合成气一步法直接制低碳烯烃双功能催化剂研究新进展

皂辉杰; 姚金刚; 刘静; 陈冠益; 易维明; 熊加林

doi:10.19906/j.cnki.JFCT.2022052

合成气一步法直接制低碳烯烃双功能催化剂研究新进展

doi: 10.19906/j.cnki.JFCT.2022052

皂辉杰^{1, 2, 3,},
姚金刚^{1, 2, 3, ,},
刘静^{1, 2, 3, ,},
陈冠益⁴,
易维明^{1, 3},
熊加林⁵

1.
山东理工大学农业工程与食品科学学院, 山东淄博 255000
2.
广东省新能源和可再生能源研究开发与应用重点实验室, 广东广州 510640
3.
山东省清洁能源工程技术研究中心, 山东淄博 255000
4.
天津大学环境科学与工程学院, 天津 300072
5.
华能(浙江)能源开发有限公司玉环分公司, 浙江玉环 317604

基金项目: 国家自然科学基金（52006129，51906129），山东省自然科学基金（ZR2020QE205）和广东省新能源和可再生能源研究开发与应用重点实验室（E039kf0701，E239kf0401）资助

详细信息

通讯作者:
Tel：15695431959，E-mail：yaojingang@sdut.edu.cn

ljing815@tju.edu.cn

中图分类号: O643.3
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出版历程
- 收稿日期: 2022-04-29
- 修回日期: 2022-06-04
- 录用日期: 2022-06-14
- 网络出版日期: 2022-07-11
- 刊出日期: 2023-01-10

New research progress on bifunctional catalysts for one-step direct production of low carbon olefins from syngas

ZAO Hui-jie^{1, 2, 3
,},
YAO Jin-gang^{1, 2, 3
, ,},
LIU Jing^{1, 2, 3
, ,},
CHEN Guan-yi⁴,
YI Wei-ming^{1, 3},
XIONG Jia-lin⁵

1.
School of Agricultural Engineering and Food Science, Shandong University of Technology, Zibo 255000, China
2.
Guangdong Provincial Key Laboratory of New and Renewable Energy Research and Development, Guangzhou 510640, China
3.
Shandong Research Center of Engineering & Technology for Clean Energy, Zibo 255000, China
4.
School of Environmental Science and Engineering, Tianjin University, Tianjin 300072, China
5.
Huaneng (Zhejiang) Energy Development Co., LTD. Yuhuan Branch, Yuhuan 317604, China

Funds: The project was supported by the National Natural Science Foundation of China (52006129, 51906129), Shandong Provincial Natural Science Foundation (ZR2020QE205) and Guangdong Provincial Key Laboratory of New and Renewable Energy Research and Development (E039kf0701, E239kf0401).

摘要

摘要: 以乙烯、丙烯和丁烯为主的低碳烯烃是重要的化工基础原料，由合成气一步法直接催化制取低碳烯烃路线因其流程短、能耗低等优势，已成为非石油路线生产低碳烯烃的主要发展方向，其主要包括经费托合成反应制备低碳烯烃的路线（FTO）和基于金属氧化物/分子筛（OX-ZEO）双功能催化剂体系的路线（SDTO）。本工作综述了近年来在合成气制备低碳烯烃方面的研究进展，重点阐述了OX-ZEO双功能催化剂的设计、不同活性位点的耦合制备方法、催化剂表界面调控对其催化性能的影响，详细解析了H₂/CO比、温度、压力、接触时间等反应条件对SDTO反应的调控机制，概括了现代表征技术在揭示OX-ZEO催化反应机理中的应用，同时总结了OX-ZEO的催化反应机理。最后对OX-ZEO双功能催化路径目前存在的挑战和未来的发展进行了展望。
- 低碳烯烃 /
- 合成气 /
- 费托合成 /
- 双功能催化剂 /
- 反应机理
Abstract: The light olefins, mainly ethylene, propylene and butene, are basic building blocks in chemical industry. The direct conversion of syngas to lower olefins considered as a new significant and attractive process for producing lower olefins from non-petroleum resources, owing to its process simplicity and low energy consumption. The light olefins can be directly produced from syngas via two routes, namely, the Fischer-Tropsch to olefins (FTO) reaction and oxide-zeolite (OX-ZEO) bifunctional catalysis strategy (SDTO). This paper mainly reviews recent developments of SDTO, with emphasis on the effects of catalyst design, catalyst preparation and interphase renovation on reactivity. The targeting control of operating parameters such as H₂/CO ratio, temperature, pressure and contact for higher production of light olefins has also been clarified. Applications of new in situ, in real-time techniques to identify the structure-function relationship and the reaction mechanism are summarized. The recent progress including the applications of new in situ, real-time techniques to identify the structure-function relationship and the reaction mechanism are reviewed in detail. With this, the authors put forward insights into significant promising tendencies and confronting challenges in the strategy of OX-ZEO.
- light olefin /
- syngas /
- Fischer-Tropsch synthesis /
- bifunctional catalyst /
- reaction mechanism

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图 1 合成气转化制备低碳烯烃路径示意图

Figure 1 Various routes for the production of lower olefins via syngas

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图 2 预测产物分布的ASF模型^[8]

Figure 2 ASF model for predicting the distribution of the product^[8]

