CN103930389A - 使用双催化剂***的芳香族化合物异构化 - Google Patents
使用双催化剂***的芳香族化合物异构化 Download PDFInfo
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- CN103930389A CN103930389A CN201280055810.6A CN201280055810A CN103930389A CN 103930389 A CN103930389 A CN 103930389A CN 201280055810 A CN201280055810 A CN 201280055810A CN 103930389 A CN103930389 A CN 103930389A
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- 150000004681 metal hydrides Chemical class 0.000 description 1
- 150000001457 metallic cations Chemical group 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- RFLFDJSIZCCYIP-UHFFFAOYSA-L palladium(2+);sulfate Chemical compound [Pd+2].[O-]S([O-])(=O)=O RFLFDJSIZCCYIP-UHFFFAOYSA-L 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- HRGDZIGMBDGFTC-UHFFFAOYSA-N platinum(2+) Chemical compound [Pt+2] HRGDZIGMBDGFTC-UHFFFAOYSA-N 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 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
- 239000002002 slurry Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000004758 synthetic textile Substances 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- DNYWZCXLKNTFFI-UHFFFAOYSA-N uranium Chemical compound [U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U] DNYWZCXLKNTFFI-UHFFFAOYSA-N 0.000 description 1
- 239000003171 wood protecting agent Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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Abstract
本发明涉及一种利用催化剂***使包含高浓度非芳香族化合物的二甲苯及乙苯的非平衡混合物异构化的方法,该催化剂***的特征为可转化非芳香族化合物并可相对于已知技术方法自该混合物获得提高产率的对二甲苯。
Description
优先权声明
本申请要求2011年11月14日申请的美国临时申请第61/559,226号的优先权。
技术领域
本发明涉及催化烃转化,更明确而言,改良分子筛催化剂***在芳香族化合物异构化中的用途。
先前技术
