℃的范围内,优选在40℃-90℃的范围内,更优选在45℃-85℃的范围内,且还更优选在50℃-80℃的范围内的温度,保持5分钟至24小时的范围内,优选在15分钟至10小时的范围内,更优选在30分钟至8小时的范围内,且还更优选在45分钟至8小时的范围内的时间段。在所述酸处理结束时,将所述混合物有利地冷却至环境温度。用蒸馏水有利地将获自该酸洗步骤的沸石或载体洗涤2-10次。所使用的蒸馏水的体积(mL)与沸石或载体的质量(g)之间的比通常在2-200的范围内,优选在5-150的范围内。通过在2000-14000rpm的范围内,优选在5000-1000rpm的范围内的速度下的离心有利地将经洗涤的沸石(酸洗涤)分离。通过过滤有利地将经洗涤的载体(酸洗涤)分离。可以用蒸馏水进行连续的洗涤直至在所述含水洗涤溶液中达到接近7的pH。将经洗涤的沸石或经洗涤的载体(酸洗涤)任选地在60℃-130℃的范围内的温度下烘干1小时至24小时的范围内的时间段。
iii)载体的制备
通过进行所述载体制备步骤iii),也称为采用基体使获自步骤ii)的所述经洗涤的沸石成型的步骤制备所述催化剂。
为了进行通过使获自步骤ii)的具有EUO结构类型的所述经洗涤的沸石,优选经洗涤的EU-1沸石成型来制备所述载体的所述步骤iii),将选自粘土、氧化镁、氧化铝、二氧化硅、氧化钛、氧化硼、氧化锆、磷酸铝、磷酸钛、磷酸锆、二氧化硅-氧化铝和碳或这些组分中的至少两种的混合物的基体用于成型。优选地,所述基体是氧化铝。
所述载体中的沸石含量在按重量计1%-90%的范围内,优选在按重量计3%-80%的范围内,且还更优选在按重量计4%-60%的范围内。
更具体地,根据所述步骤iii)的所述载体的制备由以下步骤组成:在通常通过将至少一种酸和基体粉末混合获得的基体(优选氧化铝)的湿润的凝胶中,将获自步骤ii)的所述具有EUO结构类型经洗涤的沸石,优选经洗涤的EU-1沸石混合为获得浆糊形式的良好的均匀性所必需的时间段,即例如约10分钟,然后例如传送所得的浆糊通过模头以形成例如具有0.4-4mm的直径的挤出物。也可通过成粒技术获得珠粒。在成型之后通常是干燥,然后是煅烧。干燥有利地在100℃-150℃的范围内的温度下在烘箱中进行5-20小时的范围内的时间段。煅烧有利地在250℃-600℃的范围内的温度下进行1-8小时的范围内的时间段。
iv)离子交换步骤
根据本发明,获自步骤ii)的所述经洗涤的沸石或获自步骤iii)的载体经过一个或多个离子交换以消除至少部分存在于沸石中的阳离子位置的碱性阳离子。
具有在0.2-12 M的范围内的当量浓度的含有铵前体,例如硝酸铵NH4NO3、乙酸铵CH3COONH4、氢氧化四丙基铵C12H27NO、氢氧化四甲基铵C4H13NO、或氢氧化四乙基铵C8H21NO的水溶液可以用于进行交换步骤iv)。用于进行交换的水溶液的体积(mL)与待交换的干沸石或干载体的质量(g)之间的比在2-20的范围内,并优选在5-15的范围内。将固体倒入容纳含有所述铵前体的水溶液的烧瓶或锥形瓶中。搅拌所述混合物并任选加热至在50℃-100℃的范围内的温度,保持2-10小时的范围内的时间段。然后有利地除去所述溶液并用蒸馏水漂洗固体2-10次,然后任选在60℃-130℃的范围内的温度下烘干1-24小时的范围内的时间段。所述交换步骤可以重复若干次以基本上消除可能存在于沸石中的阳离子位置中的所有碱性阳离子。然后在其中心配备有玻璃料(frit)的石英反应器中,在300℃-600℃的范围内,优选在450℃-550℃的范围内的温度下,优选在干空气中,将得到的固体有利地煅烧1-24小时的范围内的时间段,其中气体在0.5L/h/g固体至3L/h/g固体的范围内的流量下从底部移动到顶部。
