CN114054077A - 核壳型复合催化剂及其制备方法和用途 - Google Patents
核壳型复合催化剂及其制备方法和用途 Download PDFInfo
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- CN114054077A CN114054077A CN202010752882.2A CN202010752882A CN114054077A CN 114054077 A CN114054077 A CN 114054077A CN 202010752882 A CN202010752882 A CN 202010752882A CN 114054077 A CN114054077 A CN 114054077A
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- catalyst
- core
- zsm
- molecular sieve
- silicalite
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- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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Abstract
本发明涉及一种核壳型复合催化剂,其中核为尖晶石结构XYaOb催化剂,其中X和Y彼此不同且选自元素周期表第二主族、过渡元素和第三主族中的金属元素,a为1‑15之间的数,优选为1‑5之间的数,b为满足各元素化合价所需的氧原子数;壳为分子筛催化剂,优选选自ZSM‑5、ZSM‑11、ZSM‑35和MOR中的一种或多种,更优选选自ZSM‑5和ZSM‑11。该核壳型复合催化剂在用于一步法由合成气直接制备对二甲苯时,不仅工艺简便,操作简单,二甲苯产物中的对二甲苯的选择性高,合成气的转化率高,而且催化剂寿命长。此外,本发明还涉及所述核壳型复合催化剂的制备方法及其在由合成气一步制备对二甲苯中作为催化剂的用途。
Description
技术领域
本发明涉及一种核壳型复合催化剂及其制备方法,以及该催化剂在合成气一步法制备对二甲苯中的用途。
背景技术
二甲苯是重要的有机化工原料,在包装、纤维等领域有着广泛的应用。对二甲苯主要用于制造对苯二甲酸,其可用于制药行业。此外,对二甲苯也是用于生产聚酯纤维和工业塑料的重要中间体。如今,对二甲苯的工业生产方法主要有甲苯歧化与C9芳烃烷基转移、二甲苯异构化、二甲苯吸附分离等技术。在该歧化与烷基转移途径中,热力学限制了产物中的对二甲苯含量,仅可收集到约24重量%浓度的对二甲苯。聚酯纤维的生产要求对二甲苯浓度为60重量%以上,因此现有手段得到的对二甲苯浓度远不能满足工业生产的要求。为了提高对二甲苯的浓度和收率,需要进行一系列后续处理。二甲苯的三种异构体的物理性质,尤其是沸点相差较小,这给对二甲苯在C8芳烃中的分离带来了困难。因此,必须采用昂贵的吸附分离工艺,随之而来的是原材料的损耗和成本的上升。目前90%以上的芳烃来源于石油工业。但近年来石油能源日益短缺,无论是从市场需求还是从替代能源的角度出发,开发新型芳烃合成工艺路线都具有极高的价值。
合成气作为能源转化的桥梁,来源于天然气、煤炭和生物质等自然资源,又可以转化为高附加值的清洁油品,被认为是石油最有潜力的替代品之一。其中,近年来以金属催化剂与合适的分子筛组合的复合催化剂为首的多种新型催化剂成功地调控费托反应产物的分布,取得了重大进展。在成功利用费托合成生产不同碳数区间的油品之后,越来越多研究者将目光聚焦到以高选择性将合成气一步转化为高附加值化学品的工艺来。所述高附加值化学品包括低碳烯烃、低碳醇等重要化工原料。虽然合成气一步法制苯、甲苯、二甲苯等芳烃的相关研究方法不断被报道,但产物中的对二甲苯选择性通常不高且距离产业化还有相当一段距离。产物选择性的调控难以取得突破是面临的主要问题,另一个问题是催化剂容易失活,这使得难以保持催化性能的稳定性。
合成气一步法制备对二甲苯的选择性提高的关键在于高性能催化剂的研发。其中,发现由甲醇或二甲醚合成催化剂与分子筛耦合而成的复合双功能催化剂具有较好的催化性能。该反应路线衍生出一系列的串联反应:合成气加氢制甲醇和甲醇脱水制二甲醚的反应、芳构化反应、二甲苯烷基异构化反应等等。该路线对发展合成气转化工艺有很大的意义,不仅填补了相关工艺路线的空白,而且保障了国家的能源战略安全,同时也提供了一种应对世界石油能源枯竭潜在威胁的解决方案。因此,对该路线进行深入发掘,例如提高对二甲苯的选择性,降低工艺复杂性和成本,是合成气一步法制备对二甲苯亟需解决的技术难点。
