孔口催化促进双功能催化剂上合成气制异构烷烃

doi:10.1016/S1872-2067(20)63770-6

催化学报 ›› 2021, Vol. 42 ›› Issue (12): 2197-2205.DOI: 10.1016/S1872-2067(20)63770-6

孔口催化促进双功能催化剂上合成气制异构烷烃

汪孟恒^†, 韩瑶瑶^†, 刘素含, 刘志铭, 安冬丽, 张智强, 成康^*(), 张庆红, 王野^#()

厦门大学化学化工学院, 固体表面物理化学国家重点实验室, 能源材料化学协同创新中心, 醇醚酯化工清洁生产国家工程实验室, 福建厦门361005

收稿日期:2020-12-29 接受日期:2020-12-29 出版日期:2021-12-18 发布日期:2021-01-31
通讯作者: 成康,王野
作者简介:第一联系人：
^†共同第一作者.
基金资助:
科技部国家重点研究开发项目(2020YFB0606401);科技部国家重点研究开发项目(2019YFE0104400);国家自然科学基金(91945301);国家自然科学基金(22072120);国家自然科学基金(21972116);国家自然科学基金(22008203)

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

Mengheng Wang^†, Yaoyao Han^†, Suhan Liu, Zhiming Liu, Dongli An, Zhiqiang Zhang, Kang Cheng^*(), Qinghong Zhang, Ye Wang^#()

State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, National Engineering Laboratory for Green Chemical Productions of Alcohols, Ethers and Esters, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, Fujian, China

Received:2020-12-29 Accepted:2020-12-29 Online:2021-12-18 Published:2021-01-31
Contact: Kang Cheng,Ye Wang
About author:# E-mail: wangye@xmu.edu.cn
* E-mail: kangcheng@xmu.edu.cn;
First author contact:
^†These authors contributed equally to this work.
Supported by:
National Key Research and Development Program of Ministry of Science and Technology(2020YFB0606401);National Key Research and Development Program of Ministry of Science and Technology(2019YFE0104400);National Natural Science Foundation of China(91945301);National Natural Science Foundation of China(22072120);National Natural Science Foundation of China(21972116);National Natural Science Foundation of China(22008203)

摘要/Abstract

摘要：

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ZnAlO_x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ZnAlO_x/SAPO-11催化剂上异构烷烃与正构烷烃的比例(C0 iso/C0 n)达到13. 相较于ZnAlO_x/SAPO-11, ZnAlO_x/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ZnAlO_x/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C0 iso/C0 n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ZnAlO_x/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ZnAlO_x/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ZnAlO_x/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.

关键词: 孔口催化, 择形催化, 双功能, 合成气, 汽油

Abstract:

Recent studies confirm that the emerging bifunctional catalysts consisting of metal oxide and zeolites 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 investigated. Herein, three one-dimensional SAPO zeolites with diverse micropore sizes were synthesized and assembled with ZnAlO_x with spinel structure. It was found that ZnAlO_x/SAPO-41 and ZnAlO_x/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 ZnAlO_x/SAPO-11 and Co/H-meso-ZSM-5 was also made in terms of product distribution, activity, and stability.

Key words: Pore-mouth catalysis, Shape-selective catalysis, Bifunction, Syngas, Gasoline

汪孟恒, 韩瑶瑶, 刘素含, 刘志铭, 安冬丽, 张智强, 成康, 张庆红, 王野. 孔口催化促进双功能催化剂上合成气制异构烷烃[J]. 催化学报, 2021, 42(12): 2197-2205.

Mengheng Wang, Yaoyao Han, Suhan Liu, Zhiming Liu, Dongli An, Zhiqiang Zhang, Kang Cheng, Qinghong Zhang, Ye Wang. Pore-mouth catalysis boosting the formation of iso-paraffins from syngas over bifunctional catalysts[J]. Chinese Journal of Catalysis, 2021, 42(12): 2197-2205.

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图/表 7

Fig. 1. PXRD patterns of SAPO-41 (a), SAPO-11 (b) and SAPO-5 (c); SEM imaging of SAPO-41 (d), SAPO-11 (e) and SAPO-5 (f).

Table 1 Physiochemical properties of three SAPO zeolites and AlPO-11 zeolite.

Zeolites	Pore size (nm²)	Topology	Si/(Si + Al + P)^a	Peak_HT^b (°C)	D_acid^c (mmol g^-1)	Morphology^d
SAPO-41	0.41 × 0.53	AFO	0.04	308	0.12	Eight prism, 5 µm
SAPO-11	0.40 × 0.65	AEL	0.06	303	0.23	Cuboid, 1-2 µm
SAPO-5	0.73 × 0.73	AFI	0.03	265	0.15	Hexagonal prism, 2 µm
AlPO-11	0.40 × 0.65	AEL	0	—	0	Needle, 1 µm

Fig. 2. Effects of Brönsted acid sites (a), temperature (b) and pressure (c) on the catalytic behaviors of ZnAlOx/SAPO catalyst in CO hydrogenation. Reaction conditions: Wcat = 1.0 g, H2/CO = 1, P = 2-4 MPa, Fsyngas = 25 mL min-1, T = 350-400 °C, time on stream = 10 h. Catalytic performances in detail are listed in Table S5-S7.

Fig. 3. Effect of pore size of 1D SAPO zeolites on the catalytic behaviors of bifunctional ZnAlOx/SAPO catalysts in CO hydrogenation. Reaction conditions: Wcat = 1.0 g, H2/CO = 1, P = 3 MPa, Fsyngas = 25 mL min-1, T = 350 °C, time on stream = 4 h or 10 h. Catalytic performances in detail are listed in Table S9.

Fig. 4. Comparison of catalytic performance between bifunctional ZnAlOx/SAPO-11 and Co/H-meso-ZSM-5 catalyst in syngas conversion reaction after 10 h of reaction. Reaction conditions for ZnAlOx/SAPO-11: Wcat = 1.0 g, H2/CO = 1, P = 3 MPa, Fsyngas = 25 mL min-1, T = 350 °C, time on stream = 10 h. Reaction conditions for Co/H-meso-ZSM-5: Wcat = 0.5 g, H2/CO = 1, P = 2 MPa, Fsyngas = 20 mL min-1, T = 240 °C, time on stream = 10 h. Catalytic performances in detail are listed in Table S10.

Fig. 5. Comparison of (a) ZnAlOx/SAPO-11 and (b) Co/H-meso-ZSM-5 in syngas conversion. Reaction conditions for ZnAlOx/SAPO-11: Wcat = 1.0 g, H2/CO = 1, P = 3 MPa, Fsyngas = 25 mL min-1, T = 350 °C. Reaction conditions for Co/H-meso-ZSM-5: Wcat = 0.5 g, H2/CO = 1, P = 2 MPa, Fsyngas = 20 mL min-1, T = 240 °C.

Fig. 6. (a) GC-MS analysis of the gaseous product in C4-C6 cut over bifunctional ZnAlOx/SAPO-11 catalyst after 10 h of reaction; (b) Adsorption isotherms of n-butane and iso-butane over SAPO-11; (c) Schematic pore-mouth catalysis mechanism in syngas conversion over ZnAlOx/SAPO-11 catalyst.

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孔口催化促进双功能催化剂上合成气制异构烷烃

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

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