CN114570415A - 一种用于丙烷脱氢制丙烯的Pt@多级孔沸石催化剂及其制备方法 - Google Patents
一种用于丙烷脱氢制丙烯的Pt@多级孔沸石催化剂及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种用于丙烷脱氢制丙烯的Pt@多级孔沸石催化剂及其制备方法,该催化剂的特征为:以纯硅多级孔沸石为载体;活性组分为Pt,其中Pt以团簇的形式存在沸石的微孔中;助剂金属为Sn、Zn或者Ge,这些助剂金属与Pt相互作用形成合金。本发明利用介孔模板的作用一锅法合成出多级孔沸石封装的Pt@多级孔沸石催化剂,由于介孔优异的传质性能显著提高反应物和产物在孔道内的传输速率,从而最大限度的提高Pt的利用率并降低催化剂的积碳失活速率。催化剂应用于丙烷脱氢催化反应,表现出远超其他沸石催化剂的性能。
Description
技术领域
本发明涉及催化剂的制备领域,具体来说涉及一种用于丙烷脱氢制丙烯的Pt@多级孔沸石催化剂及其制备方法。
背景技术
丙烯是一种重要的石油化工基础原料,主要用于生产聚丙烯、环氧丙烷、丙烯腈、丁辛醇等化学品,这些产品广泛应用于涂料、橡胶、化妆品、塑料和纤维等领域。目前石化领域超过一半的丙烯生产都是通过传统石油裂化的技术来实现的,然而随着我国以及全球对丙烯需求量的不断增大,该技术已经不足以满足我国的实际需求,导致我国的丙烯市场存在需求缺口,只能依赖大量的进口来满足实际的需要;因此世界各国尤其是我国都在致力于发展新型专产丙烯技术。
以富含丙烷的页岩气、天然气、煤层气和炼厂气等为原料来制备丙烯,可大幅缓解丙烯市场的供需矛盾,是实现丙烯生产原料多元化的重要途径。丙烷脱氢制丙烯与其他几条丙烯生产路线相比,具有以下明显的优点:1)原料丙烷来源广泛、价格便宜;2)技术流程相对简单,装置投资相对较小;3)丙烯产率高,大约1.2吨丙烷可生产1吨丙烯。因此,丙烷脱氢制丙烯技术具有显著的成本优势,是目前扩大丙烯产能极具竞争力的路线。
全世界80%以上的丙烷脱氢装置都使用UOP公司开发的氧化铝负载的Pt系催化剂。然而该催化剂Pt分散度不高,导致Pt不能被充分利用;此外运行中由于积碳和Pt粒子的烧结,造成催化剂失活较快,需5-7天进行一次再生。因此,发明具有高活性、高稳定性的Pt基催化剂,是突破现有丙烷脱氢技术、发展新一代丙烷脱氢技术亟待解决的重大关键问题。
近年来,基于沸石孔道限域效应发展的沸石封装的Pt催化剂Pt@zeolite用于丙烷脱氢引起了广泛的关注(CN110479353A)。基于沸石特有的微孔限域效应创制的Pt@zeolite催化剂,不仅解决了Pt的高分散性问题(Pt亚纳米簇高度分散在微孔中),而且还能解决Pt纳米粒子的烧结问题(微孔中Pt亚纳米簇高温不团聚),是一类非常具有研究价值和应用前景的丙烷脱氢催化剂。然而,丙烷脱氢Pt@zeolite催化剂在未来应用方面仍然面临着两大技术问题:(1) 微孔沸石中的扩散属于典型的构型扩散,其扩散系数远低于介孔和大孔中的努森扩散,其Ф值一般都远大于1。因此,沸石晶粒内存在浓度梯度,晶粒内反应物的浓度C随距离表面的距离L的增加而减小,因此沸石孔道内活性位点的有效利用率η(近似等于tanh(Ф)/Ф)低于1。由此可见Pt@zeolite催化剂稳定性能的提高是以牺牲活性为代价实现的,这样对于Pt贵金属而言有效利用率反而下降。(2) 由于丙烯产物不能快速从微孔扩散出去,其在微孔缓慢扩散中不可避免的发生聚合反应而产生积碳。当积碳量达到一定程度会造成孔道的完全堵塞而导致催化剂失活。此外,在催化剂焙烧再生过程中,由于微孔传质、传热的限制造成积碳难以完全烧除。以上两大问题共同制约了贵金属Pt的整体利用效率,严重影响了Pt@zeolite催化剂实际应用的经济性。