Lasa等人较早报道了利用Cr-Zn/ZSM-5催化剂由合成气制芳烃的性能(Ind.Eng.Chem.Res.,1991,30,1448-1455),其中在碳氢化合物产物中,芳烃选择性可达到70%以上,但并未提及芳烃的具体产物分布。Lasa等人随后又报道了利用Cr-Zn/ZSM-5复合催化剂由合成气制芳烃(Appl.Catal.A,1995,125,81-98),在356-410℃,3.6-4.5MPa的反应条件下,碳氢化合物产物中的芳烃选择性达到75%,但是二甲苯的选择性不超过20%。南开大学关乃佳等人(Catal.Today,1996,30(1-3),207-213)采用FeMnO-ZnZSM-5复合催化剂,在270℃,1.1MPa的反应条件下,CO转化率达到98.1%,且催化剂活性连续60h保持稳定,碳氢化合物产物中的芳烃选择性高达53.1%,但是不涉及二甲苯以及碳数在9以上的苯类同系物的具体产物分布。最近,马丁与樊卫斌团队(Chem,2017,3,323-333)将Na-Zn-Fe5C2(FeZnNa)催化剂与具有多层孔道结构的介孔H-ZSM-5分子筛耦合,成功实现了合成气经烯烃中间体一步制备芳烃的转化。在340℃、2MPa的条件下,CO的转化率在85%以上,且催化体系稳定不易失活,在碳氢化合物产物中最多可以得到51重量%的芳烃,其中以轻质芳烃BTX(苯,甲苯,二甲苯)为主,然而并未提及芳烃中的对二甲苯的选择性。厦门大学王野课题组(Chem,2017,3,334-347)成功开发了Zn改性的ZrO2与H-ZSM-5的混合催化剂,CO转化率为20%,芳烃选择性达到了80%。为了提高轻质芳烃的含量,作者根据化学沉积法用TEOS(正硅酸乙酯)处理H-ZSM-5外表面使得最终产物中的BTX选择性得到显著提高,达到了60重量%,但并未提及其中二甲苯和对二甲苯的含量。2019年,日本富山市椿范立,杨国辉,高潮,柴剑宇等的相关专利申请(用于合成气直接制备对二甲苯的催化剂及其制备和应用,申请公布号CN 109590019 A)以高选择性从合成气制备对二甲苯,在最佳反应条件下一氧化碳转化率为55%,对二甲苯选择性为35.3%。该专利申请的核壳型复合催化剂虽然在一定程度上降低了分子筛催化剂的表面酸量,但由于该分子筛催化剂与金属氧化物催化剂的混合方式为物理研磨,这使得一部分中间产物(甲醇)不能立即通过分子筛催化剂进行下一步反应。因此,仍需开发更高效的催化剂。
上述催化剂尽管均可实现合成气一步得到芳烃,但产物中的对二甲苯选择性往往不高或者一氧化碳的转化率不高,而且不能有效地控制二甲苯的异构化反应。另一方面,更高效地利用催化剂的空间位置依然是个挑战。
发明内容
本发明旨在提供一种新型核壳型复合催化剂及其制备方法,及其在合成气经甲醇高选择性地制备对二甲苯中的用途。所涉及的催化剂制备方法简便,合成气转化率高,二甲苯产物中的对二甲苯选择性高,寿命长,工业应用前景大。
本发明的一个目的是提供一种核壳型复合催化剂。该核壳型复合催化剂在用于一步法转化合成气制备对二甲苯时,不仅工艺简便,操作简单,合成气的转化率高,二甲苯中的对二甲苯选择性也高,而且该核壳型复合催化剂寿命长。
本发明另一个目的是提供一种制备本发明核壳型复合催化剂的方法。
本发明的又一个目的是提供本发明核壳型复合催化剂或通过本发明的方法获得的核壳型复合催化剂在由合成气一步制备对二甲苯中作为催化剂的用途。
本发明的这些和其它目的、特征和优点在结合下文考虑后,将易于为本领域技术人员所明了。
附图说明
图1是根据实施例4制备的核壳型复合催化剂的简化结构示意图,其中核为尖晶石结构催化剂,壳为分子筛催化剂,其中核与壳之间存在一粘结剂层。
具体实施方式
根据本发明的第一个方面,提供了一种核壳型复合催化剂,其中核为尖晶石结构XYaOb催化剂,其中X和Y彼此不同且选自元素周期表第二主族、过渡元素和第三主族中的金属元素,a为1-15之间的数,优选为1-5之间的数,b为满足各元素化合价所需的氧原子数;壳为分子筛催化剂,优选选自ZSM-5、ZSM-11、ZSM-35和MOR中的一种或多种,更优选选自ZSM-5和ZSM-11。
在本发明的核壳型复合催化剂中,尖晶石结构XYaOb催化剂与分子筛催化剂的重量比为150:1-1:50,优选为20:1-1:20,更优选为10:1-1:10。
本发明核壳型复合催化剂中的核为尖晶石结构XYaOb催化剂,其中X为选自元素周期表第二主族、过渡元素和第三主族中的金属元素,优选选自Al、Ga、In、Tl、Zn、Cu、Co、Fe、Mn、Cr、Ti、Mg、Ca和Ba,更优选选自Ga、In和Zn;Y为选自元素周期表第二主族、过渡元素与和三主族中的金属元素,优选选自Al、Ga、In、Tl、Zn、Cu、Co、Fe、Mn、Cr、Ti、Mg、Ca和Ba,更优选选自Cr、Ga和Ti。优选地,尖晶石结构XYaOb催化剂为ZnCr2O4或InGa2O4。
