CN106082268A - 一种高岭土球制备可直接流化多级结构分子筛的方法 - Google Patents
一种高岭土球制备可直接流化多级结构分子筛的方法 Download PDFInfo
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Abstract
一种高岭土球制备可直接流化多级结构分子筛的方法,先将高岭土高温焙烧,测定高岭土内氧化铝和氧化硅的含量,然后用喷雾干燥法制备高岭土球,计算高岭土球的加入量,将高岭土球,外加硅源、磷酸、模板剂以及水混合形成晶化原液,再将搅拌均匀的晶化原液转移到以四氟乙烯为内衬的水热釜中,老化,老化后将水热釜放入均相反应器中进行晶化,然后将晶化后的溶液冷却,取出进行洗涤离心处理,得到的固液混合物经过过滤、洗涤、烘干,焙烧除去模板剂,得到多级结构分子筛,该分子筛能很好的抑制异丁烯在孔道中的生成与扩散,更大分子的异构烃以及芳烃将受到更加严重扩散限制,同时介孔的存在减少了目的产物低碳烯烃尤其是丙烯的扩散阻力。
Description
技术领域
本发明属于甲醇制烯烃的催化剂制备技术领域,具体涉及一种高岭土球制备可直接流化多级结构分子筛的方法。
背景技术
甲醇制烯烃工艺的催化剂以ZMS-5为主,结构为MFI型的二维交叉孔道,孔径大小分别为和由于其孔道的良好的择形效应及可控的酸性,被广泛应用于甲醇制芳烃、芳烃转化及其他分子筛催化过程当中,良好的实用价值和简易的合成方法使得ZSM-5成为目前研究最为深入的一种沸石。由于酸性过强,人们将其改性后应用于MTO过程当中并没有得到的非常好的低碳烯烃选择性,产物中大量的C5~C10烃(4.4~16.2%)及芳烃(5.7~28.6%)。
目前的研究普遍认为其0.55nm的孔道对于低碳烯烃(乙烯、丙烯)的择形效果不够,无法抑制大分子烃类的生成。因此,小孔分子筛SAPO逐渐成为甲醇制烯烃过程的研究热点。用于MTO反应SAPO类分子筛,得到的SAPO-34与SAPO-18分子筛分别为CHA和AEI结构,晶体结构为三方晶系和六方晶系,都是由硅、铝、磷三种元素与氧原子组成的XO4四面体构成的六元环结构,但是六元环的排列方式的不同,六元环垂直于环面的排列方式决定了分子筛的种类和六元环排列形成的笼型结构。SAPO-34的椭球笼型结构的大小为1.1*0.65nm,并通过侧面的6个八元环形成三围的孔道结构,该八元环的孔径即为SAPO-34分子筛的微孔孔道大小为相比与SAPO-34,SAPO-18笼型结构要更大一些达到1.1*0.92nm,其孔径大小与SAPO-34分子筛相同,小分子正构烃类可以自由进出SAPO-34与SAPO-18的微孔孔道。
专利CN03121112.7以及CN200710043956.X公开了Na改性后的ZSM-5催化剂用于甲醇转化反应,得到99%的甲醇转化率,丙烯选择性为38~49%,然而并未提及催化剂失活的问题。
专利CN201310462721.X提出了采用金属Ca,Mg,La,Ru和Na等对分子筛ZSM-5,SAPO,USY和Beta等进行改性,以减少强酸性位点上的积碳,与改性前相比催化剂的稳定性有显著提高,稳定性最佳的Ru改性分子筛反应12h后丙烯选择性仍能达到40%,然而采用贵金属改性催化剂成本较高,不适于大规模生产使用。
专利CN201110293745.8采用两种金属氧化物对分子筛进行改性,一种氧化物选自Fe、Co、Mo等,另一种选自Ti、V、Cr等氧化物,效果最佳的0.2%Zn0.5%V0.2%Mo-HZSM-5在甲醇完全转化的情况下选择性达40%,但是催化剂制备过程较为繁琐,同时催化剂积碳问题仍未得到解决。
上述报道的专利文献中,虽然采用了各种方法对分子筛进行改性,但是由于SAPO分子筛本身孔结构的特点,采用负载其他金属的方法并不能从根本上解决扩散阻力的问题,分子筛的微孔结构对目的产物低碳烯烃的扩散阻力很大,导致低碳烯烃进一步反应生成积碳,因此整个反应过程中原料甲醇的利用率较差,催化剂易失活,目的产物丙烯选择性低,不符合绿色化学的要求。