为有效解决现有Pt@zeolite催化剂在丙烷脱氢反应中催化效率低、容易结碳的问题,本发明专利提出在常规沸石中引入介孔构建多级孔沸石以强化传质,实现扩散与反应的协调,构筑出高性能的丙烷脱氢催化剂。
CN107303497A和CN 112619690A报道了多级孔脱氢催化剂及其制备方法,公开了一种以多级孔 ZSM-5沸石为载体,Pt为活性组分,Sn等为助剂的催化剂。利用该法制备的催化剂具有高的丙烷转化率和丙烯选择性。这些方法通过多步法来合成多级孔沸石负载的Pt催化剂,即先合成常规ZSM-5沸石,再通过碱或者铵处理得到多级孔沸石,最后将Pt等组分浸渍到沸石上。这种方法具有明显的缺点:1.多步合成法过程复杂、而且经济性差;2. 浸渍不能很好的将Pt组分分散到沸石的多级孔道中,Pt组分在沸石晶体表面。
本发明利用介孔模板通过原位一锅法合成出多级孔沸石封装的Pt@多级孔沸石催化剂,过程不仅简单,而且能够将Pt分散到沸石的微孔道中。该催化剂利用介孔优异的传质性能显著提高反应物和产物在孔道内的传输速率,从而最大限度的提高Pt的利用率并降低催化剂的积碳失活速率。
发明内容
本发明专利采用介孔模法一锅法合成出多级孔沸石封装的Pt@多级孔沸石催化剂,由于介孔优异的传质性能显著提高反应物和产物在孔道内的传输速率,从而最大限度的提高Pt的利用率并降低催化剂的积碳失活速率。催化剂应用于丙烷脱氢催化反应,表现出远超其沸石催化剂的活性和稳定性。
为了实现上述目的,本发明采用了如下技术方案:
一种用于丙烷脱氢制丙烯的Pt@多级孔沸石催化剂及其制备方法:该方法制备的催化剂主要由多级孔沸石、负载在载体上的主活性组分和助剂这三种组分构成。其中该催化剂采用介孔模板一锅法合成,负载在沸石上的主要活性组分为Pt,助剂主要为Zn、Ga或Sn等组分。该催化剂的制备方法主要是水热合成法。本方法工艺简单,适用范围广,催化剂性能优异。
一种用于丙烷脱氢制丙烯的Pt@多级孔沸石催化剂,所述催化剂以纯硅多级孔沸石为载体;活性组分为Pt,其中Pt以团簇的形式存在于沸石的微孔中;助剂金属为Sn、Zn或者Ge,这些助剂金属与Pt相互作用形成合金,其中以催化剂为基准,活性组分Pt的负载量0.20-0.30wt%,助剂金属的负载量为0.20-0.50wt%;纯硅多级孔沸石中,介孔大小为10-30nm,介孔体积为0.30-0.50 cm3/g。所述的纯硅多级孔沸石为多级孔结构的ZSM-5沸石、MCM-22沸石、β沸石、丝光沸石中的一种。
一种用于丙烷脱氢制丙烯的Pt@多级孔沸石催化剂的制备方法,具体包括以下步骤:
(1)将硅源、介孔模板剂、结构导向剂和水进行均匀混合,之后充分搅拌一夜,得到沸石前驱体,将Pt化合物和助剂金属化合物加入到沸石前驱体中,进行充分搅拌;
(2)将步骤(1)中制备的溶液转移到聚四氟乙烯内衬放入反应釜中之后放到烘箱中进行晶化反应;
(3)晶化过程结束后,将反应釜进行冷却并打开,将生成的沸石产物经过过滤以及多次洗涤之后进行干燥,得到含有助剂的沸石;
(4)将步骤(3)得到的含有助剂的沸石固体研磨成粉末,之后放到马弗炉中进行高温焙烧从而除去介孔模板剂以及结构导向剂;