本发明的尖晶石结构XYaOb催化剂可通过本领域的任何常规方法制备,例如顺序浸渍法、共浸渍法和共沉淀法,优选共沉淀法。对于包含第一金属组分X和第二金属组分Y的尖晶石结构催化剂,当通过前述方法制备该催化剂时,都涉及将包含第一金属组分X和第二金属组分Y的金属盐水溶液混合。在制备完催化剂后,将其干燥并焙烧。焙烧气氛为空气;焙烧温度为500-600℃,优选550-600℃;焙烧时间为5-9h,优选5-6h。
例如,当以共沉淀法制备尖晶石结构XYaOb催化剂时,通常将X和Y的可溶性金属盐的水溶液混合,然后干燥和焙烧。在混合过程中,可加入沉淀剂,从而将pH值始终控制在8-9之间。所述可溶性盐例如为硝酸盐、氯化物等。所述沉淀剂例如为碱性物质,例如NaOH、Na2CO3、NaHCO3、(NH4)2CO3、NH4OH或氨水。混合在加热和搅拌下进行。加热温度为50-100℃,优选为60-90℃,更优选为70-80℃。反应时间为0.5-5h,优选为1-4h。在反应后,将反应混合物在反应温度下陈化。陈化时间为0.5-10h,优选为1-5h。
优选地,在共沉淀法中,分别借助泵将包含X和Y的混合溶液a以及沉淀剂的溶液b加入到反应器中,二者的添加速率应确保由已经加入的溶液a与已经加入的溶液b实时形成的混合物的pH值为8-9。
以共沉淀法制备作为尖晶石结构XYaOb催化剂的ZnCr2O4为例:为了制备该催化剂,通常将铬、锌各自的硝酸盐用去离子水按所需的铬/锌比例配成混合硝酸盐水溶液;将该溶液与碳酸铵水溶液(也可使用其它沉淀剂,例如碳酸钠、氢氧化钠、氢氧化铵)用泵同时滴加到烧杯中进行共沉淀。在共沉淀过程中不断搅拌,保持沉淀温度为50-100℃,同时通过这两种溶液相对添加速度来将pH值始终控制在8-9之间;在滴加完毕后,停止搅拌,并于反应温度下保持3-5h以进行陈化;过滤陈化后的沉淀物并用去离子水洗涤;将洗涤后的产物干燥;再进行焙烧,即得ZnCr2O4催化剂。
本发明核壳型复合催化剂中的壳为分子筛催化剂,优选选自ZSM-5、ZSM-11、ZSM-35和MOR中的一种或多种,更优选选自ZSM-5和ZSM-11。
本发明的分子筛催化剂可商购获得,或者通过本领域的任何常规方法制备,例如通过水热合成法、浸渍法、离子交换法、气相沉积法、液相沉积法等制备。通常,分子筛催化剂可通过水热合成法制备。
以HZSM-5沸石分子筛的水热合成法为例:将硅源(例如TEOS)、铝源(例如Al(NO3)3·9H2O)、有机模板剂(例如四丙基氢氧化铵(TPAOH))、乙醇和去离子水配制成混合物,室温搅拌2-10h得到溶胶,然后将搅拌好的溶胶转移入水热合成釜中,然后密封,在160-200℃的温度下以2-5rpm的旋转速度晶化12-72h。晶化结束后冷却至室温,将所得的产物洗涤至滤液pH=7-8,干燥过夜,然后置于马弗炉中以0.1-3℃/min升温速率升至400-650℃,焙烧4-8h后,得到ZSM-5分子筛,其为HZSM-5。所述ZSM-5分子筛中SiO2/Al2O3为10-1000。
本发明的分子筛催化剂可呈H形式或其中H部分或全部被M替代的改性分子筛形式,其中M选自Zn、Ga、Cr、Mn、Fe、Ni、Zr、Cu、La、In和Ca中的一种或多种,优选为Zn。
呈M改性形式的分子筛催化剂可以以H形式的分子筛为原料,采用离子交换法、浸渍法、气相沉积法或液相沉积法等制备。
当使用浸渍法制备呈M改性形式的分子筛催化剂时,可将H形式的分子筛催化剂用金属M的可溶性盐水溶液进行浸渍处理,再干燥和焙烧,从而使得M负载在分子筛催化剂上。所述可溶性盐例如为硝酸盐、氯化物盐等。
当使用离子交换法制备呈M改性形式的分子筛催化剂时,可将H形式的分子筛催化剂用金属M的可溶性盐水溶液进行离子交换处理,然后干燥和焙烧。
以离子交换方法制备Zn-ZSM-5分子筛为例:将HZSM-5分子筛加入到硝酸锌水溶液中,在60-100℃下不断搅拌10-20h,进行离子交换。离子交换结束后冷却至室温,将所得产物洗涤至滤液pH=7-8,干燥过夜,然后置于400-600℃马弗炉中焙烧4-6h,从而得到Zn-ZSM-5分子筛。
在元素M改性的分子筛中,元素M占分子筛总重量的0.1-15重量%,优选0.5-10重量%,更优选0.7-5重量%,更优选0.7-2重量%。
所述分子筛催化剂的粒径大小通常为0.01-20μm,优选为0.1-15μm。
在本发明的一个实施方案中,可对分子筛催化剂进行表面修饰。当所用的分子筛是M改性的分子筛时,表面修饰在用M改性之后进行。表面修饰使用表面修饰材料进行。优选地,本发明所用的表面修饰材料选自金属氧化物、石墨烯、活性炭、Silicalite-1、Silicalite-2、MOF、COF、二氧化硅、树脂、生物质(如海带、葡萄糖、果糖)和碳纳米管中的一种或多种,更优选选自活性炭、Silicalite-1和Silicalite-2中的一种或多种。
表面修饰覆盖或去除分子筛催化剂露在表面的酸性位点,从而减少副反应的产生,由此提高目标产物对二甲苯的选择性。
