CN110586179B - 一种对低碳烯烃具有较高的选择性的催化剂及其制备方法 - Google Patents
一种对低碳烯烃具有较高的选择性的催化剂及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种对低碳烯烃具有较高的选择性的催化剂及其制备方法,其中,制备方法包括以下步骤:(1)以硅源、去离子水、模板剂、碱源、硼源和晶种溶液为原料经过晶化和焙烧制备得到B‑ZSM‑5分子筛母体‑1;(2)将NaOH、Al(NO3)3和水混合制成处理液,并加入B‑ZSM‑5分子筛母体‑1,经搅拌和焙烧制备得到B‑ZSM‑5分子筛母体‑2;(3)经过铵交换制备得到B‑ZSM‑5分子筛母体‑3;(4)经过压片和过筛制备得到最终的ZSM‑5分子筛。本发明的有益之处在于:(1)制得的ZSM‑5分子筛既可用在MTO工艺中,也可用在MTP工艺中;(2)无论是在MTO工艺中还是在MTP工艺中,制得的ZSM‑5分子筛对C2‑C4烯烃都具有较高的总选择性;(2)制得的ZSM‑5分子筛催化稳定性得到了提高。
Description
技术领域
本发明涉及一种催化剂及其制备方法,具体涉及一种对低碳烯烃具有较高的选择性的催化剂及其制备方法,属于催化剂技术领域。
背景技术
乙烯、丙烯等低碳烯烃是重要的基本化工原料,随着我国国民经济的发展,特别是现代化学工业的发展,我国对低碳烯烃的需求日渐攀升,供需矛盾也将日益突出。
甲醇制乙烯、丙烯等低碳烯烃的MTO工艺和甲醇制丙烯的MTP工艺,是目前重要的化工技术。该类技术以煤或天然气合成的甲醇为原料,生产低碳烯烃,是发展非石油资源生产乙烯、丙烯等产品的核心技术。
目前,在甲醇制乙烯、丙烯等低碳烯烃的MTO工艺中,普遍使用ZSM-5分子筛作为催化剂,现有的ZSM-5分子筛多为颗粒状,在实际使用中发现其存在以下一些问题:
1、催化稳定性较差;
2、低碳烯烃的总选择性较低。
发明内容
为解决现有技术的不足,本发明的目的在于提供一种催化稳定性较好并且低碳烯烃的总选择性较高的催化剂及其制备方法。
为了实现上述目标,本发明采用如下的技术方案:
一种对低碳烯烃具有较高的选择性的催化剂的制备方法,其特征在于,包括以下步骤:
Step1:制备B-ZSM-5分子筛母体-1
向聚四氟乙烯反应釜中依次加入硅源、去离子水、模板剂、碱源、硼源和晶种溶液,搅拌均匀后在空气氛围下于170℃晶化3d,然后离心、洗涤、烘干、研磨,在空气氛围下于550℃焙烧6h,得到B-ZSM-5分子筛母体-1;
Step2:碱处理
将NaOH、Al(NO3)3和水混合制成处理液,将盛有处理液的烧杯置于65℃水浴锅中,待恒温后加入B-ZSM-5分子筛母体-1,搅拌30min,然后取出离心、洗涤、烘干、研磨,在空气氛围下于500℃焙烧4h,制得B-ZSM-5分子筛母体-2;
Step3:铵交换
将盛有NH4Cl溶液的烧杯置于60℃水浴锅中,待恒温后加入B-ZSM-5分子筛母体-2,搅拌2h,然后取出离心、洗涤,完成1次铵交换操作,重复前述铵交换操作2次,最后将产物烘干、研磨,在空气氛围下于500℃焙烧4h,制得B-ZSM-5分子筛母体-3;
Step4:成型
将B-ZSM-5分子筛母体-3压片成型,然后用筛子筛成20-40目的颗粒,得到最终的ZSM-5分子筛。
前述的制备方法,其特征在于,在Step1中,前述硅源选用的是硅溶胶、正硅酸乙酯或白炭黑。
前述的制备方法,其特征在于,在Step1中,前述模板剂选用的是四丙基溴化铵、四丙基氢氧化铵或正丁胺。