高度有利地,存在于本发明的催化剂中的具有改性的EUO结构类型的沸石是其质子化形式(氢H +形式)。优选地,在其质子化形式的所述沸石中的碱性阳离子含量小于按重量计3000ppm。
v)金属沉积步骤
用于制备所述催化剂的步骤v)由以下组成:以使得所述金属相对于最终的催化剂的重量的重量百分数为0.01%-4%,优选0.05%-2%的方式,使至少一种来自元素周期分类表的第VIII族的金属沉积在获自步骤iv)的所述经交换的沸石上或获自步骤iv)的所述经交换的载体上。
根据本发明,所述催化剂包含至少一种来自第VIII族的金属,其选自铁、钴、镍、钌、铑、钯,锇、铱和铂,优选选自来自第VIII族的贵金属,高度优选选自钯和铂,且还更优选铂。
通过化学吸附,例如通过H2-O2滴定或通过一氧化碳化学吸附测定来自第VIII族的一种或多种金属的分散率(dispersion)在50%-100%的范围内,优选在60%-100%的范围内,且还更优选在70%-100%的范围内。由使用Castaing微探针测定的其曲线(profile)获得的来自第VIII族的一种或多种金属的宏观分布系数(被定义为来自第VIII族的一种或多种金属在颗粒(grain)的芯部处的浓度相对于所述同一颗粒的边界处的浓度的比)在0.7-1.3的范围内,优选在0.8-1.2的范围内。接近1的该比率的值是来自第VIII族的一种或多种金属在所述催化剂中分布均匀的证据。
所述催化剂任选地进一步包含相对于最终催化剂的重量的按重量计至少0.01%-2%,优选按重量计0.05%-1%的选自来自元素周期分类表的第IIIA、IVA和VIIB族的金属,并优选选自镓、铟、锡和铼的其它金属。所述其它金属优选选自铟、锡和铼。
为了沉积来自元素周期分类表的第VIII族的金属,本领域技术人员已知的任何沉积技术和这样的金属的任何前体都可以是合适的。
当一种或多种金属沉积在载体上时,控制在沉积过程中使用的各种参数,特别是使用的来自第VIII族的一种或多种金属的前体的性质,意味着所述一种或多种金属的沉积可被主要定向在所述基体上或所述改性的沸石上。
因此,为了将来自第VIII族的金属,优选铂和/或钯主要引入到所述基体上,可以在竞争试剂(例如盐酸)的存在下,采用六氯铂酸和/或六氯钯酸进行阴离子交换,沉积通常在煅烧步骤之后进行,所述煅烧例如在350℃-550℃的范围内的温度下并进行1-4小时的范围内的时间段。采用这种类型的前体,来自第VIII族的一种或多种金属主要沉积在所述基体上并且所述一种或多种金属具有良好的分散率以及通过所述催化剂的颗粒的良好的宏观分布。
还可以设想以使得所述一种或多种金属主要沉积在所述改性的沸石上的方式通过阳离子交换沉积来自第VIII族的一种或多种金属,优选铂和/或钯。因此,在铂的情况下,所述前体可以例如选自氨的化合物,例如具有式Pt(NH3)4X2的四胺铂(II)的盐、具有式Pt(NH3)6X4 的六胺铂(IV)的盐、具有式(PtX(NH3)5)X3的五胺卤化铂(IV)的盐、具有式PtX4(NH3)2的二胺N-四卤化铂的盐和具有式H(Pt(acac)2X)的卤化盐;X为选自氯、氟、溴和碘的卤素,X优选为氯,并且“acac”表示乙酰丙酮化物基团(具有经验式C5H7O2),乙酰丙酮的衍生物。采用这种类型的前体,来自第VIII族的一种或多种金属主要沉积在所述沸石上并且所述一种或多种金属具有良好的分散率以及通过所述催化剂颗粒的良好的宏观分布。