表面修饰可采用本领域的任何常规方法进行。作为修饰方法,可以提及水热合成法、气相沉积法、涂覆法、浸渍法、溅射法、法等,这可以根据表面修饰材料的性质进行常规选择。例如,当使用Silicalite-1和Silicalite-2进行表面修饰时,可采用水热合成法;当使用活性炭、石墨烯或碳纳米管进行修饰时,可采用气相沉积法;当使用金属氧化物进行修饰时,可采用浸渍法和溅射法;当使用二氧化硅进行修饰时,可采用法;当使用树脂或生物质进行修饰时,可以采用涂覆法或浸渍法,然后将所得的表面修饰分子筛在惰性气体,例如氮气下进行焙烧,从而得到碳表面修饰的分子筛催化剂。
以Silicalite-1通过水热合成法修饰H-ZSM-5得到H-ZSM-5@Silicalite-1为例:将硅源(例如TEOS)、有机模板剂(例如TPAOH)、乙醇和去离子水按配制成混合物,室温搅拌2-6h,得到Silicalite-1分子筛前体溶液。将H-ZSM-5分子筛连同所得Silicalite-1分子筛前体溶液一起转移入水热釜中,然后密封,在100-200℃的温度下以2-5rmp的旋转速度晶化12-72h。晶化结束后冷却至室温,将所得产物用去离子水洗涤至滤液pH=7-8,在室温下干燥过夜,然后置于马弗炉中以0.1-3℃/min的升温速率升至500-650℃,焙烧2-8h后,得到H-ZSM-5@Silicalite-1。
在得到的表面修饰分子筛催化剂中,分子筛催化剂与表面修饰材料的重量比为100:1-2:1,优选为50:1-2:1,更优选为10:1-2:1,特别优选为5:1-2:1。
在本发明的一个实施方案中,本发明的核壳型复合催化剂额外包含介于核和壳之间的粘结剂层。所述粘结剂层由含硅物质制成,所述含硅物质优选选自硅溶胶、γ-氨丙氧三乙氧基硅烷(APTES)、γ-氨丙氧三甲氧基硅烷(APTMS)、γ-缩水甘油醚氧丙基三甲氧基硅烷和γ-(甲基丙烯酰氧)丙基三甲氧基硅烷,更优选为硅溶胶。
在本发明的第二个方面中,提供了一种制备本发明的核壳型复合催化剂的方法,包括:
1)提供呈颗粒形式的核,
2)提供呈颗粒形式的分子筛催化剂,以及
3)用分子筛催化剂对核进行包覆。
在步骤3)的包覆之前,可用粘结剂涂覆核,然后用分子筛催化剂对核进行包覆。所述粘结剂可为选自如下的含硅物质:硅溶胶、γ-氨丙氧三乙氧基硅烷(APTES)、γ-氨丙氧三甲氧基硅烷(APTMS)、γ-缩水甘油醚氧丙基三甲氧基硅烷和γ-(甲基丙烯酰氧)丙基三甲氧基硅烷,优选为硅溶胶。可将核在粘结剂中浸渍,使得核上均匀地沾有粘结剂,然后将浸渍有粘结剂的核加入分子筛催化剂的粉末中进行包覆。浸渍和包覆过程可重复2-10次。
在包覆后,对所得产物进行干燥和焙烧。干燥可在室温至120℃下,优选在室温至60℃下,最优选在室温下进行;干燥时间可为3-30小时,优选为6-20小时。焙烧可在马弗炉中在空气气氛下进行。焙烧温度为350-750℃,优选为400-600℃,焙烧时间为1-6h,优选为2-4h。
令人惊讶地发现,当使用粘结剂制备本发明的核壳型复合催化剂时,转化率和对二甲苯的选择显著提高。
由本发明方法制备的催化剂为核壳型复合催化剂,该核壳型复合催化剂可以用于由合成气一步制备对二甲苯。合成气一步制备对二甲苯大体可以分为两部分,第一部分是合成气转化为甲醇,另一部分为甲醇转化为对二甲苯。本发明核壳型复合催化剂中的尖晶石结构催化剂能够将合成气以高转化率和高选择性转化为甲醇,分子筛催化剂则能将由合成气转化来的甲醇进一步催化转化为对二甲苯。本发明的核壳型复合催化剂使得二甲苯产物中的对二甲苯选择性大幅度提高。本发明人发现,在使用本发明的核壳型复合催化剂时,一氧化碳转化率明显提高、对二甲苯在二甲苯产物中的选择性也大幅度提高。此外,本发明的核壳型复合催化剂具有寿命长、制备简单且易于重复的优势,具有良好的应用前景。
在本发明的第三个方面中,提供了本发明的核壳型复合催化剂在由合成气一步制备对二甲苯中作为催化剂的用途。
在本发明的第四个方面中,提供了一种由合成气一步制备对二甲苯的方法,其中使用本发明的核壳型复合催化剂或通过本发明的方法制备的核壳型复合催化剂。
在将本发明的复合催化剂用于催化合成气制对二甲苯之前,可以对其进行还原预处理。有利地,还原预处理的工艺条件如下:还原气为纯氢气;预处理温度为200-800℃,优选为300-500℃;预处理压力为0.1-1.5MPa,优选为0.1-0.7MPa;预处理氢气体积空速为300-7500标准立方米/小时,优选为600-4500标准立方米/小时;和/或预处理还原时间为2-24h,优选为6-8h。在还原预处理之后,通入合成气进行反应以制得对二甲苯。为此使用的合成气中的氢气与一氧化碳的摩尔比为0.1-10,优选为2-5;反应压力为1-20MPa,优选为2-10MPa;反应温度为100-700℃,优选为350-500℃;和/或,空速为300-7500标准立方米/小时,优选为600-4500标准立方米/小时。