二甲苯(对二甲苯、间二甲苯及邻二甲苯)是在化学合成中具有广泛及多种应用的重要中间体。对二甲苯在氧化时产生用于制造合成纺织纤维及树脂的对苯二甲酸。间二甲苯用于制造塑化剂、偶氮染料、木材防腐剂等。邻二甲苯是生产邻苯二甲酸酐的原料。
来自催化重整或其它来源的二甲苯异构体一般不符合作为化学中间体所要求的比例,且另外包括难以分离或转化的乙苯。特定而言,对二甲苯是需求快速增长的主要化学中间体,但含量仅为典型C8芳香族化合物流的20-25%。可通过组合二甲苯异构体回收(如用于对二甲苯回收的吸附)与异构化以产生额外量的所需异构体来实现按需要调整异构体比例。异构化是将缺乏所需二甲苯异构体的二甲苯异构体的非平衡混合物转化成达到平衡浓度的混合物。
已开发不同的催化剂及方法以进行二甲苯异构化。在选择适宜的技术上,需要使异构化处理尽可能接***衡以使对二甲苯产率最大化;然而,与此相关的是由于副反应所引起的更大环状C8损失。所用的达到平衡的方法是在高转化率下(即极接***衡)的高环状C8损失与由于未转化C8芳香族化合物的高再循环比率所引起的高资源成本之间的最佳折中。因此,基于活性、选择性及稳定性的有利平衡评估催化剂。
近几十年来,包含分子筛的催化剂已在二甲苯异构化中变得突出。例如,US3,856,872教导利用包含ZSM-5、-12或-21沸石的催化剂进行二甲苯异构化及乙苯转化。US4,899,011教导利用两种沸石(各与强氢化金属结合)进行C8芳香族化合物异构化。US6,142,941、US7,297,830B2及US7,525,008B2公开用于C8芳香族化合物异构化的沸石催化剂且通过引用的方式并入本文中。尽管这些参考文献教导本发明的个别元素,但没有文献提出这些元素的组合以获得本发明催化剂***的关键特征。
通常通过处理与二甲苯异构体相关的乙苯的方式对用于C8芳香族化合物异构化的催化剂进行分类。乙苯不易异构化成二甲苯,但其通常在异构化单元中转化,因为通过超精馏或吸附自二甲苯分离极其昂贵。一种广泛使用的方法是在使二甲苯异构化成***衡混合物时,使乙苯去烷基化以主要形成苯。另一方法是在具有氢化-脱氢功能的固体酸催化剂存在下,经由转化成环烷烃及由其再转化而使乙苯反应形成二甲苯混合物。前一方法通常产生更高的乙苯转化率及更有效的二甲苯异构化,因此降低在异构化/对二甲苯回收的回路中的再循环量及减少相伴的处理成本。
发明概述
本发明的一个主要目的在于提供一种用于烷基芳香族烃的异构化的新颖催化剂及方法。更具体而言,本发明是关于一种用于包含相当浓度的非芳香族化合物的C8芳香族烃的异构化以生成高纯度产物的催化剂***。
因此,本发明的一个广泛实施方案是关于一种用于转化包括高浓度非平衡C8芳香族化合物及低浓度非芳香族化合物的烃进料混合物的方法,其通过使该混合物与双催化剂***(其包括含有钨组分及至少一种沸石铝硅酸盐中的一者或两者的第一催化剂及基于元素计含有0.01至0.2质量%的至少一种铂族金属组分的第二催化剂)于包括300℃至550℃的温度、100kPa至5MPa的压力及就该双催化剂***而言为0.5至50hr-1的液时空速的烃转化条件下接触,以获得包括比在该进料混合物中浓度减小的乙苯及浓度减小的非芳香族化合物的转化产物。
在一个实施方案中,本发明包括一种用于转化包括高浓度非平衡C8芳香族化合物及低浓度非芳香族化合物的烃进料混合物的方法,其通过使该混合物与双催化剂***(其包括含有10至99质量%的至少一种沸石铝硅酸盐的第一催化剂及基于元素计含有0.01至0.2质量%的至少一种铂族金属组分的第二催化剂)于包括300℃至550℃的温度、100kPa至5MPa的压力及就该双催化剂***而言为0.5至50hr-1的液时空速的烃转化条件下接触,以获得包括比在该进料混合物中比例更高的至少一种二甲苯异构体、浓度减小的乙苯及浓度减小的非芳香族化合物的转化产物。