将来自第VIII族的金属干浸渍在成型的沸石(载体)上导致所述金属沉积在所述基体和所述金属沸石二者上。
在其中本发明的催化剂还包含至少一种选自来自第IIIA、IVA和VIIB族的金属的金属的情况下,本领域技术人员已知的任何用于沉积该类型的金属的技术和这样的金属的任何前体都可以是合适的。
可以在至少一个单一步骤中分别或同时加入来自第VIII族的一种或多种金属以及来自第IIIA、IVA和VIIB族的一种或多种金属。当分别加入来自第IIIA、IVA和VIIB族的至少一种金属时,优选在来自第VIII族的金属之后加入。
选自来自第IIIA、IVA和VIIB族的金属的其它金属可经由诸如来自第IIIA、IVA和VIIB族的金属的氯化物、溴化物和硝酸盐的化合物引入。作为在铟的情况下的实例,可以有利地使用硝酸盐或氯化物,而在铼的情况下,有利地使用高铼酸。也可以至少一种选自所述金属的配合物,特别是所述金属和烃基金属(例如烷基、环烷基、芳基、烷基芳基和芳基烷基金属)的聚酮配合物的有机化合物的形式引入选自来自第IIIA、IVA和VIIB族的金属的其它金属。在后一种情况下,有利地借助于所述金属的有机金属化合物在有机溶剂中的溶液引入所述金属。也可以使用所述金属有机卤化化合物。在锡的情况下,可以举出的有机金属化合物的具体实例是四丁基锡,而在铟的情况下是三苯基铟。
如果在来自第VIIB族的金属之前引入选自来自第IIIA、IVA和VIIB族的金属的其它金属,则所使用的来自第IIIA、IVA和/或VIIB族的金属的化合物通常选自金属卤化物、硝酸盐、乙酸盐、酒石酸盐、碳酸盐和草酸盐。所述引入有利地在水溶液中进行。但是,也可以借助于金属的有机金属化合物(例如四丁基锡)的溶液引入所述其它金属。在这种情况下,在继续引入至少一种来自第VIII族的金属之前,在空气中进行煅烧。
另外,例如可以在各种金属的连续沉积之间应用中间处理,例如煅烧和/或还原。
可以例如在450℃-600℃的温度下,在氢气物流中进行最终催化剂的非原位预先还原,持续0.5-4小时的时间段。
所述催化剂任选包含使得硫的原子数目与来自第VIII族的一种或多种金属的原子数目的比在0.5-2的范围内的量的硫。
在其中所述催化剂不含硫的情况下,在注入进料之前在氢中原位进行所述金属的还原。
在其中本发明的催化剂含有硫的情况下,将所述硫在催化反应之前原位或非原位地引入到已被煅烧的含有上文提及的一种金属或多种金属的成型的催化剂上。在还原之后进行任何硫化。在原位硫化的情况下,如果催化剂尚未被还原,则在硫化之前进行还原。在非原位硫化的情况下,在硫化之后进行还原。在氢的存在下使用本领域技术人员公知的任何硫化剂(例如二甲基硫(dimethyl sulphide)或硫化氢)进行硫化。举例而言,在氢的存在下采用含有二甲基硫的进料以使得硫/金属原子比为1.5的浓度处理催化剂。然后在注入进料之前将所述催化剂在约400℃下在氢气流中保持约3小时。
表征技术
初始EU-1沸石的总Si/Al原子比通过X射线荧光法测量。X射线荧光法是可用于分析从硼开始的所有的周期表元素的普通的元素分析技术。可以测定从仅几ppm(百万分之一)到高达100%。在本发明中,这种技术被用于测定沸石中硅和铝(作为重量百分数),并从而可以被用于计算Si/Al原子比。使用Thermofischer Scientific Advant-X仪器在粉末上进行铝和硅的XRF分析。