采用本发明的核壳型复合催化剂进行合成气的转化,合成气转化率可以达到65%以上,对二甲苯在二甲苯产物中的选择性可达到80%以上,对二甲苯的选择性明显提高。本发明的核壳型复合催化剂可将合成气一步转化为对二甲苯,无需使用包含多种不同类型催化剂的多段反应器,反应流程更为简单,易于操作。此外,本发明的核壳型复合催化剂在用于将合成气一步转化为对二甲苯时,能够在至少2000h内保持高转化率和选择性,因此具有长寿命。
实施例
实施例1
a.ZnCr2O4催化剂的制备
将24.0g的Cr(NO3)3·9H2O和8.9g的Zn(NO3)2·6H2O溶于90ml去离子水中。将所得的混合硝酸盐水溶液与1mol/L的(NH4)2CO3水溶液(将19.2g的(NH4)2CO3溶于200ml去离子水中制得)同时滴加到盛有2L去离子水的烧杯中进行共沉淀。共沉淀过程中不断搅拌,在75℃下恒温3h。pH值保持在8左右,这由两种溶液的相对流速来控制。共沉淀结束后在75℃下静置陈化3h。将沉淀物过滤,然后用去离子水洗涤3次。将洗净的沉淀物在烘箱中于120℃下干燥12h,再在马弗炉中于500℃下焙烧5h。得甲醇合成催化剂,记为ZnCr2O4催化剂。
b.H-ZSM-5分子筛的制备
将硅源(TEOS)、铝源(Al(NO3)3·9H2O)、有机模板剂(TPAOH)、乙醇和去离子水按摩尔比(2TEOS:0.02Al2O3:0.68TPAOH:8EtOH:120H2O)配制成混合物,室温搅拌6h,得到溶胶。然后将搅拌好的溶胶转移入水热合成釜中,而后密封,在180℃的温度下以2rmp速度旋转晶化24h。晶化结束后冷却至室温,将所得产物用去离子水洗涤至滤液pH=7,在室温下干燥过夜,然后置于马弗炉中以1℃/min升温速率升至550℃,焙烧6h后得到ZSM-5分子筛,为H-ZSM-5。所述HZSM-5分子筛中Si/Al摩尔比为46。
c.ZnCr2O4@H-ZSM-5催化剂的制备
用10g硅溶胶(ALDRICH,30wt.%suspension in H2O)浸渍3g ZnCr2O4颗粒状催化剂表面,随后滗出多余的硅溶胶,然后将表面湿润状态的ZnCr2O4放入盛有1g粉末状H-ZSM-5的圆底烧瓶中,快速有力地旋转圆底烧瓶以确保ZnCr2O4表面全部被H-ZSM-5包覆。再重复该包覆过程2次,每次均在盛有1g粉末状H-ZSM-5的圆底烧瓶中进行包覆。最后将催化剂在室温下干燥过夜,在马弗炉中于550℃下焙烧3h制得ZnCr2O4@H-ZSM-5催化剂,其中ZnCr2O4为核,H-ZSM-5为壳,其中ZnCr2O4催化剂与H-ZSM-5分子筛的质量比为1:1。记为ZnCr2O4@H-ZSM-5催化剂。
d.催化实验
将0.5g ZnCr2O4@H-ZSM-5催化剂以固定床形式填充在固定床高压反应器中,连续通入H2与CO的摩尔比为2.1的合成气,控制反应压力为4MPa,合成气空速为1200标准立方米/小时,反应温度为400℃。反应4h后对反应产物和原料气用气相色谱在线分析,反应结果见表1。
实施例2
a.ZnCr2O4催化剂的制备
重复实施例1中的“ZnCr2O4催化剂的制备”,得到ZnCr2O4催化剂。
b.H-ZSM-5催化剂的制备
重复实施例1中的“H-ZSM-5分子筛的制备”,得到H-ZSM-5分子筛。
c.H-ZSM-5@Silicalite-1催化剂的制备
将硅源(TEOS)、有机模板剂(TPAOH)、乙醇和去离子水按摩尔比(1.0TEOS:0.06TPAOH:16.0EtOH:240H2O)配制成混合物,室温搅拌4h,得到Silicalite-1分子筛前驱体溶液。将b.中制备的H-ZSM-5催化剂同所得Silicalite-1分子筛前驱体溶液一起转移入聚四氟乙烯水热釜中,而后密封,在180℃的温度下以2rmp旋转速度晶化24h。晶化结束后冷却至室温,将所得产物用去离子水洗涤至滤液pH=7,在室温下干燥过夜,然后置于马弗炉中以1℃/min升温速率升至550℃,焙烧4h后,得到H-ZSM-5@Silicalite-1,其中H-ZSM-5与Silicalite-1分子筛的重量比为3:1。
d.ZnCr2O4@H-ZSM-5@Silicalite-1催化剂的制备
重复实施例1中的“ZnCr2O4@H-ZSM-5催化剂的制备”,但是使用H-ZSM-5@Silicalite-1代替H-ZSM-5,得到ZnCr2O4@H-ZSM-5@Silicalite-1催化剂。
e.催化实验
重复实施例1中的“催化实验”,但是使用ZnCr2O4@H-ZSM-5@Silicalite-1催化剂代替ZnCr2O4@H-ZSM-5催化剂。反应结果见表1。
实施例3
a.ZnCr2O4催化剂的制备
重复实施例1中的“ZnCr2O4催化剂的制备”,得到ZnCr2O4催化剂。
b.H-ZSM-5催化剂的制备
重复实施例1中的“H-ZSM-5分子筛的制备”,得到H-ZSM-5分子筛。
c.Zn-ZSM-5分子筛的制备