发明内容
为了克服上述现有技术的缺点,本发明的目的在于提供一种高岭土球制备可直接流化多级结构分子筛的方法,该分子筛包含介孔和微孔,使所制备的催化剂不易失活,稳定性好,能很好的抑制异丁烯在孔道中的生成与扩散,更大分子的异构烃以及芳烃将受到更加严重扩散限制,同时介孔的存在减少了目的产物低碳烯烃尤其是丙烯的扩散阻力。
为了达到上述目的,本发明采取的技术方案为:
一种高岭土球制备可直接流化多级结构分子筛的方法,包括如下步骤:
1)将高岭土在550℃~1100℃高温焙烧,使用XRF测定高岭土内氧化铝Al2O3和氧化硅SiO2的含量;
2)用喷雾干燥法制备高岭土球;
3)以步骤1)中得到的结果为依据来计算高岭土球的加入量,将高岭土球,外加硅源、磷酸、模板剂以及水混合形成晶化原液,模板剂为三乙胺TEA或者吗啡啉,按照测定高岭土Al2O3的含量计算,磷酸按照P2O5计算,P2O5:Al2O3=1:2~3:1,TEA或吗啡啉:Al2O3=2:1~6:1,H2O:Al2O3=60:1~100:1,外加硅源使晶化原液SiO2:Al2O3=1:2~3:1,搅拌0.5h以上;
4)将搅拌均匀的晶化原液转移到以四氟乙烯为内衬的水热釜中,老化0-24h,老化后将水热釜放入均相反应器中进行晶化,晶化温度为160℃-220℃,均相反应器的压力为自生压力,晶化时间为10-48h;
5)将晶化后的溶液冷却,取出进行洗涤离心处理,直至上清液的pH=6-8;
6)对步骤5)得到的固液混合物经过过滤、洗涤、烘干,在400-800℃焙烧除去模板剂,得到多级结构分子筛。
本发明的有益效果为:
在固定流化床反应器上对合成的多级结构分子筛进行反应表征,以甲醇作为原料,水为稀释剂,水:甲醇=1:1,反应温度为450℃,压力为常压,甲醇质量空速为1.5h-1,将产物中的气相组成,通过气相色谱进行分析,得到了多级结构分子筛在甲醇制烯烃过程中的反应性能。
(1)催化剂的甲醇单程转化率以及C2 =-C4 =总烯烃单程选择性高,反应60min后可分别达到100%和85%,乙烯丙烯单程选择性可达65%,丙烯单程选择性可达55%,副产物丙烷的选择性低,且催化剂抗积碳性能较好,在反应120min后甲醇单程转化率以及总烯烃单程选择性仍分别可达83%和76%。
(2)催化剂诱导期短,很快达到最佳转化率和选择性,且选择性高,低附加值副产物(主要是丙烷等)少,寿命长。
(3)催化剂可再生性好,通入空气,在500℃下烧炭3h,催化剂的甲醇单程转化率以及C2 =-C4 =总烯烃单程选择性高,反应60min后可分别达到100%和85%以上,乙烯丙烯单程选择性可达65%,丙烯单程选择性可达55%。
具体实施方式
下面结合具体实施例对本发明作详细描述。
实施例1
以高岭土球为硅源和铝源的多级结构分子筛的合成采用水热法,以30wt%硅溶胶为外加硅源,不外加铝源;以正磷酸溶液为合成原料中的磷源;以三乙胺为分子筛合成的模板剂。
一种高岭土球制备可直接流化多级结构分子筛的方法,包括如下步骤:
1)将高岭土在850℃高温焙烧,使用XRF测定高岭土内氧化铝Al2O3和氧化硅SiO2的含量;
2)用喷雾干燥法制备高岭土球;
3)以步骤1)中得到的结果为依据来计算高岭土球的加入量,将高岭土球,外加硅源、磷酸、模板剂、以及水混合形成晶化原液,模板剂为三乙胺TEA,按照测定高岭土Al2O3的含量计算,磷酸按照P2O5计算,P2O5:Al2O3=2:1,TEA:Al2O3=2:1,H2O:Al2O3=90:1,外加硅源使晶化原液SiO2:Al2O3=1:1,搅拌0.5h;
4)将搅拌均匀的晶化原液转移到以四氟乙烯为内衬的水热釜中,老化12h,老化后将水热釜放入均相反应器中进行晶化,晶化温度为190℃,均相反应器的压力为自生压力,晶化时间为48h;
5)将晶化后的溶液冷却,取出进行洗涤离心处理,直至上清液的pH=7;