在它们的质子化形式(在所述离子交换步骤之后)的各种沸石中的钠含量通过原子吸收光谱法或发射光谱法测量。使用发射光谱仪(ICP-OES)SPECTRO,ARCOS SOP确定钠含量。
初始EUO沸石和改性EUO沸石的质构(textural)特性通过在-196℃下的氮吸附/解吸测量。使用BET法计算比表面积。使用“t-曲线(t-plot)”方法得到微孔体积(Vmicro)以及外表面积(Sext),使用Harkins和Jura公式计算统计学厚度。通过从总孔体积减去微孔体积获得中孔体积(Vmeso)。术语“总孔体积”是指在0.95的相对氮气压力(P/P0)下被吸附的氮的体积。在Micromeritics ASAP2024孔度计上进行样品的吸附-解吸等温线测量。预先使用预处理舱(bay)进行固体的脱气操作。通过在两个阶段加热进行脱气:第一恒温阶段在100℃下持续2小时,随后的第二恒温阶段在500℃下持续6小时;温度攀升速率为约20摄氏度每分钟。
使用X射线衍射技术以验证所用的沸石的晶体结构是否确实存在于各个样品中。这通过将实验衍射图与理论衍射图(文件号JCPDS 04-007-2506)对比来进行。在PANanyticalX'Pert PRO MPD θ-θ上,使用铜Kα线 (λ= 1.5402 Å)和X'Celerator检测器进行所述分析。在分析过程中,扫描在2°和72°之间,在环境温度下以0.02°的阶梯(step),而且每个阶梯的测量周期为6秒进行。
透射电子显微镜(TEM)用来评估沸石微晶的典型尺寸。使用具有200kV的加速电压的JEOL 21000F-FEG(场致发射枪)显微镜进行TEM观察。
在芳族C8馏分异构化方法中使用催化剂
本发明还涉及用于使包含至少一种每分子含有8个碳原子的芳族化合物的馏分异构化的方法,所述方法包括使所述芳族馏分至少与根据本发明的所述催化剂接触。
特别地,包含至少一种每分子含有8个碳原子的芳族化合物的所述芳族馏分唯一地包含二甲苯的混合物、或唯一地包含乙苯、或包含一种或多种二甲苯与乙苯的混合物作为每分子含有8个碳原子的芳族化合物。
所述异构化方法通常根据以下操作条件进行:300℃-500℃,优选320℃-450℃,且更优选340℃-430℃的温度; 0.3-1.5MPa,优选0.4-1.2MPa,且更优选0.7-1.2MPa的氢的分压;0.45-1.9MPa,优选0.6-1.5MPa的总压力;和以每千克催化剂每小时引入的进料(芳族馏分)的千克数表示的0.25-30h-1,优选1-10h-1,且还更优选2-6 h-1的进料空速。
下列实施例举例说明本发明,但是不限制其范围。
实施例1(不根据本发明):EU-1沸石的制备
根据在专利EP B1 0 042 226中的公开内容,使用有机模板1,6- N,N,N,N',N',N'-六甲基六亚甲基二铵合成EU-1沸石。为了制备这种类型的沸石,反应混合物具有以下摩尔组成:60 SiO2:10.6 Na2O:5.27 NaBr:1.5 Al2O3:19.5Hexa-Br2:2777 H2O。
Hexa-Br2是1,6-N,N,N,N',N',N'-六甲基六亚甲基二铵,其中溴为抗衡离子。将反应混合物放入高压釜中,并在180℃下搅拌(300rpm)5天。