将1.5g的H-ZSM-5分子筛加入到1mol/L的硝酸锌水溶液中,在80℃下不断搅拌15h,进行离子交换。离子交换结束后冷却至室温,将所得的产物洗涤至滤液pH=7,在室温下干燥过夜,然后置于550℃马弗炉中焙烧,焙烧5h后,得到Zn-ZSM-5。基于Zn-ZSM-5分子筛的总重量,Zn的含量为1%。记为Zn-ZSM-5分子筛。
d.ZnCr2O4@Zn-ZSM-5催化剂的制备
重复实施例1中的“ZnCr2O4@H-ZSM-5催化剂的制备”,但是使用Zn-ZSM-5代替H-ZSM-5,得到ZnCr2O4@Zn-ZSM-5分子筛。
e.催化实验
重复实施例1中的“催化实验”,但是使用ZnCr2O4@Zn-ZSM-5催化剂代替ZnCr2O4@H-ZSM-5催化剂。反应结果见表1。
实施例4
a.ZnCr2O4催化剂的制备
重复实施例1中的“ZnCr2O4催化剂的制备”,得到ZnCr2O4催化剂。
b.H-ZSM-5催化剂的制备
重复实施例1中的“H-ZSM-5分子筛的制备”,得到H-ZSM-5分子筛。
c.Zn-ZSM-5分子筛的制备
重复实施例3中的“Zn-ZSM-5分子筛的制备”,得到Zn-ZSM-5分子筛。
d.Zn-ZSM-5@Silicalite-1催化剂的制备
重复实施例2中的“H-ZSM-5@Silicalite-1催化剂的制备”,但是使用Zn-ZSM-5代替H-ZSM-5,得到Zn-ZSM-5@Silicalite-1分子筛。
e.ZnCr2O4@Zn-ZSM-5@Silicalite-1催化剂的制备
重复实施例1中的“ZnCr2O4@H-ZSM-5催化剂的制备”,但是使用Zn-ZSM-5@Silicalite-1代替H-ZSM-5,得到ZnCr2O4@Zn-ZSM-5@Silicalite-1分子筛。
f.催化实验
重复实施例1中的“催化实验”,但是使用ZnCr2O4@Zn-ZSM-5@Silicalite-1催化剂代替ZnCr2O4@H-ZSM-5催化剂。反应结果见表1。
实施例5
a.InGa2O4催化剂的制备
将10.6g的In(NO3)3·3H2O和23.9g的Ga(NO3)2·8H2O溶于90ml去离子水中。将所得的混合硝酸盐水溶液与1mol/L的(NH4)2CO3水溶液(将19.2g的(NH4)2CO3溶于200ml去离子水中制得)同时滴加到盛有2L去离子水的烧杯中进行共沉淀。共沉淀过程中不断搅拌,在75℃下恒温3h。pH值保持在8左右,这由两种溶液的相对流速来控制。共沉淀结束后在75℃下静置陈化3h。将沉淀物过滤,然后用去离子水洗涤3次。将洗净的沉淀物在烘箱中于120℃下干燥12h,再在马弗炉中于500℃下焙烧5h。得甲醇合成催化剂,记为InGa2O4催化剂。
b.H-ZSM-5催化剂的制备
重复实施例1中的“H-ZSM-5分子筛的制备”,得到H-ZSM-5分子筛。
c.Zn-ZSM-5催化剂的制备
重复实施例3中的“Zn-ZSM-5分子筛的制备”,得到Zn-ZSM-5分子筛。
d.Zn-ZSM-5@Silicalite-1催化剂的制备
重复实施例2中的“H-ZSM-5@Silicalite-1催化剂的制备”,但是使用Zn-ZSM-5代替H-ZSM-5,得到Zn-ZSM-5@Silicalite-1分子筛。
e.InGa2O4@Zn-ZSM-5@Silicalite-1催化剂的制备
重复实施例1中的“ZnCr2O4@H-ZSM-5催化剂的制备”,但是使用Zn-ZSM-5@Silicalite-1代替H-ZSM-5,并且使用InGa2O4代替ZnCr2O4,得到InGa2O4@Zn-ZSM-5@Silicalite-1催化剂。
f.催化实验
重复实施例1中的“催化实验”,但是使用InGa2O4@Zn-ZSM-5@Silicalite-1催化剂代替ZnCr2O4@H-ZSM-5催化剂。反应结果见表1。
实施例6
a.ZnCr2O4催化剂的制备
重复实施例1中的“ZnCr2O4催化剂的制备”,得到ZnCr2O4催化剂。
b.H-ZSM-11分子筛的制备
将硅源(TEOS)、铝源(Al(NO3)3·9H2O)、有机模板剂(四丁基氢氧化铵(TBAOH))、乙醇和去离子水按摩尔比(2TEOS:0.02Al2O3:0.68TBAOH:8EtOH:120H2O)配制成混合物,室温搅拌6h,得到溶胶。然后将搅拌好的溶胶转移入水热合成釜中,而后密封,在180℃的温度下以2rmp速度旋转晶化24h。晶化结束后冷却至室温,将所得产物用去离子水洗涤至滤液pH=7,在室温下干燥过夜,然后置于马弗炉中以1℃/min升温速率升至550℃,焙烧6h后得到H-ZSM-11分子筛,为H-ZSM-11。所述H-ZSM-11分子筛中Si/Al摩尔比为46。
c.Zn-ZSM-11催化剂的制备
重复实施例3中的“Zn-ZSM-5分子筛的制备”,但是使用H-ZSM-11代替H-ZSM-5,得到Zn-ZSM-11分子筛。
d.Zn-ZSM-11@Silicalite-1催化剂的制备