在另一实施方案中,本发明包括一种用于转化包括高浓度非平衡C8芳香族化合物及低浓度非芳香族化合物的烃进料混合物的方法,其通过使该混合物与双催化剂***(其包括含有钨组分的第一催化剂及基于元素计含有0.01至0.2质量%的至少一种铂族金属组分的第二催化剂)于包括300℃至550℃温度、100kPa至5MPa的压力及就该双催化剂***而言为0.5至50hr-1的液时空速的烃转化条件下接触,以获得包括比在该进料混合物中浓度减小的乙苯及浓度减小的非芳香族化合物的转化产物。
这些以及其它目的及实施方案将自本发明的以下详细描述变得明晰。
实施方案
芳香族化合物异构化的原料包括具有通式C6H(6-n)Rn的可异构化烷基芳香族烃,其中n为2至5的整数且R为CH3、C2H5、C3H7或C4H9,其可呈任何组合及包括其所有异构体以获得更具价值的烷基芳香族异构体。适宜的烷基芳香族烃包括例如(但不限于)邻二甲苯、间二甲苯、对二甲苯、乙苯、乙基甲苯、三甲基苯、二乙基苯、三乙基苯、甲基丙基苯、乙基丙基苯、二异丙基苯及其混合物。
包含乙苯及二甲苯的C8芳香族混合物的异构化是本发明催化剂***的一个特别优选的应用。这样的混合物一般具有位于1至50质量%范围内的乙苯含量、位于0至35质量%范围内的邻二甲苯含量、位于20至95质量%范围内的间二甲苯含量及位于0至30质量%范围内的对二甲苯含量。前述C8芳香族化合物优选包括非平衡混合物,即至少一种C8芳香族异构体以实质上不同于在异构化条件下的平衡浓度的浓度存在。该非平衡混合物通常通过从自芳香族化合物制备方法获得的新鲜C8芳香族混合物中除去对-、邻-和/或间二甲苯而制得。
烷基芳香族烃可以如在来自各种精炼石油流的适宜馏分中所见的形式(例如呈通过催化裂化或重整烃的选择性分馏及蒸馏所获得的个别组分或某一沸点范围内的馏分)用于本发明中。不必浓缩可异构化芳香族烃;本发明方法允许含烷基芳香族化合物流(如催化重整物)异构化,进行或不进行后续芳香族化合物的萃取(extraction),以产生特定二甲苯异构体及尤其产生对二甲苯。本发明方法的C8芳香族化合物进料可包含最多30质量%的含量的非芳香族烃,即环烷烃及链烷烃。本发明尤其可用于处理含有在其它方法中会带来问题的非芳香族化合物浓度的原料。
根据本发明的方法,使优选与氢气混合的烷基芳香族烃进料混合物与下文所述类型的两种或更多种催化剂在烷基芳香族烃异构化区中接触。可利用呈固定床***、移动床***、流化床***、浆液***或沸腾床***的催化剂***或以分批操作方式进行接触。鉴于有价值催化剂的磨耗损失的风险及更简单操作,优选使用固定床***。在该***中,通过适宜的加热方式将富氢气体及该进料混合物预热至所需反应温度且接着使其进入包含一个或多个两种或更多种催化剂的固定床的异构化区。该转化区可为一个或多个独立反应器,其间具有适宜的装置,以确保在各区域的入口处维持所需异构化温度。反应物可以向上、向下或辐射流动方式与该催化剂床接触,且当与催化剂接触时,反应物可呈液相、混合液-气相或气相形式。
第一及第二催化剂可包含于不同的反应器中、在相同的反应器中依次排列、物理混合或作为单一催化剂复合。催化剂优选依次排列,其中该进料接触第一催化剂以转化非芳香族化合物而产生中间体流,其可通过第二催化剂处理以转化乙苯及使芳香族化合物异构化而产生异构化产物。
将催化剂放置于不同的反应器中容许独立控制操作条件,尤其是温度及空间速度。然而,通过利用单一反应器,可实现节约管道、仪器及其它附属设备。催化剂的物理混合可促进催化剂的协同反应,但催化剂组分的分离及回收会更困难。可以任选地在一个或多个其它阶段重复该催化剂***,即在另一序列的该两种催化剂中处理来自接触该进料的反应物。
因此,在本发明的另一实施方案中,该反应器包含第一及第二催化剂的物理混合物。在此实施方案中,颗粒经机械混合以提供本发明的催化剂***。可利用已知技术(如研磨)完全混合颗粒以紧密地掺合该物理混合物。尽管第一及第二颗粒可具有相似尺寸及形状,但颗粒优选具有不同尺寸和/或密度以便于分离以在其用于烃处理后再生或复原。
在本发明的又一实施方案中,第一及第二催化剂的物理混合物包含于相同催化剂颗粒内。在此实施方案中,可将分子筛一起或分开研磨或磨碎以形成具有适宜尺寸(优选小于100微米)的颗粒,并使颗粒负载于适宜的基质中。该基质最优选选自上述无机氧化物。