这种EU-1沸石首先在550℃下在干空气物流中经过称为干煅烧的煅烧10小时,以消除有机模板。然后在回流4小时下将固体放置在硝酸铵的溶液(100mL溶液每克固体,硝酸铵的浓度为10M)中,以用铵离子交换碱性阳离子。将该交换步骤进行四次。然后将固体在管式炉中在550℃下煅烧4小时。如此得到的固体被给予标记EU-1(1),并具有15的Si/Al原子比以及73 ppm的钠含量。通过X射线衍射的分析证实确实已经获得EU-1沸石。透射电子显微镜显示出具有在20-80nm的范围内的典型尺寸的微晶的存在,这些微晶形成附聚物。通过氮孔隙度法分析所述EU-1(1)沸石,以确定它的质构特征(表1)。
实施例2(根据本发明):改性EU-1沸石的制备
将EU-1(1)沸石置于配备有机械搅拌器的回流烧瓶中,在其中它经过在以下条件下的碱处理:
•处理温度:85℃,
•水溶液中的氢氧化钠的浓度:1M,
•处理时间:45分钟,
•溶液的体积/EU-1(1)的质量的比:15mL/g,
•机械搅拌器的速度:330rpm。
然后用蒸馏水将改性沸石洗涤三次并通过离心(8000rpm)分离,然后在110℃下烘干12小时。在该碱处理结束时,获得被表示为EU-1(2)的以其钠形式的改性沸石。在回流4小时下将固体放置在硝酸铵的溶液(100mL溶液每克固体,硝酸铵的浓度为10M)中,以用铵离子交换碱性阳离子。将该交换步骤进行五次。然后将固体在管式炉中在550℃下煅烧4小时。然后所述沸石为其质子化形式并被表示为沸石EU-1(3)。该沸石的钠含量为95ppm并且X射线衍射分析证实EU-1沸石的特征衍射峰仍然存在。通过氮孔隙度法分析所述沸石EU-1(3),以确定它的质构特征(表1)。
实施例3(根据本发明):改性EU-1沸石的制备
将实施例2中得到的EU-1(2)沸石置于烧瓶中,在其中它经过在下列条件下的酸处理:
•处理温度:65℃,
•水溶液中的盐酸的浓度:0.1M,
•处理时间:360分钟,
•溶液的体积/EU-1(2)的质量的比:100mL/g,
•机械搅拌器的速度:330rpm。
然后用蒸馏水将该沸石洗涤三次并且通过离心(8000rpm)分离,然后在110℃下烘干12小时。
在该酸处理结束时,得到表示为EU-1(4)的改性沸石。在回流4小时下将固体放置在硝酸铵的溶液(100mL溶液每克固体,硝酸铵的浓度为10M)中,以用铵离子交换碱性阳离子。将该交换步骤进行五次。然后将固体在管式炉中在550℃下煅烧4小时。然后所述沸石为其质子化形式并被表示为沸石EU-1(5)。该沸石的钠含量为70ppm并且X射线衍射分析证实EU-1沸石的特征衍射峰仍然存在。通过氮孔隙度法分析所述沸石EU-1(5),以确定它的质构特征(表1)。
实施例4(不根据本发明):改性EU-1沸石的制备
将EU-1(1)沸石置于配备有机械搅拌器的回流烧瓶中,在其中它经过在以下条件下的碱处理:
•处理温度:65℃,
•水溶液中的氢氧化钠的浓度:0.05M,
•处理时间:60分钟,
•溶液体积/EU-1(1)的质量的比:15mL/g,
•机械搅拌器的速度:330rpm。
然后用蒸馏水将改性沸石洗涤三次并通过离心(8000rpm)分离,然后在110℃下烘干12小时。
在该碱处理结束时,得到表示为EU-1(6)的以其钠形式的改性沸石。在回流4小时下将固体放置在硝酸铵的溶液(100mL溶液每克固体,硝酸铵的浓度为10M)中,以用铵离子交换碱性阳离子。将该交换步骤进行五次。然后将固体在管式炉中在550℃下煅烧4小时。然后所述沸石为其质子化形式并被表示为沸石EU-1(7);其钠含量为92ppm。通过X射线衍射分析证实EU-1沸石的特征衍射峰仍然存在。通过氮孔隙度法分析所述沸石EU-1(7),以确定它的质构特征(表1)。