重复实施例2中的“H-ZSM-5@Silicalite-1催化剂的制备”,但是使用Zn-ZSM-11代替H-ZSM-5,得到Zn-ZSM-11@Silicalite-1分子筛。
e.ZnCr2O4@Zn-ZSM-11@Silicalite-1催化剂的制备
重复实施例1中的“ZnCr2O4@H-ZSM-5催化剂的制备”,但是使用Zn-ZSM-11@Silicalite-1代替H-ZSM-5,得到ZnCr2O4@Zn-ZSM-11@Silicalite-1催化剂。
f.催化实验
重复实施例1中的“催化实验”,但是使用ZnCr2O4@Zn-ZSM-11@Silicalite-1催化剂代替ZnCr2O4@H-ZSM-5催化剂。反应结果见表1。
实施例7
a.ZnCr2O4催化剂的制备
重复实施例1中的“ZnCr2O4催化剂的制备”,得到ZnCr2O4催化剂。
b.H-ZSM-5催化剂的制备
重复实施例1中的“H-ZSM-5分子筛的制备”,得到H-ZSM-5分子筛。
c.Zn-ZSM-5催化剂的制备
重复实施例3中的“Zn-ZSM-5分子筛的制备”,得到Zn-ZSM-5分子筛。
d.Zn-ZSM-5@C催化剂的制备
将1.5g浓度为1mol/L的葡萄糖水溶液浸渍在1.0g的Zn-ZSM-5上,在室温下干燥过夜,然后置于600℃管式炉中,在氮气保护下焙烧,焙烧5h后,得到Zn-ZSM-5@C催化剂。记为Zn-ZSM-5@C。
e.ZnCr2O4@Zn-ZSM-5@C催化剂的制备
重复实施例1中的“ZnCr2O4@H-ZSM-5催化剂的制备”,但是使用Zn-ZSM-5@C代替H-ZSM-5,得到ZnCr2O4@Zn-ZSM-5@C催化剂。
f.催化实验
重复实施例1中的“催化实验”,但是使用ZnCr2O4@Zn-ZSM-5@C催化剂代替ZnCr2O4@H-ZSM-5催化剂。反应结果见表1。
对比例1
催化剂制备方法与实施例1基本相同,但是使用物理混合物法将核催化剂与壳催化剂直接物理混合,并且改变核与壳重量的比例,使得所得核壳型复合催化剂中ZnCr2O4催化剂与H-ZSM-5分子筛的重量比为1:1。
按照实施例1所述,将所得催化剂应用于合成气直接制得对二甲苯,结果见表1。
对比例2
催化剂制备方法与实施例2基本相同,但改变H-ZSM-5与Silicalite-1分子筛的重量比为1:1。
按照实施例2所述,将所得催化剂应用于合成气直接制得对二甲苯,结果见表1。
对比例3
催化剂制备方法与实施例2基本相同,但改变H-ZSM-5与Silicalite-1分子筛的重量比为1:3。
按照实施例2所述,将所得催化剂应用于合成气直接制得对二甲苯,结果见表1。
对比例4
催化剂制备方法与实施例4基本相同,但改变ZnCr2O4与H-ZSM-5@Silicalite-1的混合方式为物理研磨法。
按照实施例4所述,将所得催化剂应用于合成气直接制得对二甲苯,结果见表1。
对比例5
催化剂制备方法与“用于合成气直接制备对二甲苯的催化剂及其制备和应用”(申请公布号CN 109590019 A)中实施例2相同。
本发明催化剂的寿命测试
a.ZnCr2O4催化剂的制备
重复实施例1中的“ZnCr2O4催化剂的制备”,得到ZnCr2O4催化剂。
b.H-ZSM-5催化剂的制备
重复实施例1中的“H-ZSM-5分子筛的制备”,得到H-ZSM-5分子筛。
c.Zn-ZSM-5分子筛的制备
重复实施例3中的“Zn-ZSM-5分子筛的制备”,得到Zn-ZSM-5分子筛。
d.Zn-ZSM-5@Silicalite-1催化剂的制备
重复实施例2中的“H-ZSM-5@Silicalite-1催化剂的制备”,但是使用Zn-ZSM-5代替H-ZSM-5,得到Zn-ZSM-5@Silicalite-1分子筛。
e.ZnCr2O4@Zn-ZSM-5@Silicalite-1催化剂的制备
重复实施例1中的“ZnCr2O4@H-ZSM-5催化剂的制备”,但是使用Zn-ZSM-5@Silicalite-1代替H-ZSM-5,得到ZnCr2O4@Zn-ZSM-5@Silicalite-1分子筛。
f.寿命实验
将0.5g ZnCr2O4@Zn-ZSM-5@Silicalite-1催化剂以固定床形式填充在固定床高压反应器中,连续通入H2与CO的体积比为2.1的合成气,控制反应压力为4MPa,合成气空速为1200标准立方米/小时,反应温度为400℃。用气相色谱在线分析反应2000h内反应产物和原料气组成,反应结果见表2。
表1
注:
MeOH:甲醇
DME:二甲醚
C2-C5:C2-C5烃
其余:所有其余产物
MX:间二甲苯
OX:邻二甲苯
PX:对二甲苯
PX/X:对二甲苯在二甲苯中的选择性
表2
注:
MeOH:甲醇
DME:二甲醚
C2-C5:C2-C5烃
其余:所有其余产物
MX:间二甲苯
OX:邻二甲苯
PX:对二甲苯
PX/X:对二甲苯在二甲苯中的选择性