(5)将步骤(4)制得的催化剂前体在一定温度下在H2气氛中进行还原从而得到用于丙烷脱氢制丙烯的Pt@多级孔沸石催化剂。
进一步的,步骤合成中所述混合物中各物质摩尔比例满足:
结构导向剂(微孔模板):硅源=0 .05 ~ 0.30:1;
介孔模板:硅源=0 .05 ~ 0.10:1;
Pt金属盐:助剂金属盐:SiO2=0 .015 ~ 0 .030:0 .015 ~ 0 .090:1;
H2O:SiO2=10 ~ 60:1;
其中,硅源的摩尔数以SiO2的摩尔数计;模板剂的摩尔数以模板剂自身的摩尔数计;Pt金属盐和助剂金属盐摩尔数以金属元素的摩尔数计。
进一步的,所用的硅源为白炭黑、正硅酸四乙脂或者硅溶胶;所用的结构导向剂为四丙基氢氧化铵、四乙基氢氧化铵、六亚甲基亚胺中的任意一种;Pt金属有机化合物包括Pt(HACAC)2、Pt(COD)Cl2和Pt(COD)(Me)2、H2PtCl6·6H2O等之中的任意一种;助剂金属化合物包括HSnBu3、Sn(HAC)2、HSnPh3和GaCl3、Ga(NO3)3·xH2O、Ga2(SO4)3·18H2O和Zn(NO3)2·6H2O、ZnSO4·7H2O、ZnCl2中的任意一种;所用的介孔模板剂为聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物(P123)、聚二烯丙基二甲基氯化铵(PDDA)、聚乙烯醇之中的任意一种。
进一步的,步骤(2)中所述晶化反应的温度为140-170℃,晶化反应时间为2-7天。
进一步的,步骤(4)中所述高温焙烧工艺中焙烧温度为500~600℃,焙烧时间为3h~5h。
进一步的,步骤(5)中H2气氛中还原反应的工艺参数为:还原所用的温度为500℃~630℃,还原时间为4 h~8 h。
应用:所述Pt@多级孔沸石催化剂用于丙烷脱氢制丙烯反应,反应温度为570℃~600℃,丙烷的质量空速WHSV为5.3 h-1,丙烷脱氢反应在固定床反应器中进行反应。
本发明的有益效果在于:
本发明通过简单的一锅法合成Pt@多级孔沸石催化剂,过程简单、放大容易且经济性好。该催化剂利用介孔优异的传质性能显著提高反应物和产物在孔道内的传输速率,从而最大限度的提高Pt的利用率并降低催化剂的积碳失活速率。
附图说明
图1为实施例1得到催化剂的STEM图;从图中可以看出Pt金属团簇和纳米粒子高度分散在沸石的微孔孔道中。
具体实施方式
为了进一步理解该发明的具体内容,下面结合了具体的实施方式和附图做了进一步的详细说明,但并不限制本发明保护范围。
实施例1
称取27.10g TEOS于250ml烧杯中,加入11.60g去离子水并室温下搅拌1h,之后加入10.5g PDDA并搅拌2h。称取24g 四丙基氢氧化铵于200ml烧杯中并加入24g去离子水稀释后加入到溶液中,将制得的透明溶液在室温下搅拌一夜使之水解完全从而合成ZSM-5的前驱物。之后称取0.1075g Zn(NO3)2·6H2O和0.0550g H2PtCl6·6H2O加入到沸石前驱物中充分搅拌后转移到200ml聚四氟乙烯内衬放入反应釜中在170℃下晶化3天。晶化结束后用蒸馏水将生成的白色固体洗干净并在120℃下烘干,之后550℃下煅烧4h,再经过氢气550℃还原4h,制得Pt-Zn@多级孔ZSM-5沸石催化剂(Pt的负载量0.25wt%,Zn的负载量为0.30wt%)。催化剂的介孔大小为25 nm, 介孔体积为0.40 cm3/g。