6)对步骤5)得到的固液混合物经过过滤、洗涤、烘干,在600℃焙烧除去模板剂,得到多级结构分子筛。
本实施例的效果:在固定流化床反应器上对合成的多级结构分子筛进行反应表征,以甲醇作为原料,水为稀释剂,水:甲醇=1:1,反应温度为450℃,压力为常压,甲醇质量空速为1.5h-1,将产物中的气相组成,通过气相色谱进行分析,得到了本实施例催化剂在甲醇制烯烃过程中的反应性能,反应200min后对催化剂进行再生,再生温度为500℃,在空气中烧炭再生2h。该催化剂的活性评价结果见表1。
比较例1
以30wt%的硅溶胶和拟薄水铝石为硅源和铝源的SAPO分子筛的合成采用水热法,以正磷酸溶液为合成原料中的磷源,以三乙胺为模板剂,包括如下步骤:
1)将30wt%的硅溶胶、拟薄水铝石、磷酸、三乙胺TEA以及水溶液混合形成晶化原液,磷酸按照P2O5计算,SiO2:Al2O3=1:1,P2O5:Al2O3=2:1,TEA:Al2O3=2:1,H2O:Al2O3=90:1,搅拌0.5h;
2)将搅拌均匀的晶化原液转移到以四氟乙烯为内衬的水热釜中,老化12h,老化后将水热釜放入均相反应器中进行晶化,晶化温度为190℃,均相反应器的压力为自生压力,晶化时间为48h;
3)将晶化后的溶液冷却,取出进行洗涤离心处理,直至上清液的pH=7;
4)对步骤3)得到的固液混合物经过过滤、洗涤、烘干,在600℃焙烧除去模板剂,得到多级结构分子筛。
本比较例的效果:给多级结构分子筛加入硅溶胶和惰性载体制备浆液,浆液的组成为分子筛25wt%,硅溶胶40wt%,惰性载体35wt%进行喷雾造粒。
反应条件同实施实例1
结果在下面表1中进行比较。
表1
通过比较得出如下结论
(1)高岭土制备的可直接流化多级结构分子筛催化剂各方面指标均优于传统催化剂,其甲醇单程转化率以及C2 =-C4 =总烯烃单程选择性高,反应60min后可分别达到100%和85%,乙烯丙烯单程选择性可达65%,丙烯单程选择性可达55%,副产物丙烷的选择性低,且催化剂抗积碳性能较好,在反应120min后甲醇单程转化率以及总烯烃单程选择性仍分别可达83%和76%。
(2)催化剂诱导期短,很快达到最佳转化率和选择性,且选择性高,低附加值副产物(主要是丙烷等)少,寿命长。
(3)催化剂可再生性好,通入空气,在500℃下烧炭3h,催化剂的甲醇单程转化率以及C2 =-C4 =总烯烃单程选择性高,反应60min后可分别达到100%和85%以上,乙烯丙烯单程选择性可达65%,丙烯单程选择性可达55%。
实施例2
以高岭土球为硅源和铝源多级结构分子筛的合成采用水热法,以30wt%硅溶胶为外加硅源,不外加铝源;以正磷酸溶液为合成原料中的磷源;以三乙胺为模板剂,调整外加硅源含量,得到晶化原液SiO2:Al2O3=1:2;1:1;2:1;3:1,其余步骤同实施例1。
实施例2的效果:反应条件同实施实例1,该催化剂的活性评价结果见表2
表2
实施例3
以高岭土球为硅源和铝源多级结构分子筛的合成采用水热法,以30wt%硅溶胶为外加硅源,不外加铝源;以正磷酸溶液为合成原料中的磷源,以吗啡啉为模板剂,调整外加硅源含量,得到晶化原液SiO2:Al2O3=1:2;1:1;2:1;3:1;其余步骤同实施例1。
实施例3的效果:反应条件同实施实例1,该催化剂的活性评价结果见表3
表3
实施例4
以高岭土球为硅源和铝源多级结构分子筛的合成采用水热法,以30wt%硅溶胶为外加硅源,不外加铝源,以正磷酸溶液为合成原料中的磷源,以三乙胺为模板剂,调整外加磷酸含量,晶化原液P2O5:Al2O3=1:2;1:1;2:1;3:1,其余步骤同实施例1。
实施例4的效果:反应条件同实施实例1,该催化剂的活性评价结果见表4
表4
实施例5
以高岭土球为硅源和铝源多级结构分子筛的合成采用水热法,以30wt%硅溶胶为外加硅源,不外加铝源,以正磷酸溶液为合成原料中的磷源,以三乙胺为模板剂,调整外加模板剂的含量,TEA:Al2O3=1:2;1:1;2:1;3:1,其余步骤同实施例1。