该烷基芳香族进料混合物(优选C8芳香族化合物的非平衡混合物)与该催化剂***在适宜的烷基芳香族转化条件下接触。这样的条件包括100℃至600℃或更高及优选位于300℃至550℃范围内的温度。压力一般为100kPa至5MPa绝对压力,优选小于3MPa。异构化区中包含足量的该催化剂***所包含的两种催化剂以提供就烃进料混合物而言为0.5至50hr-1及就该催化剂***所包含的各催化剂而言优选0.5至25hr-1的液时空速,空间速度在1至100hr-1的范围内。最佳地,使该烃进料混合物以与氢气以0.5:1至25:1的氢气/烃摩尔比混合的形式反应。可存在其它惰性稀释剂,如氮气、氩气及轻质烃。若两种或更多种催化剂包含于分开的床中,则可在各床内使用以上限制范围内的不同操作条件以实现最佳总体结果。
用于从该异构化区的反应器的流出物中回收异构化产物的特定方案对于本发明而言被视为不关键,且可使用现有技术中已知的任何有效的回收方案。通常,将浓缩该反应器流出物并通过快速分离从中移除氢气及轻质烃组分。然后使浓缩液体产物分馏以除去轻质和/或重质副产物并获得异构化产物。在一些情况下,可通过选择性分馏从该异构化产物中回收某些产物种类(如邻二甲苯)。通常,任选通过结晶作用处理来自C8芳香族化合物异构化的产物以选择性回收对二甲苯异构体。根据US3,201,491,以利用结晶型铝硅酸盐的选择性吸附优选。该优选吸附回收方法的改良及替代方法描述于以引用的方式并入本文中的US3,626,020、US3,696,107、US4,039,599、US4,184,943、US4,381,419及US4,402,832中。
在与乙苯/二甲苯混合物的处理相关的分离/异构化处理组合中,将新鲜C8芳香族进料与来自异构化反应区的包含C8芳香族化合物及环烷烃的异构化产物组合并馈入对二甲苯分离区中;将包括C8芳香族化合物的非平衡混合物的贫对二甲苯流馈入异构化反应区中,其中使C8芳香族异构体异构化至***衡程度以获得异构化产物。在此处理方案中,未回收的C8芳香族异构体优选经再循环直到其因转化成对二甲苯或副反应损失耗尽。也可在对二甲苯分离的前对新鲜C8芳香族进料或异构化产物或其组合进行邻二甲苯分离(优选通过分馏)。
第二催化剂可为适用于乙苯转化及二甲苯异构化的已知技术中的催化剂。优选的催化剂如US6,143,941中所公开的包括沸石铝硅酸盐、铂族金属组分及无定型磷酸铝粘合剂的球体催化剂。通过第一催化剂转化含于原料中的非芳香族化合物允许使用这样的催化剂。
第一催化剂对第二催化剂的摩尔比主要取决于原料组成及所需产物分布,其中第一:第二催化剂的摩尔比优选1:20至50:1且尤其优选1:10至20:1。本发明的催化剂***可包括其它分子筛型或无定型催化剂。
当存在于该第一及第二催化剂中时,沸石的相对比例可在10至99质量%的范围内,优选20至90质量%。
粘合剂应为具有25至500m2/g的表面积、组成均匀及在烃转化处理中所用的条件下相对耐火的多孔吸附载体。术语“组成均匀”表示该载体未分层,不具有组成中的固有物质的浓度梯度,及在组成上完全均质。因此,若该载体为两种或更多种耐火物质的混合物,则这些物质的相对含量在整个载体中将恒定及均一。在本发明的范围内意欲包括已传统地用于烃转化催化剂中的载体物质,如:(1)耐火无机氧化物,如氧化铝、二氧化钛、氧化锆、氧化铬、氧化锌、氧化镁、氧化钍、氧化硼、二氧化硅-氧化铝、二氧化硅-氧化镁、氧化铬-氧化铝、氧化铝-氧化硼、二氧化硅-氧化锆等;(2)陶瓷、瓷、铝矾土;(3)二氧化硅或硅胶、碳化硅、粘土及硅酸盐(包括经合成制备及天然生成的那些,其可经或不经酸处理,例如凹凸棒粘土、硅藻土(diatomaceous earth)、漂白土、高岭土、硅藻土(kieselguhr)等;(4)天然生成或合成制备的结晶型沸石铝硅酸盐,如FAU、MEL、MFI、MOR、MTW(IUPAC Commission on Zeolite Nomenclature),其可呈氢形式或呈已与金属阳离子交换的形式;(5)尖晶石如MgAl2O4、FeAl2O4、ZnAl2O4、CaAl2O4,及其它具有式MO-Al2O3(其中M为2价金属)的类似化合物;及(6)来自这些组中一个或多个的物质的组合。