前述的制备方法,其特征在于,在Step1中,前述碱源选用的是乙胺、氢氧化钠或偏铝酸钠。
前述的制备方法,其特征在于,在Step1中,前述硼源选用的是硼酸或氧化硼。
前述的制备方法,其特征在于,在Step1中,前述晶种溶液是由正硅酸乙酯、四丙基氢氧化铵和去离子水以5:7:3的质量比混合并于80℃下老化72h得到的,晶种的粒径分布在10-100nm范围内。
前述的制备方法,其特征在于,在Step2中,前述处理液中NaOH的浓度为0.2mol/L,Al(NO3)3的浓度为26.6μmol/L。
前述的制备方法,其特征在于,在Step3中,前述NH4Cl溶液的浓度为0.4mol/L。
前述的制备方法,其特征在于,在Step1、Step2和Step3中,前述烘干均是在空气氛围下于80℃烘干。
本发明的有益之处在于:
(1)经过碱处理和加铝后,得到的催化剂强酸位降低,出现了弱酸中心,这十分有利于低碳烯烃的生成,所以无论是在甲醇制乙烯、丙烯等低碳烯烃的MTO工艺中,还是在甲醇制丙烯的MTP工艺中,该催化剂对C2-C4烯烃都具有较高的总选择性,其中,在甲醇制乙烯、丙烯等低碳烯烃的MTO工艺中,该催化剂对C2-C4烯烃的总选择性达到了85.83%;
(2)经过碱处理后,介孔结构被引入到了催化剂中,改善了积炭前驱体在催化剂孔道内的扩散性能,所以无论是在甲醇制乙烯、丙烯等低碳烯烃的MTO工艺中,还是在甲醇制丙烯的MTP工艺中,催化剂的催化稳定性都得到了提高;
(3)该催化剂既可用在甲醇制乙烯、丙烯等低碳烯烃的MTO工艺中,还可用在甲醇制丙烯的MTP工艺中,使用范围比较广。
附图说明
图1是B-ZSM-5分子筛母体-1放大15.00K倍时的扫描电镜图片;
图2是B-ZSM-5分子筛母体-1放大30.00K倍时的扫描电镜图片;
图3是B-ZSM-5分子筛母体-2放大15.00K倍时的扫描电镜图片;
图4是B-ZSM-5分子筛母体-2放大30.00K倍时的扫描电镜图片;
图5是B-ZSM-5分子筛母体-3放大15.00K倍时的扫描电镜图片;
图6是B-ZSM-5分子筛母体-3放大30.00K倍时的扫描电镜图片。
具体实施方式
以下结合附图和具体实施例对本发明作具体的介绍。
第一部分、制备ZSM-5分子筛
Step1:制备B-ZSM-5分子筛母体-1
向聚四氟乙烯反应釜中依次加入333.3g二氧化硅含量为30wt%的硅溶胶(硅源)、225g去离子水(反应介质)、66.7g四丙基溴化铵(模板剂)、111.3g浓度为65wt%的乙胺水溶液(碱源)、8.24g硼酸(硼源)和10.4g晶种溶液,搅拌均匀后在空气氛围下于170℃晶化3d,然后离心,用去离子水洗涤3次,之后在空气氛围下于80℃烘干,取出研磨并转移至坩埚中,在空气氛围下于550℃焙烧6h,得到B-ZSM-5分子筛母体-1。
晶种溶液的制备方法如下:将50g的正硅酸乙酯(TEOS)、70g的四丙基氢氧化铵(TPAOH)和30g的去离子水混合搅拌配成溶液,于80℃下老化72h,得到晶种溶液,晶种的粒径分布在10-100nm范围内。
硅源:除了硅溶胶以外,还可以选用白炭黑或正硅酸乙酯。
模板剂:除了四丙基溴化铵以外,还可以选用四丙基氢氧化铵(TPAOH)或正丁胺。
碱源:除了乙胺以外,还可以选用氢氧化钠或偏铝酸钠。
硼源:除了硼酸以外,还可以选用氧化硼。
B-ZSM-5分子筛母体-1放大15.00K倍和30.00K倍时,扫描电镜图片分别如图1和图2所示。