本实施例的效果:反应条件同实施实例1。该催化剂的活性评价结果见表5
表5
实施例6
以高岭土球为硅源和铝源多级结构分子筛的合成采用水热法,以30wt%硅溶胶为外加硅源,不外加铝源,以正磷酸溶液为合成原料中的磷源;以三乙胺为模板剂,调整外加水溶液的含量,得到,H2O:Al2O3=60:1;80:1;90:1;100:1其余步骤同实施例1。
本实施例的效果:反应条件同实施实例1,该催化剂的活性评价结果见表6
表6
实施例7
以高岭土球为硅源和铝源多级结构分子筛的合成采用水热法,以30wt%硅溶胶为外加硅源,不外加铝源,以正磷酸溶液为合成原料中的磷源,以三乙胺为模板剂,改变晶化前的老化时间,分别进行0h,12h,24h老化,其余步骤同实施例1。
本实施例的效果:反应条件同实施实例1,该催化剂的活性评价结果见表7
表7
实施例8
以高岭土球为硅源和铝源多级结构分子筛的合成采用水热法,以30wt%硅溶胶为外加硅源,不外加铝源,以正磷酸溶液为合成原料中的磷源,以三乙胺为模板剂。改变晶化温度,分别在170℃,190℃,200℃,210℃进行晶化,其余步骤同实施例1。
本实施例的效果:反应条件同实施实例1。该催化剂的活性评价结果见表8
表8
实施例9
以高岭土球为硅源和铝源多级结构分子筛的合成采用水热法,以30wt%硅溶胶为外加硅源,不外加铝源,以正磷酸溶液为合成原料中的磷源,以三乙胺为模板剂,改变晶化时间,分别进行10h,12h,24h,48h晶化,其余步骤同实施例1。
本实施例的效果:反应条件同实施实例1。该催化剂的活性评价结果见表9
表9
Claims (2)
1.一种高岭土球制备可直接流化多级结构分子筛的方法,其特征在于,包括如下步骤:
1)将高岭土在550℃~1100℃高温焙烧,使用XRF测定高岭土内氧化铝Al2O3和氧化硅SiO2的含量;
2)用喷雾干燥法制备高岭土球;
3)以步骤1)中得到的结果为依据来计算高岭土球的加入量,将高岭土球,外加硅源、磷酸、模板剂以及水混合形成晶化原液,模板剂为三乙胺TEA或者吗啡啉,按照测定高岭土Al2O3的含量计算,磷酸按照P2O5计算,P2O5:Al2O3=1:2~3:1,TEA或吗啡啉:Al2O3=2:1~6:1,H2O:Al2O3=60:1~100:1,外加硅源使晶化原液SiO2:Al2O3=1:2~3:1,搅拌0.5h以上;
4)将搅拌均匀的晶化原液转移到以四氟乙烯为内衬的水热釜中,老化0-24h,老化后将水热釜放入均相反应器中进行晶化,晶化温度为160℃-220℃,均相反应器的压力为自生压力,晶化时间为10-48h;
5)将晶化后的溶液冷却,取出进行洗涤离心处理,直至上清液的pH=6-8;
6)对步骤5)得到的固液混合物经过过滤、洗涤、烘干,在400-800℃焙烧除去模板剂,得到多级结构分子筛。
2.根据权利要求1所述的一种高岭土球制备可直接流化多级结构分子筛的方法,其特征在于,包括如下步骤:
1)将高岭土在850℃高温焙烧,使用XRF测定高岭土内氧化铝Al2O3和氧化硅SiO2的含量;
2)用喷雾干燥法制备高岭土球;
3)以步骤1)中得到的结果为依据来计算高岭土球的加入量,将高岭土球,外加硅源、磷酸、模板剂、以及水混合形成晶化原液,模板剂为三乙胺TEA,按照测定高岭土Al2O3的含量计算,磷酸按照P2O5计算,P2O5:Al2O3=2:1,TEA:Al2O3=2:1,H2O:Al2O3=90:1,外加硅源使晶化原液SiO2:Al2O3=1:1,搅拌0.5h;
4)将搅拌均匀的晶化原液转移到以四氟乙烯为内衬的水热釜中,老化12h,老化后将水热釜放入均相反应器中进行晶化,晶化温度为190℃,均相反应器的压力为自生压力,晶化时间为48h;
5)将晶化后的溶液冷却,取出进行洗涤离心处理,直至上清液的pH=7;
6)对步骤5)得到的固液混合物经过过滤、洗涤、烘干,在600℃焙烧除去模板剂,得到多级结构分子筛。
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