用于本发明的优选耐火无机氧化物为氧化铝。适宜的氧化铝材料称为γ-、η-及θ-氧化铝的结晶型氧化铝,其中γ-或η-氧化铝产生最佳结果。理想地,该无机氧化物为氧化铝,如γ-氧化铝。该γ-氧化铝可来自勃姆石或拟勃姆石氧化铝(下文可统称为“勃姆石氧化铝”)。该勃姆石氧化铝可与沸石混合并挤出。在氧化(或煅烧)期间,该勃姆石氧化铝可转化成γ-氧化铝。一种用作初始材料的所需勃姆石氧化铝为UOP,LLC,Des Plaines,III出售的VERSAL-251。另一勃姆石氧化铝可由Sasol North America,Houston,Tex以商标名称CATAPAL C出售。氧化铝结合球体的制法一般包括将分子筛、铝溶胶及胶凝剂的混合物滴入维持在升高的温度下的油浴中。可用于该方法中的胶凝剂的实例包括六亚甲基四胺、脲及其混合物。胶凝剂可在升高的温度下释放氨,其使得水溶胶球体转变或转化成水凝胶球体。接着可从该油浴中回收球体且通常在油及氨溶液中进行特定老化处理以进一步改善其物理特性。一示例性油滴法公开于US2,620,314中。
另一粘合剂是无定型二氧化硅形式。有利的无定型二氧化硅分类为湿法水合二氧化硅的合成白色无定型二氧化硅粉末。此类型二氧化硅通过在水溶液中的化学反应产生,并自该水溶液沉淀为超细球状颗粒。该二氧化硅的BET表面积优选120至160m2/g。希望具有低硫酸盐含量,优选小于0.3重量%。尤其优选地,该无定型二氧化硅粘合剂为非酸性,例如,5%水悬浮液的pH为中性或碱性(pH7或更大)。
该复合物的一种优选形状为通过熟知的油滴法连续制造的球体。氧化铝结合球体的制法一般包括将分子筛、氧化铝溶胶及胶凝剂的混合物滴入维持在升高的温度下的油浴中。或者,可利用油滴法进行二氧化硅水溶胶的胶凝作用。一种使该混合物胶凝的方法包括将胶凝剂与该混合物组合及接着将所得的组合混合物分散于已加热至升高的温度的油浴或塔中,以使得凝胶作用伴随形成球体颗粒而发生。在该方法中可使用的胶凝剂为六亚甲基四胺、脲或其混合物。胶凝剂在升高的温度下释放氨,其使水溶胶球体定型或转化成水凝胶球体。接着从该油浴中连续回收球体且通常在油及氨溶液中进行特定老化处理以进一步改善其物理特性。
催化剂复合物的一种替代形状为挤出物。熟知的挤出法起初包括在添加金属组分之前或之后将非沸石分子筛与粘合剂及适宜的胶溶剂混合以形成具有恰当水含量的均质胶糊(dough)或稠糊剂(thick paste),从而允许形成具有可接受完整性的挤出物以经受直接煅烧。可挤出性由该胶糊的水含量分析而测定,其中以位于30至50重量%范围内的水含量优选。然后,经由刺穿有多个孔的模具挤出该胶糊且根据现有技术中熟知的技术切割该意大利面形挤出物以形成颗粒。可容许多种不同的挤出物形状,其包括(但不限于)圆柱体、苜蓿叶、哑铃及对称及非对称多叶形。在本发明的范围内也可进一步通过一步制粒法或现有技术中已知的任何其它方法使挤出物形成任何所需形式,如球体。
接着,优选地,洗涤所得复合物并在50℃至200℃的相对低温下干燥并在450℃至700℃的温度下进行煅烧步骤达1至20小时。
各催化剂可经蒸汽处理以调节酸活性。可在处理的任何阶段进行蒸汽处理,但通常在并入铂族金属之前对沸石及粘合剂的复合物进行。蒸汽处理条件包括5至100体积%的水浓度、100kPa至2MPa的压力及介于600℃与1200℃之间的温度;蒸汽处理温度优选介于650℃与1000℃之间,更优选至少750℃及任选地可为775℃或更高。在一些情形中,可使用800℃至850℃或更高的温度。该蒸汽处理应进行至少1小时,并且优选6至48小时。另外或除该蒸汽处理之外,可利用硝酸铵溶液、无机酸和/或水中的一者或多者洗涤该复合物。可在制备的任何阶段进行洗涤,且可使用两或多阶段洗涤。