表1显示了由氮吸附等温线确定的沸石EU-1(1)(母体)和改性的EU-1、EU-1(3)、EU-1(5)和EU-1(7)的质构特征。所述母体EU-1沸石EU-1(1)与沸石EU-1(7)的质构特性的比较显示在未根据本发明的条件下在所述EU-1沸石上进行碱处理并没有让母体沸石的外表面积得到显著的发展,也没有增加中孔体积。相比而言,在根据本发明的条件下进行碱处理(EU-1(3))意味着所述外表面积从35 m2/g增加到94 m2/g,并且中孔体积从0.24mL/g增加到0.41mL/g。在根据本发明的条件下的碱处理之后继续进行酸处理(EU-1(5))进一步增加了外表面积(获得160m2/g的值)以及中孔体积(获得0.59mL/g的值)。另外,所述酸处理允许微孔被释放,与已经经过碱处理但没有然后用酸处理的固体(EU- 1(3))的0.004mL/g不同,微孔体积达到0.103mL/g的值。
表1:沸石EU-1(1)(母体)和改性的EU-1、EU-1(3)、EU-1(5)和EU-1(7)的质构特征
沸石的标记 | SBET (m2/g) | Sext(m2/g) | Vmeso (mL/g) | Vmicro(mL/g) |
EU-1(1) (母体) | 456 | 35 | 0.24 | 0.150 |
EU-1(3) | 103 | 94 | 0.41 | 0.004 |
EU-1(5) | 398 | 160 | 0.59 | 0.103 |
EU-1(7) | 175 | 39 | 0.21 | 0.061 |
实施例5(不根据本发明):包含未改性的EU-1沸石的催化剂A的制备
将来自实施例1的沸石EU-1(1)(母体)与由Condéa-Sasol提供的SB3型氧化铝凝胶混合。将混合的浆糊挤出通过1.4mm模头。在110℃下烘干过夜之后,将挤出物在干空气的冲洗床(flushed bed)中(2 NL/h/g固体) 在500℃下煅烧两小时(温度攀升5℃/分钟)。然后在作为竞争试剂的盐酸的存在下使挤出物与六氯铂酸进行阴离子交换,以沉积相对于催化剂的重量的按重量计0.5%的铂。然后在120℃下将湿润的固体干燥12小时并且在500℃的温度下在干空气流中煅烧1小时。
得到的催化剂A含有按重量计10%的沸石EU-1(1)、89.5 %的氧化铝和0.5%的铂。
实施例6(根据本发明):包含改性的EU-1沸石的催化剂B的制备
将来自实施例2的沸石EU-1(3)(母体)与由Condéa-Sasol提供的SB3型氧化铝凝胶混合。将混合的浆糊挤出通过1.4mm模头。在110℃下烘干过夜之后,将挤出物在干空气的冲洗床中(2 NL/h/g固体)在500℃下煅烧两小时(温度攀升5℃/分钟)。然后在作为竞争试剂的盐酸的存在下使挤出物与六氯铂酸进行阴离子交换,以沉积相对于催化剂的重量的按重量计0.5%的铂。然后在120℃下将湿润的固体干燥12小时并且在500℃的温度下在干空气流中煅烧1小时。
由此得到的催化剂B含有按重量计10%的改性的EU-1(3)沸石、89.5 %的氧化铝和0.5%的铂。
实施例7(根据本发明):包含改性的EU-1沸石的催化剂C的制备
将来自实施例3的沸石EU-1(5)与由Condéa-Sasol提供的SB3型氧化铝凝胶混合。将混合的浆糊挤出通过1.4mm模头。在110℃下烘干过夜之后,将挤出物在干空气的冲洗床中(2 NL/h/g固体)在500℃下煅烧两小时(温度攀升5℃/分钟)。然后在作为竞争试剂的盐酸的存在下使挤出物与六氯铂酸进行阴离子交换,以沉积相对于催化剂的重量的按重量计0.5%的铂。然后在120℃下将湿润的固体干燥12小时并且在500℃的温度下在干空气流中煅烧1小时。