Claims (19)
1.一种核壳型复合催化剂,其中核为尖晶石结构XYaOb催化剂,其中X和Y彼此不同且选自元素周期表第二主族、过渡元素和第三主族中的金属元素,a为1-15之间的数,优选为1-5之间的数,b为满足各元素化合价所需的氧原子数;壳为分子筛催化剂,优选选自ZSM-5、ZSM-11、ZSM-35和MOR中的一种或多种,更优选选自ZSM-5和ZSM-11。
2.根据权利要求1的核壳型复合催化剂,其中X和Y选自Al、Ga、In、Tl、Zn、Cu、Co、Fe、Mn、Cr、Ti、Mg、Ca和Ba;优选地,X为Ga、In或Zn,和/或,Y为Cr、Ga或Ti。
3.根据权利要求1或2的核壳型复合催化剂,其中所述分子筛催化剂呈H形式或其中H部分或全部被M替代的改性分子筛形式,其中M选自Zn、Ga、Cr、Mn、Fe、Ni、Zr、Cu、La、In和Ca中的一种或多种,优选为Zn。
4.根据权利要求1-3中任一项的核壳型复合催化剂,其中尖晶石结构XYaOb催化剂与分子筛催化剂的重量比为150:1-1:50,优选为20:1-1:20,更优选为10:1-1:10。
5.根据权利要求1-4中任一项的核壳型复合催化剂,其中所述分子筛催化剂经表面修饰材料修饰,所述表面修饰材料选自金属氧化物、石墨烯、活性炭、Silicalite-1、Silicalite-2、MOF、COF、二氧化硅、树脂、生物质(如海带、葡萄糖、果糖)和碳纳米管中的一种或多种,更优选选自活性炭、Silicalite-1和Silicalite-2中的一种或多种。
6.根据权利要求5的核壳型复合催化剂,其中在得到的表面修饰分子筛催化剂中,分子筛催化剂与表面修饰材料的重量比为100:1-2:1,优选为50:1-2:1,更优选为10:1-2:1,特别优选为5:1-2:1。
7.根据权利要求1-6中任一项的核壳型复合催化剂,其额外包含介于核和壳之间的粘结剂层。
8.根据权利要求7的核壳型复合催化剂,所述粘结剂层由含硅物质制成,所述含硅物质优选选自硅溶胶、γ-氨丙氧三乙氧基硅烷(APTES)、γ-氨丙氧三甲氧基硅烷(APTMS)、γ-缩水甘油醚氧丙基三甲氧基硅烷和γ-(甲基丙烯酰氧)丙基三甲氧基硅烷,更优选为硅溶胶。
9.根据权利要求1-8中任一项的核壳型复合催化剂,其中所述尖晶石结构XYaOb催化剂为ZnCr2O4或InGa2O4。
10.一种制备根据权利要求1-9中任一项的核壳型复合催化剂的方法,包括:
1)提供呈颗粒形式的核,
2)提供呈颗粒形式的分子筛催化剂,以及
3)用分子筛催化剂对核进行包覆。
11.根据权利要求10的方法,其中在用分子筛催化剂对核进行包覆之前,用粘结剂涂覆核。
12.根据权利要求10或11的方法,其中粘结剂为选自如下的含硅物质:硅溶胶、γ-氨丙氧三乙氧基硅烷(APTES)、γ-氨丙氧三甲氧基硅烷(APTMS)、γ-缩水甘油醚氧丙基三甲氧基硅烷和γ-(甲基丙烯酰氧)丙基三甲氧基硅烷,优选为硅溶胶。
13.根据权利要求10-12中任一项的方法,其中在用分子筛催化剂对核进行包覆之前,用表面修饰材料对分子筛催化剂进行表面修饰。
14.根据权利要求10-13中任一项的方法,其中表面修饰材料选自金属氧化物、石墨烯、活性炭、Silicalite-1、Silicalite-2、MOF、COF、二氧化硅、树脂、生物质(如海带、葡萄糖、果糖)和碳纳米管中的一种或多种,更优选选自活性炭、Silicalite-1和Silicalite-2中的一种或多种。
15.根据权利要求10-14中任一项的方法,其中在用分子筛催化剂对核进行包覆之后,将得到的产物焙烧。
16.根据权利要求1-9中任一项的核壳型复合催化剂或通过根据权利要求10-15中任一项的方法制备的核壳型复合催化剂在由合成气一步制备对二甲苯中作为催化剂的用途。
17.一种由合成气一步制备对二甲苯的方法,其中使用根据权利要求1-9中任一项的核壳型复合催化剂或通过根据权利要求10-15中任一项的方法制备的核壳型复合催化剂。
18.根据权利要求17的方法,其中合成气中的氢气与一氧化碳的摩尔比为0.1-10,优选为2-5;反应压力为1-20MPa,优选为2-10MPa;反应温度为100-700℃,优选为350-500℃;和/或,空速为300-7500标准立方米/小时,优选为600-4500标准立方米/小时。
19.根据权利要求17或18的方法,其中在通入合成气进行反应之前,对所述催化剂进行还原预处理,优选还原预处理的工艺条件如下:
还原气为纯氢气;
预处理温度为200-800℃,优选为300-500℃;
预处理压力为0.1-1.5MPa,优选为0.1-0.7MPa;
预处理氢气体积空速为300-7500标准立方米/小时,优选为600-4500标准立方米/小时;和/或
预处理还原时间为2-24h,优选为6-8h。
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