钨为第一催化剂的优选组分。钨酸根离子通过(例如)利用浓度通常0.1至20质量%的钨及优选1至15质量%的钨的偏钨酸铵处理而并入催化复合物中。可使用可在煅烧时形成钨酸根离子的化合物(如偏钨酸、钨酸钠、钨酸铵、仲钨酸铵)作为替代性来源。优选地,利用偏钨酸铵提供钨酸根离子并形成固体强酸催化剂。最终催化剂的钨酸根含量基于元素计通常位于0.5至30质量%及优选1至25质量%的范围内。该钨酸盐复合物经干燥,接着优选在450℃至1000℃的温度下进行煅烧(尤其若欲在钨酸盐处理之后并入铂族金属)。
包括铂、钯、铑、钌、锇及铱中的一者或多者的铂族金属为本发明各催化剂复合物的高度优选的组分。优选铂族金属为铂。第一及第二催化剂的各者的相对铂族金属含量为本发明的一个特征。若存在,该铂族金属基于元素计算一般占最终第一催化剂的0.01至0.5质量%,优选0.5至0.3质量%;该第二催化剂基于元素计算优选包括0.01至0.5质量%,优选小于0.2质量%及尤其0.02至0.08质量%的铂族金属。
该铂族金属组分可呈化合物(如氧化物、硫化物、卤化物、氧硫化物等)或呈元素金属或以与该催化剂复合物的一种或多种其它成份组合的形式存在于最终催化剂复合物中。据信当实质上所有铂族金属组分以还原态存在时,可获得最佳结果。可以任何适宜的方式将该铂族金属组分并入催化剂复合物中。一种制备该催化剂的方法包括利用铂族金属的水溶性可分解化合物浸渍煅烧的分子筛/粘合剂复合物。或者,可在复合分子筛组分及粘合剂时添加铂族金属化合物。可用于浸渍溶液、与分子筛及粘合剂共挤出或通过其它已知方法添加的铂族金属的络合物包括氯铂酸、氯钯酸、氯铂酸铵、溴铂酸、三氯化铂、四氯化铂水合物、二氯羰基二氯化铂、四胺氯化铂、二硝基二胺基铂、四硝基铂(II)酸钠、氯化钯、硝酸钯、硫酸钯、氢氧化二胺钯(II)、氯化四胺钯(II)等。优选地,该铂族金属组分通过现有技术中已知的任何方法集中于该催化剂的粘合剂组分上。一种进行该优选金属分布的方法通过在共挤出该分子筛及粘合剂之前复合该金属组分与该粘合剂。
在本发明的范围内,本发明催化剂复合物可包含已知用于改变该铂族金属组分的作用的其它金属组分。这样的金属改性剂可包括铼、锡、锗、铅、钴、镍、铟、镓、锌、铀、镝、铊、及其混合物。可通过现有技术中已知的任何方法将催化有效量的这样的金属改性剂并入该催化剂中以实现均质或分层分布。
本发明的催化剂可包含卤素组分,其包括氟、氯、溴、碘或其混合物,优选氯。然而,优选地,该催化剂不包含除与其它催化剂组分有关的卤素以外的额外的卤素。
各催化剂复合物在100℃至320℃的温度下干燥2至24或更多小时,且通常在400℃至650℃的温度下及空气氛围中煅烧0.1至10小时。若需要,可通过在该空气氛围中并入任选的卤素或含卤素化合物来调节可选卤素组分。
最优地,对所得的煅烧复合物进行实质上无水的还原步骤,以确保特定金属组分的均匀及微细的分散。该还原作用可任选地在本发明的处理设备中进行。优选地,使用实质上纯的干燥氢气(即小于20体积ppm H2O)作为该步骤中的还原剂。该还原剂在可有效将实质上所有VIII族金属组分还原成金属态的条件(包括200℃至650℃的温度及0.5至10小时的时间)下与该催化剂接触。在一些情形中,也可通过现有技术中已知的方法对所得的还原催化剂复合物有利地进行预硫化作用,以将基于元素计算为0.05至1.0质量%的硫并入该催化剂复合物中。
实施例
以下实施例仅为了说明本发明的某些具体实施方案而提供,且不应被视为限制申请专利范围内所阐明的本发明范围。本领域技术人员将认识到在本发明的主旨范围内存在许多可能的其它变化。
制备与C8芳香族化合物混合物的非芳香族化合物的转化有关的第一催化剂的样品并在试验工厂中进行对比测试。
实施例I
根据US7,525,008B2制备包括与氧化铝复合的MTW沸石的挤出颗粒的催化剂。利用氯铂酸溶液浸渍颗粒,干燥,氧化,还原并硫化,以产生包含0.05质量%铂的催化剂。将该催化剂命名为催化剂A。