在装填有200mg实施例1所制备的催化剂的固定床管式反应器内,脱氢反应的反应物为丙烷,反应的温度为570℃,丙烷的质量空速WHSV为5.3 h-1,反应的压力为常压的条件下,丙烷的初始转化率为50%,丙烯的选择性为99.5%,催化剂反应72小时后转化率为49.5%,积碳量为0.4%。
实施例2
称取7.35g 白炭黑于250ml烧杯中,加入11.60g去离子水并室温下搅拌1h,之后加入2.8g P123并搅拌2h。称取24g四乙基氢氧化铵于200ml烧杯中并加入24g去离子水稀释后加入到溶液中,将制得的透明溶液在室温下搅拌一夜使之水解完全从而合成ZSM-5的前驱物。之后称取0.0440g Pt(HACAC)2和0.0864g Sn(HAC)2加入到沸石前驱物中充分搅拌后转移到200ml聚四氟乙烯内衬放入反应釜中在140℃下晶化4天。晶化结束后用蒸馏水将生成的白色固体洗干净并在100℃下烘干,之后550℃下煅烧4h,再经过氢气600℃还原4h,从而制得Pt-Sn@多级孔Beta沸石催化剂(Pt的负载量0.30wt%,Sn的负载量为0.39wt%)。催化剂的介孔大小为20 nm, 介孔体积为0.50 cm3/g。
在装填有200mg实施例2所制备的催化剂的固定床管式反应器内,脱氢反应的反应物为丙烷,反应的温度为565℃,丙烷的质量空速WHSV为5.3 h-1,反应的压力为常压的条件下,丙烷的转化率为46%,丙烯的选择性为99.3%,催化剂反应72小时后转化率为45.5%,积碳量为0.3%。
实施例3
称取25.20g 硅溶胶(SiO2含量40%)于250ml烧杯中,加入13.80g去离子水并室温下搅拌1h,之后加入2g 聚乙烯醇并搅拌2h。称取3g 六亚甲基亚胺于200ml烧杯中并加入32g去离子水稀释后加入到溶液中,将制得的透明溶液在室温下搅拌一夜使之水解完全从而合成沸石的前驱物。之后称取0.0555g Pt(COD)Cl2和0.1335g GaCl3加入到沸石的前驱物中充分搅拌后转移到200ml聚四氟乙烯内衬放入反应釜中在120℃下晶化4天。晶化结束后用蒸馏水将生成的白色固体洗干净并在120℃下烘干,之后550℃下煅烧4h,再经过氢气600℃还原6h,制得Pt-Ga@多级孔MCM-22催化剂(Pt的负载量0.30wt%,Ga的负载量为0.50wt%)。催化剂的介孔大小为25 nm, 介孔体积为0.55 cm3/g。
在装填有200mg实施例3所制备的催化剂的固定床管式反应器内,脱氢反应的反应物为丙烷,反应的温度为575℃,丙烷的质量空速WHSV为5.3 h-1,反应的压力为常压的条件下,丙烷的转化率为42%,丙烯的选择性为99%,催化剂反应72小时后转化率为41.5%,积碳量为0.3%。
实施例4
称取29.10g 硅溶胶于250ml烧杯中,加入11.60g去离子水并室温下搅拌1h,之后加入1.8g 聚乙烯醇并搅拌4h。称取28g TPAOH于200ml烧杯中并加入28g去离子水稀释后加入到溶液中,将制得的透明溶液在室温下搅拌一夜使之水解完全从而合成ZSM-5的前驱物。之后称取0.0600g Pt(COD)(Me)2 和0.1854g Ga(NO3)3·xH2O加入到ZSM-5前驱物中充分搅拌后转移到200ml聚四氟乙烯内衬放入反应釜中在170℃下晶化7天。晶化结束后用蒸馏水将生成的白色固体洗干净并在120℃下烘干,之后550℃下煅烧4h,再经过氢气550℃还原7h,从而得到Pt-Ga@多级孔ZSM-5沸石催化剂(Pt的负载量0.29wt%,Ga的负载量为0.42wt%)。催化剂的介孔大小为30 nm, 介孔体积为0.50 cm3/g。