由图1和图2可知:B-ZSM-5分子筛母体-1外表面形貌很规整。
Step2:碱处理
配制处理液:称取0.48g NaOH固体于100ml烧杯中,量筒量取60ml去离子水倒入烧杯中,搅拌均匀后再加入0.02gAl(NO3)3·9H2O,搅拌均匀,配制成处理液,每升处理液中含有0.2molNaOH、26.6μmolAl(NO3)3。
将盛有60ml处理液的烧杯置于65℃水浴锅中,待恒温后加入2g B-ZSM-5分子筛母体-1,搅拌30min,然后取出离心,去离子水洗涤3次,在空气氛围下于80℃烘干,取出研磨并转移至坩埚中,在空气氛围下于500℃焙烧4h,制得B-ZSM-5分子筛母体-2。
在碱处理过程中,主要发生了以下一些变化:
(1)处理液脱除了B-ZSM-5分子筛母体-1上的大量硅,B-ZSM-5分子筛母体-1上少量的铝也被脱除了下来;
(2)处理液刻蚀硅,将介孔结构引入了B-ZSM-5分子筛母体-1中,改善了积炭前驱体在B-ZSM-5分子筛母体-1孔道内的扩散性能,这可以提高最终的ZSM-5分子筛在甲醇制低碳烯烃的MTO工艺中的催化稳定性;
(3)处理液中的铝缓慢沉积到B-ZSM-5分子筛母体-1的表面,对硅起到了保护作用,避免了过度刻蚀,使得处理得到的B-ZSM-5分子筛母体-2具有均匀的介孔分布(我们在配制处理液时,设置了对照组,令处理液中只含有0.2mol/LNaOH,不含Al(NO3)3,最后经计算,最终的ZSM-5分子筛的产率为65%,比加铝的实验组的产率低了10%,这证实了:铝能够避免过度刻蚀)。
经过碱处理和加铝后,得到的B-ZSM-5分子筛母体-2强酸位降低,出现了弱酸中心,这十分有利于低碳烯烃的生成。
B-ZSM-5分子筛母体-2放大15.00K倍和30.00K倍时,扫描电镜图片分别如图3和图4所示。
由图3和图4可知:B-ZSM-5分子筛母体-2分散性比较好,体现出了一定的解聚作用。
Step3:铵交换
称取0.3209g NH4Cl固体于25ml烧杯中,量筒量取15ml去离子水倒入烧杯中,搅拌均匀,配制成浓度为0.4mol/L的NH4Cl溶液。
将盛有15ml NH4Cl溶液的烧杯置于60℃水浴锅中,待恒温后加入1.5g B-ZSM-5分子筛母体-2,搅拌2h,然后取出离心,去离子水洗涤3次,完成1次铵交换操作。重复前述铵交换操作2次。最后将产物在空气氛围下于80℃烘干,取出后研磨并转移至坩埚中,在空气氛围下于500℃焙烧4h,制得B-ZSM-5分子筛母体-3。
铵交换是将B-ZSM-5分子筛母体-2(钠型分子筛)中的Na+置换为NH4 +,减少杂质离子的引入,最后通过焙烧即可将NH4 +除去。
B-ZSM-5分子筛母体-3放大15.00K倍和30.00K倍时,扫描电镜图片分别如图5和图6所示。
由图5和图6可知:B-ZSM-5分子筛母体-3表面比较规整,分散性好。
Step4:成型
取一定量的B-ZSM-5分子筛母体-3,经过压片成型,然后用筛子筛成20-40目的颗粒,得到最终的ZSM-5分子筛。
经计算,ZSM-5分子筛的产率为75%。
第二部分、对ZSM-5分子筛的选择性和催化稳定性进行评价称取1g ZSM-5分子筛,装入石英管中,然后在固定床催化剂评价装置上对ZSM-5分子筛的选择性和催化稳定性进行评价。
评价条件:MTO工艺,床层温度472℃,WHSV=1.5h-1。
测定结果:
由上表可知:
(1)采用MTO工艺时,ZSM-5分子筛对乙烯和丁烯的选择性随着时间的增长而增加,对乙烯的选择性最高达到了24.61%,对丁烯的选择性最高达到了11.16%,而对丙烯的选择性则是随着时间的增长而下降,虽然在下降,但选择性仍在43%以上,对低碳烯烃(C2-C4)的总选择性在79%以上,最高达到了85.83%;
(2)采用MTO工艺时,在床层温度472℃下反应5h后,低碳烯烃(C2-C4)的总选择性虽有所下降(下降了7%),但是下降得不是很多。
由此可见,在甲醇制乙烯、丙烯等低碳烯烃的MTO工艺中,本发明提供的ZSM-5分子筛对低碳烯烃具有较高的选择性,并且自身还具有较好的催化稳定性。
需要说明的是,上述实施例不以任何形式限制本发明,凡采用等同替换或等效变换的方式所获得的技术方案,均落在本发明的保护范围内。
Claims (10)
1.一种对低碳烯烃具有较高的选择性的催化剂的制备方法,其特征在于,包括以下步骤:
Step1:制备B-ZSM-5分子筛母体-1
向聚四氟乙烯反应釜中依次加入硅源、去离子水、模板剂、碱源、硼源和晶种溶液,搅拌均匀后在空气氛围下于170℃晶化3d,然后离心、洗涤、烘干、研磨,在空气氛围下于550℃焙烧6h,得到B-ZSM-5分子筛母体-1;
Step2:碱处理
将NaOH、Al(NO3)3和水混合制成处理液,将盛有处理液的烧杯置于65℃水浴锅中,待恒温后加入B-ZSM-5分子筛母体-1,搅拌30min,然后取出离心、洗涤、烘干、研磨,在空气氛围下于500℃焙烧4h,制得B-ZSM-5分子筛母体-2;
Step3:铵交换
将盛有NH4Cl溶液的烧杯置于60℃水浴锅中,待恒温后加入B-ZSM-5分子筛母体-2,搅拌2h,然后取出离心、洗涤,完成1次铵交换操作,重复前述铵交换操作2次,最后将产物烘干、研磨,在空气氛围下于500℃焙烧4h,制得B-ZSM-5分子筛母体-3;
Step4:成型
将B-ZSM-5分子筛母体-3压片成型,然后用筛子筛成20-40目的颗粒,得到最终的ZSM-5分子筛。
2.根据权利要求1所述的制备方法,其特征在于,在Step1中,所述硅源选用的是硅溶胶、正硅酸乙酯或白炭黑。
3.根据权利要求1所述的制备方法,其特征在于,在Step1中,所述模板剂选用的是四丙基溴化铵、四丙基氢氧化铵或正丁胺。
4.根据权利要求1所述的制备方法,其特征在于,在Step1中,所述碱源选用的是乙胺或氢氧化钠。
5.根据权利要求1所述的制备方法,其特征在于,在Step1中,所述硼源选用的是硼酸或氧化硼。
6.根据权利要求1所述的制备方法,其特征在于,在Step1中,所述晶种溶液是由正硅酸乙酯、四丙基氢氧化铵和去离子水以5:7:3的质量比混合并于80℃下老化72h得到的,晶种的粒径分布在10-100nm范围内。
7.根据权利要求1所述的制备方法,其特征在于,在Step2中,所述处理液中NaOH的浓度为0.2mol/L,Al(NO3)3的浓度为26.6μmol/L。
8.根据权利要求1所述的制备方法,其特征在于,在Step3中,所述NH4Cl溶液的浓度为0.4mol/L。
9.根据权利要求1所述的制备方法,其特征在于,在Step1、Step2和Step3中,所述烘干均是在空气氛围下于80℃烘干。
10.一种对低碳烯烃具有较高的选择性的催化剂,其特征在于,该催化剂由权利要求1至9任意一项所述的制备方法制备而来,其具有介孔结构和弱酸中心。
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