由此得到的催化剂C含有按重量计10%的改性的EU-1(5)沸石、89.5 %的氧化铝和0.5%的铂。
实施例8(不根据本发明):包含改性的EU-1沸石的催化剂D的制备
将来自实施例4的沸石EU-1(7)与由Condéa-Sasol提供的SB3型氧化铝凝胶混合。将混合的浆糊挤出通过1.4mm模头。在110℃下烘干过夜之后,将挤出物在干空气的冲洗床中(2 NL/h/g固体)在500℃下煅烧两小时(温度攀升5℃/分钟)。然后在作为竞争试剂的盐酸的存在下使挤出物与六氯铂酸进行阴离子交换,以沉积相对于催化剂的重量的按重量计0.5%的铂。然后在120℃下将湿润的固体干燥12小时并且在500℃的温度下在干空气流中煅烧1小时。
由此得到的催化剂D含有按重量计10%的改性的EU-1(7)沸石、89.5 %的氧化铝和0.5%的铂。
实施例9:评估催化剂A、B、C和D在乙苯的异构化中的催化特性
在等温条件下操作的反应器中的冲洗床中,在各种催化剂上使仅由乙苯组成的进料异构化,并且损失氢气。连续评估催化剂A、B、C和D对乙苯的异构化的催化特性。在催化测试前,每种催化剂经过在氢气流中的在以下操作条件下的还原步骤:
•总压力:1.3MPa;
•氢气流量:4 NL/h/g催化剂;
•自环境温度到450℃的温度攀升为10℃/分钟;
•一小时的450℃下的恒温阶段;
•自450℃到480℃的温度攀升为5℃/分钟;
•两小时的480℃下的恒温阶段。
在还原步骤之后,将温度和压力调节至目标测试值并注入乙苯进料。用于异构化的操作条件如下:
•温度:400℃;
•总压力:1MPa;
•氢分压:0.8MPa;
•进料:乙苯;
•进料空速,以每千克催化剂每小时引入的进料的千克数表示,等于10h-1。
就乙苯转化率和针对二甲苯选择率而言对催化剂进行评估。
使用生产的二甲苯的收率计算针对二甲苯的选择率。由使用气相色谱法(FID检测器)通过每种流出物(effluent)的在线分析得到的生产的二甲苯的重量百分数来确定二甲苯收率。
乙苯转化率为消耗的乙苯的百分数。
表2:在4000分钟反应之后在催化剂A、B、C和D上的乙苯的转化率和针对二甲苯的
选择率
催化剂 A | 催化剂B | 催化剂C | 催化剂D | |
乙苯转化率(%) | 20.0 | 27.1 | 35.2 | 20.1 |
针对二甲苯的选择率(%) | 68.1 | 68.3 | 71.1 | 68.2 |
二甲苯的收率(%) | 13.6 | 18.5 | 25.0 | 13.7 |
表1中呈现的结果表明:就乙苯转化率而言,各自包含根据本发明所描述的方法改性的EU-1沸石的催化剂B和催化剂C产生了比使用包含未改性的EU-1沸石的催化剂A以及使用包含使用未根据本发明的方法改性的EU-1沸石的催化剂D获得的催化性能好得多的催化性能。根据本发明的催化剂B和C因而比现有技术催化剂A和比催化剂D要更具活性得多。另外,根据本发明的催化剂B和C具有基本上可与催化剂A和D的选择率相比的选择率。因此,根据本发明的催化剂B和C产生的二甲苯的收率远远优于用比较催化剂A和D得到的二甲苯的收率。
Claims (11)
1.用于由具有在5-100的范围内的总Si/Al原子比、具有EUO结构类型的初始沸石制备催化剂的方法,所述催化剂用于包含至少一种每分子含有8个碳原子的芳族化合物的芳族馏分的异构化,所述催化剂包含至少一种基体和至少一种来自第VIII族的金属,所述方法包括至少以下步骤:
i)通过悬浮在具有在0.5-2 N的范围内的当量浓度的基于氢氧化锂LiOH、氢氧化钠NaOH、氢氧化钾KOH或氢氧化铯CsOH的含水碱性溶液中,在100-1000rpm的范围内的搅拌速度下搅拌,并加热至在40℃-100℃的范围内的温度,保持5分钟-24小时的范围内的时间段使所述具有EUO结构类型的初始沸石脱硅的步骤;
ii)用蒸馏水洗涤获自步骤i)的所述沸石的步骤;和
iii)通过以使得所述沸石相对于载体的重量的重量百分数在1%-90%的范围内的方式,采用基体使EUO沸石成型来制备载体的步骤;
其中,
在步骤iii)之前,所述方法进一步包括如下步骤:
iv)至少一个以使得消除至少部分存在于所述沸石中的阳离子位置的碱性阳离子的方式使获自步骤ii)的经洗涤的沸石离子交换的步骤;和
v)以使得所述金属相对于所述催化剂的重量的重量百分数为0.01%-4%的方式使至少一种来自元素周期分类表的第VIII族的金属沉积在获自于步骤iv)的经交换的沸石上的步骤;
或者,
在步骤iii)之后,所述方法进一步包括如下步骤:
iv')至少一个以使得消除至少部分存在于所述沸石中的阳离子位置的碱性阳离子的方式使获自步骤iii)的载体离子交换的步骤;和
v')以使得所述金属相对于所述催化剂的重量的重量百分数为0.01%-4%的方式使至少一种来自元素周期分类表的第VIII族的金属沉积在获自步骤iv')的经交换的载体上的步骤。
2.根据权利要求1所述的方法,其中所述具有EUO结构类型的初始沸石选自EU-1沸石、TPZ-3沸石和ZSM-50沸石。
3.根据权利要求1或权利要求2所述的方法,其中所述初始沸石是经煅烧的形式。
4.根据权利要求1或权利要求2所述的方法,其中在于步骤iii)之前进行的离子交换步骤iv)之前,使获自步骤ii)的经洗涤的EUO沸石通过悬浮在含水酸性溶液中经受酸处理,或者在于步骤iii)之后进行的离子交换步骤iv')之前,使获自步骤iii)的所述载体的沸石通过悬浮在含水酸性溶液中经受酸处理。
5.根据权利要求1或权利要求2所述的方法,其中用于使所述载体成型的所述基体选自粘土、氧化镁、氧化铝、二氧化硅、氧化钛、氧化硼、氧化锆、磷酸铝、磷酸钛、磷酸锆、二氧化硅-氧化铝和碳或这些组分中的至少两种的混合物。
6.根据权利要求1或权利要求2所述的方法,其中所述来自第VIII族的金属选自铁、钴、镍、钌、铑、钯、锇、铱和铂。
7.根据权利要求1或权利要求2所述的方法,其中所述催化剂进一步包含按重量计至少0.01%-2%的选自来自元素周期分类表的第IIIA、IVA和VIIB族的金属的其它金属。
8.能够使用根据前述权利要求任一项的方法得到的催化剂。
9.用于使包含至少一种每分子含有8个碳原子的芳族化合物的馏分异构化的方法,所述方法包括使所述芳族馏分至少与根据权利要求1-7任一项制备的催化剂或者根据权利要求8的催化剂接触。
10.根据权利要求9的方法,所述方法在300℃-500℃的温度,0.3-1.5MPa的氢分压,0.45-1.9MPa的总压力,和以每千克催化剂每小时引入的进料的千克数表示的0.25-30h-1的进料空速下进行。
11.根据权利要求9或权利要求10的方法,其中所述芳族馏分唯一地包含二甲苯的混合物或唯一地包含乙苯或包含一种或多种二甲苯与乙苯的混合物作为每分子含有8个碳原子的芳族化合物。
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