在装填有200mg实施例4所制备的催化剂的固定床管式反应器内,脱氢反应的反应物为丙烷,反应的温度为560℃,丙烷的质量空速WHSV为5.3 h-1,反应的压力为常压的条件下,丙烷的转化率为42%,丙烯的选择性为98.5%,催化剂反应72小时后转化率为41.7%,积碳量为0.4%。
实施例5
称取4.72g 白炭黑于250ml烧杯中,加入11.60g去离子水并室温下搅拌1h,之后加入18.6g PDDA并搅拌4h。称取36g 四乙基氢氧化铵于200ml烧杯中并加入36g去离子水稀释后加入到溶液中,将制得的透明溶液在室温下搅拌一夜使之水解完全从而合成ZSM-5的前驱物。之后称取0.025g Pt(COD)Cl2和0.0645g Zn(NO3)2·6H2O加入到沸石前驱物中充分搅拌后转移到200ml聚四氟乙烯内衬放入反应釜中在150℃下晶化6天。晶化结束后用蒸馏水将生成的白色固体洗干净并在100℃下烘干,之后550℃下煅烧4h,再经过氢气500℃还原8h,从而制得Pt-Zn@多级孔Beta沸石催化剂(Pt的负载量0.27wt%,Zn的负载量为0.30wt%)。催化剂的介孔大小为30 nm, 介孔体积为0.56 cm3/g。
在装填有200mg实施例5所制备的催化剂的固定床管式反应器内,脱氢反应的反应物为丙烷,反应的温度为580℃,丙烷的质量空速WHSV为5.3 h-1,反应的压力为常压的条件下,丙烷的转化率为41%,丙烯的选择性为99.6%,催化剂反应72小时后转化率为40.7%,积碳量为0.5%。
实施例6
称取25.6g TEOS于250ml烧杯中,加入16.60g去离子水并室温下搅拌1h,之后加入3.3g P123并搅拌6h。称取3g 六亚甲基亚胺于200ml烧杯中并加入22g去离子水稀释后加入到溶液中,将制得的透明溶液在室温下搅拌一夜使之水解完全从而合成ZSM-5的前驱物。之后称取0.0572g 无水SnCl4加入到沸石前驱物中充分搅拌后转移到200ml聚四氟乙烯内衬放入反应釜中先120℃晶化2天,之后150℃晶化3天。晶化结束后用蒸馏水将生成的白色固体洗干净并在110℃下烘干,之后在马弗炉中560℃下煅烧6h。将0.038g H2PtCl6·6H2O固体加入56.40g乙醇中配成浸渍溶液,以1g沸石催化剂加入3.2g浸渍液的比例进行浸渍,静置一段时间后在110℃下烘干, 之后550℃下煅烧4h,再经过氢气630℃还原4h,从而制得Pt-Sn@多级孔MCM-22沸石催化剂(Pt的负载量0.20wt%,Sn的负载量为0.34wt%)。催化剂的介孔大小为25 nm, 介孔体积为0.50 cm3/g。
在装填有200mg实施例6所制备的催化剂的固定床管式反应器内,脱氢反应的反应物为丙烷,反应的温度为560℃,丙烷的质量空速WHSV为5.3 h-1,反应的压力为常压的条件下,丙烷的转化率为43%,丙烯的选择性为98.5%,催化剂反应72小时后转化率为42.7%,积碳量为0.3%。
对比催化剂1:(未加入介孔模板剂)