实施例II
利用US6,143,941的教导制备催化剂。使根据实施例I制备的包括沸石及无定型磷酸铝粘合剂的滴油型球体催化剂参照物与硫酸铵(0.82g硫酸铵+10g去离子水每克载体)在60℃下进行离子交换;在倾析之后,重复该离子交换并利用10g去离子水每克载体洗涤所得球体4次。在120℃干燥球体1小时且在350℃及550℃下于干燥空气中煅烧2小时。利用四胺氯化铂浸渍具有0.7质量%的硫含量的球体以达到0.04质量%的铂含量,在525℃下于空气中利用3%蒸汽煅烧2小时且在425℃下于氢气中还原4小时。将所得催化剂命名为催化剂B。
实施例III
根据US2,620,314制备球体氧化铝颗粒并利用偏钨酸铵进行金属浸渍,所述偏钨酸铵添加有NH4OH,其pH为9-10,以形成包含10质量%钨的固体强酸催化剂。于350℃及550℃下在干燥空气中干燥并煅烧该复合物3小时。利用pH9至10的氯铂酸及盐酸的水溶液浸渍该复合物,在350℃下干燥,以50℃/小时斜升至550℃,用氮气吹扫,在565℃下于氢气中还原1小时并将其命名为催化剂C。
实施例IV
根据US7,297,830制备在1/16英寸γ-氧化铝核上包含MTW沸石活性层的颗粒,以产生10%MTW(40Si/Al2比)的150微米层。另外,利用偏钨酸铵浸渍颗粒,添加NH4OH至pH10,以形成包含10质量%钨的固体强酸催化剂,其经蒸汽处理及在干燥空气中于350℃及550℃下煅烧3小时。根据US7,297,830的实施例III,利用氯铂酸及盐酸(pH9至10)的水溶液浸渍该复合物,以产生超过90%的铂集中于外部沸石层中的催化剂。干燥及煅烧该复合物,然后根据US7,297,830的实施例III,利用氯铂酸及盐酸的水溶液浸渍,以产生超过90%的铂集中于外部沸石层中的含有0.28质量%铂的催化剂。煅烧及还原颗粒以产生催化剂D。
实施例V
利用处理具有以质量%表示的以下组成的非平衡C8芳香族进料的试验工厂流动反应器评估该四种催化剂A-D对C8芳香族化合物中的非芳香族化合物的转化的作用:
实施例VI
在以下条件下测试该四种催化剂:
12重时空速
4氢气/烃摩尔比
在385℃/395℃/405℃下各持续1-2小时
Claims (9)
1.一种用于转化包括高浓度非平衡C8芳香族化合物及低浓度非芳香族化合物的烃进料混合物的方法,其通过使该混合物与双催化剂***在包括300℃至550℃的温度、100kPa至5MPa的压力及就该双催化剂***而言为0.5至50hr-1的液时空速的烃转化条件下接触,以获得包括比在该进料混合物中浓度减小的乙苯及浓度减小的非芳香族化合物的转化产物,所述双催化剂***包括含有钨组分及至少一种沸石铝硅酸盐中的一者或两者的第一催化剂及基于元素计含有0.01至0.2质量%的至少一种铂族金属组分的第二催化剂。
2.如权利要求1的方法,其中非芳香族化合物的浓度为该进料混合物的0.5至10质量%。
3.如权利要求1的方法,其中该第一催化剂基于元素计包括0.01至0.3质量%的铂。
4.如权利要求1的方法,其中该至少一种沸石铝硅酸盐包括MTW。
5.如权利要求1的方法,其中该第一催化剂包括分层球体。
6.如权利要求1的方法,其中第一及第二催化剂依次层叠。
7.如权利要求1的方法,其中该催化剂***为第一及第二催化剂的物理混合物。
8.如权利要求1的方法,其中第一及第二催化剂含于相同催化剂颗粒上。
9.如权利要求8的方法,其中该第一催化剂构成在该第二催化剂的表面上的层。
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CN1177783C (zh) * | 1998-08-25 | 2004-12-01 | 埃克森美孚石油公司 | 对-二甲苯的生产方法 |
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