孔口催化促进双功能催化剂上合成气制异构烷烃

随着我国国民经济的快速发展,碳基能源需求量在不断上升,能源供需矛盾日益凸显.在可再生能源替代传统化石能源之前,着手开发合成气催化转化补充石油路线获得油料和大宗化学品成为形势所需,其中的关键点之一是高效催化剂的开发以实现对产物选择性的精准调控.近年来,利用氧化物/分子筛双功能催化剂将甲醇合成和C–C偶联有效集成的催化体系开辟了合成气转化乃至C1转化的新路径.随着合成气直接制低碳烯烃和芳烃等一系列研究取得重大进展,合成气定向转化为高品质汽油作为C1化学领域另一极具挑战性的研究课题也受到了科研工作者们的广泛关注.然而,目前对氧化物/分子筛双功能催化剂体系中异构烷烃的形成机理尚不明确,与传统的分子筛负载费托合成催化剂之间的性能差异还缺乏系统的研究.基于此,本文利用水热合成法制备了三种具有不同微孔尺寸的一维SAPO分子筛(SAPO-41、SAPO-11和SAPO-5),分别与尖晶石结构的ZnAlOx氧化物耦合,并将其应用于合成气制汽油反应中.结果表明,以具有中等微孔尺寸的SAPO-41和SAPO-11分子筛作为C–C偶联功能组分时,合成气直接转化产物中C5–C11选择性分别高达71％和79％,且该馏分以异构烷烃产物为主.其中ZnAlOx/SAPO-11催化剂上异构烷烃与正构烷烃的比例(C0iso/C0n)达到13.相较于ZnAlOx/SAPO-11,ZnA-lOx/SAPO-41催化剂在反应4 h后迅速失活,反应稳定性较差.在优化ZnAlOx/SAPO-11催化剂性能后,分别从产物分布、活性和稳定性三方面入手,将其与经典的Co/H-meso-ZSM-5催化剂进行对比分析.结果表明,Co/H-meso-ZSM-5在低温下仍具有较强的CO活化能力,产物中C5–C11选择性可达70％,但C0iso/C0n仅为2.3.此外,由于钴基催化剂的加氢能力较强,甲烷选择性较高.在稳定性方面,虽然二者均有不同程度的失活,但ZnAlOx/SAPO-11催化剂在反应100 h后,C5–C11选择性依然保持在75％左右,而Co/H-meso-ZSM-5上C5–C11选择性降至64％.通过对ZnAlOx/SAPO-11催化剂上产物的细致分析,发现异构烷烃以单支链的异构体为主.结合正丁烷和异丁烷的等温吸附实验以及的动力学尺寸,推断异构烷烃的形成遵循孔口催化机理,即线性烃类的异构化只能在SAPO-11分子筛的孔口附近发生.生成单支链碳氢化合物是孔口催化的一个特征.由于单支链烷烃相对于双支链烷烃不易裂解,因而生成的单支链C5–C11异构烷烃在ZnAlOx/SAPO-11催化剂上稳定存在,抑制了裂解副反应的发生.综上所述,本文发展了一类氧化物/分子筛双功能催化剂用于转化合成气直接制C5–C11异构烷烃,证实了异构烷烃的生成遵循孔口催化机理,是孔口催化在合成气转化中的应用案例.同时本文系统比较了其与传统的分子筛负载费托合成催化剂之间的性能差异,为设计双功能催化剂实现特定目标产物的选择性合成提供了研究思路.

Pore-mouth catalysis boosting the formation of iso-paraffins from syngas over bifunctional catalysts

Recent studies confirm that the emerging bifunctional catalysts consisting of metal oxide and zeo-lites can directly convert syngas into high-quality gasoline, however, the formation mechanism of iso-paraffins and the difference with the conventional FT/zeolite catalyst have not been investigat-ed. Herein, three one-dimensional SAPO zeolites with diverse micropore sizes were synthesized and assembled with ZnAlOx with spinel structure. It was found that ZnAlOx/SAPO-41 and ZnA-lOx/SAPO-11 with medium micropore sizes favored the formation of C5–C11 hydrocarbons with a high content of iso-paraffins. The characterizations pointed out that the formation of iso-paraffins over SAPO-11 followed a pore-mouth catalysis mechanism, which means the isomerization of linear hydrocarbons can only take place near the pore mouth region of zeolites. This mechanism only allows the formation of mono-branched iso-paraffins in the C5–C11 range, which are less prone to be cracked than their di-branched isomers. A careful comparative analysis between ZnAlOx/SAPO-11 and Co/H-meso-ZSM-5 was also made in terms of product distribution, activity, and stability.