称取27.10g TEOS于250ml烧杯中,加入11.60g去离子水并室温下搅拌1h。称取24g四丙基氢氧化铵于200ml烧杯中并加入24g去离子水稀释后加入到溶液中,将制得的透明溶液在室温下搅拌一夜使之水解完全从而合成ZSM-5的前驱物。之后称取0.1075g ZnSO4·7H2O和0.055g H2PtCl6·6H2O加入到沸石前驱物中充分搅拌后转移到200ml聚四氟乙烯内衬放入反应釜中在170℃下晶化72h。晶化结束后用蒸馏水将生成的白色固体洗干净并在120℃下烘干,之后在马弗炉中550℃下煅烧4h,再经过氢气550℃还原4h,制得微孔沸石封装的Pt-Zn@ZSM-5沸石催化剂(Pt的负载量0.25wt%,Zn的负载量为0.30wt%)。催化剂的介孔大小为7 nm, 介孔体积为0.04 cm3/g,介孔含量少。
在装填有200mg所制备的催化剂的固定床管式反应器内,脱氢反应的反应物为丙烷,反应的温度为570℃,丙烷的质量空速WHSV为5.3 h-1,反应的压力为常压的条件下,丙烷的初始转化率为35%,丙烯的选择性为90.5%,催化剂反应72小时后转化率为25.5%,积碳量为2.4%。
对比催化剂2:(通过浸渍负载金属组分)
称取27.10g TEOS于250ml烧杯中,加入11.60g去离子水并室温下搅拌1h。称取24g四丙基氢氧化铵于200ml烧杯中并加入24g去离子水稀释后加入到溶液中,将制得的透明溶液在室温下搅拌一夜使之水解完全从而合成ZSM-5沸石的前驱物。混合液充分搅拌后转移到200ml聚四氟乙烯内衬放入反应釜中在170℃下晶化72h。晶化结束后用蒸馏水将生成的白色固体洗干净并在120℃下烘干,之后550℃下煅烧4h,再经过氢气550℃还原4h,制得ZSM-5沸石(Pt的负载量0.25wt%,Zn的负载量为0.30wt%)。沸石的介孔大小为25 nm, 介孔体积为0.25 cm3/g。
将制备的ZSM-5沸石在室温下通过0.10 M的NaOH处理24小时得到介孔ZSM-5,然后再通过浸渍法将含0.1075g ZnSO4·7H2O和0.055g H2PtCl6·6H2O的混合液负载到ZSM-5沸石上,得到制得Pt-Zn@ZSM-5沸石催化剂。
在装填有200mg所制备的催化剂的固定床管式反应器内,脱氢反应的反应物为丙烷,反应的温度为570℃,丙烷的质量空速WHSV为5.3 h-1,反应的压力为常压的条件下,丙烷的初始转化率为33%,丙烯的选择性为87.5%,催化剂反应72小时后转化率为22.5%,积碳量为3.1%。
由催化剂对比数据可以看出,本发明专利制备的催化剂含有大量的介孔,介孔体积可增加到0.40cm3/g以上。合成的催化剂在丙烷脱氢反应中活性高、失活速率低、积碳量少等优点,因此该催化剂具有较好的工业应用潜力。该催化剂优异的性能主要利用介孔优异的传质性,能显著提高反应物和产物在孔道内的传输速率,从而最大限度的提高Pt的利用率并降低催化剂的积碳失活速率。
以上所述的实例仅仅为本发明较好的实施实例,凡是依本发明申请专利范围所做的变化与修饰,皆应属于本发明的涵盖范围。
Claims (10)
1. 一种用于丙烷脱氢制丙烯的Pt@多级孔沸石催化剂,其特征在于:所述Pt@多级孔沸石催化剂以纯硅多级孔沸石为载体;活性组分为Pt,其中Pt以团簇的形式存在于沸石的微孔中;助剂金属为Sn、Zn或者Ge,这些助剂金属与Pt相互作用形成合金,其中活性组分Pt的负载量0.20-0.30wt%,助剂金属的负载量为0.20-0.50wt%;纯硅多级孔沸石中,介孔大小为10-30nm,介孔体积为0.30-0.50 cm3/g。