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图 3 碳氢化合物在含有不同沸石的复合催化剂上的分布^[6]

Figure 3 Hydrocarbon distribution over composite catalysts containing different zeolites^[6](with permission from Science Publications)

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图 4 OX-ZEO双功能催化剂的催化性能^[6]

Figure 4 Performance of the bifunctional OX-ZEO catalyst in the conversion of syngas to olefins^[6](with permission from Science Publications)

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图 5 金属粒径对催化效果的影响^[47]

Figure 5 Effect of metal particle size on the catalytic effect^[47](with permission from RSC Publications)

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图 6 煅烧过的SAPO-34的扫描电子显微图^[62]

Figure 6 SEM images of the calcined zeotype^[62](with permission from Fuel Publications)

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图 7 金属氧化物Zn-ZrO₂和分子筛SSZ-13的接近程度对双功能催化剂的催化行为的影响^[29]

Figure 7 Effects of the proximity of bifunctional OX-ZEO catalysts on syngas conversion^[29](with permission from RSC Publications)

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图 8 双功能催化剂表面合成气制备低碳烯烃的反应路径^[29]

Figure 8 Reaction pathways for the preparation of low carbon olefins from syngas on bifunctional catalyst surfaces^[29]

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表 1 基于OX/ZEO体系的合成气直接制取低碳烯烃

Table 1 Summary of direct production of low carbon olefins from syngas over OX/ZEO catalysts

Catalyst	CO conv./%	Selectivity of hydrocarbons^h /C%
Catalyst	CO conv./%	CH₄	${\rm{C}}_2^= - {\rm{C}}_4^= $	C_{5 +}	CH₃OH	DME
ZnCr₂O₄	2.4^a	1.6	4	1.1	47	26
ZnO-ZrO₂	2.0^b	8.1	11	4.9	66	−
ZnAl₂O₄	3.1^c	8.0	0.8	0.2	14	77
ZnCr₂O₄/SAPO-34	11^d	8.0	64	3.0	−	−
ZnO-ZrO₂/SAPO-34	7.0^e	4.0	69	2.0	−	−
ZnAl₂O₄/SAPO-34	24^f	3.5	80	2.4	−	−
ZnZrO₄/SSZ-13	29^g	2.0	77	3.0	−	−
ZnCrO_x/SSZ-13	20ⁱ	6.0	72	7.5	−	−
ZnAlO_x/SAPO-18	21^j	3.0	71	10	−	−
^a,c,d H₂/CO=2，400 ℃，3.0 MPa，GHSV =4800 mL/(h·g_cat)；^b,e H₂/CO=2，400 ℃，1.0 MPa，GHSV =4800 mL/(h·g_cat)；ⁱ H₂/CO=2， 400 ℃，1.0 MPa，GHSV =6000 mL/(h·g_cat)；^j H₂/CO=2，400 ℃，3.0 MPa，GHSV =3000 mL/(h·g_cat)；^hProduct obtained based on C mole calculations, excluding CO₂

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表 2 OX/ZEO催化反应条件对合成气催化转化的影响

Table 2 Influence of different reaction conditions on syngas conversion over OX/ZEO catalysts

Metal oxide	Zeolite	Topology	CO conv. /%	Light olefin selectivity /%^h	Selectivity of hydrocarbons^h/C%			CO₂ sel. /%
Metal oxide	Zeolite	Topology	CO conv. /%	Light olefin selectivity /%^h	CH₄	${\rm{C}}^0_{2-4} $	C_5–11	CO₂ sel. /%
ZnCrO_x	MASPO	CHA	17^a	80	6	13	11	50
ZnZrO_x	SAPO-34	TON	9.5^b	63	6	29	2.2	−
ZnZrO_x	SSZ-13	CHA	23^c	75	< 4	15	< 4	−
ZnCrO_x	AlPO-18	AEI	16.6^d	43	< 2	< 2	5	47
ZnAl₂O₃	SAPO-34	CHA	6.12^e	54	10.42	31.48	14.5	47
ZnCrO_x	H-SSZ-13	CHA	20.9^f	70.8	6	16.9	6.3	48
^a ZnCrO_x/Zeolite =1∶1.4 (%)，H₂/CO=1.5，400 ℃，2.5 MPa，GHSV =4800 mL/(h·g_cat)；^b ZnZrO_x/Zeolite =1∶1.0 (%)，Zn /ZrO₂=1∶4.0 (%)，H₂/CO=1.0，400 ℃，1.5 MPa；^c ZnZrO_x/ Zeolite =1∶1.0 (%)，Zn /ZrO₂=1∶16 (%)，H₂/CO=2.0，400 ℃，1.0 MPa；^d ZnCrO_x/ Zeolite =1∶1.0 (%)，H₂/CO=1.0，390 ℃，4.0 MPa，GHSV =3600 mL/(h·g_cat)；^e ZnCrO_x/ Zeolite =1∶2.0 (%)，Zn/Al₂O₃=1∶2 (%)，H₂/CO=2.0，350 ℃，2.0 MPa，GHSV =4800 mL/(h·g_cat)；^f ZnCrO_x/ Zeolite = 1∶2.0 (%)，H₂/CO=3.0，380 ℃，4.0 MPa，GHSV =6000 mL/(h·g_cat)；^hProduct obtained based on C mole calculations, excluding CO₂

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