2.根据权利要求1所述的Pt@多级孔沸石催化剂,其特征在于:所述的纯硅多级孔沸石为多级孔结构的ZSM-5沸石、MCM-22沸石、β沸石、丝光沸石中的一种。
3.根据权利要求1所述的一种用于丙烷脱氢制丙烯的Pt@多级孔沸石催化剂的制备方法,其特征在于:具体包括以下步骤:
(1)将硅源、介孔模板剂、结构导向剂和水进行均匀混合,之后充分搅拌一夜,得到沸石前驱体,将Pt化合物和助剂金属化合物加入到沸石前驱体中,进行充分搅拌;
(2)将步骤(1)中制备的溶液转移到聚四氟乙烯内衬放入反应釜中之后放到烘箱中进行晶化反应;
(3)晶化过程结束后,将反应釜进行冷却并打开,将生成的沸石产物经过过滤以及多次洗涤之后进行干燥,得到含有助剂的沸石;
(4)将步骤(3)得到的含有助剂的沸石固体研磨成粉末,之后放到马弗炉中进行高温焙烧从而除去介孔模板剂以及结构导向剂;
(5)将步骤(4)制得的催化剂前体在一定温度下在H2气氛中进行还原从而得到用于丙烷脱氢制丙烯的Pt@多级孔沸石催化剂。
4.根据权利要求3所述的方法,其特征在于,步骤合成中所述混合物中各物质摩尔比例满足:
结构导向剂:硅源=0 .05 ~ 0.30:1
介孔模板:硅源=0 .05 ~ 0.10:1;
Pt化合物:助剂金属化合物:SiO2=0 .015 ~ 0 .030:0 .015 ~ 0 .090:1;
H2O:SiO2=10 ~ 60:1;
其中,硅源的摩尔数以SiO2的摩尔数计;模板剂的摩尔数以模板剂自身的摩尔数计;Pt化合物和助剂金属化合物摩尔数以金属元素的摩尔数计。
5.根据权利要求3所述的方法,其特征在于,所用的硅源为白炭黑、正硅酸四乙脂或者硅溶胶;所用的结构导向剂为四丙基氢氧化铵、四乙基氢氧化铵、六亚甲基亚胺中的任意一种;Pt化合物包括Pt(HACAC)2、Pt(COD)Cl2和Pt(COD)(Me)2、H2PtCl6·6H2O等之中的任意一种;助剂金属化合物包括HSnBu3、Sn(HAC)2、HSnPh3和GaCl3、Ga(NO3)3·xH2O、Ga2(SO4)3·18H2O和Zn(NO3)2·6H2O、ZnSO4·7H2O、ZnCl2中的任意一种。
6.根据权利要求3所述的制备方法,其特征在于:所用的介孔模板剂为聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物P123、聚二烯丙基二甲基氯化铵PDDA、聚乙烯醇之中的任意一种。
7.根据权利要求3所述的制备方法,其特征在于:步骤(2)中所述晶化反应的温度为140-170℃,晶化反应时间为2-7天。
8.根据权利要求3所述的制备方法,其特征在于:步骤(4)中所述高温焙烧工艺中焙烧温度为500~600℃,焙烧时间为3h~5h。
9. 根据权利要求3所述的制备方法,其特征在于:步骤(5)中H2气氛中还原反应的工艺参数为:还原所用的温度为500℃~630℃,还原时间为4 h~8 h。
10.根据权利要求1所述的Pt@多级孔沸石催化剂的应用,其特征在于:所述Pt@多级孔沸石催化剂用于丙烷脱氢制丙烯反应,反应温度为570℃~600℃,丙烷的质量空速WHSV为5.3 h-1,丙烷脱氢反应在固定床反应器中进行反应。
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