调控Co2C局域浸润环境实现高碳效合成气直接制烯烃

doi:10.1016/S1872-2067(23)64410-9

催化学报 ›› 2023, Vol. 48: 150-163.DOI: 10.1016/S1872-2067(23)64410-9

调控Co₂C局域浸润环境实现高碳效合成气直接制烯烃

刘培功^a, 林铁军^a^,^b^,^*(), 郭磊^a, 刘晓哲^b^,^c, 龚坤^b^,^c, 尧泰真^b^,^c, 安芸蕾^b, 钟良枢^a^,^b^,^*()

^a上海科技大学物质科学与技术学院, 上海 201210
^b中国科学院上海高等研究院, 低碳转化科学与工程重点实验室, 上海 201210
^c中国科学院大学, 北京 100049

收稿日期:2022-11-26 接受日期:2023-01-19 出版日期:2023-05-18 发布日期:2023-04-20
通讯作者: * 电话: (021)20608002; 传真: (021)20350867; 电子信箱: lintj@sari.ac.cn (林铁军),zhongls@sari.ac.cn (钟良枢)
基金资助:
国家自然科学基金(91945301);国家自然科学基金(U22B20136);国家自然科学基金(22072177);上海市自然科学基金(21ZR1471700);上海市自然科学基金(22JC1404200);上海市学术带头人计划(20XD1404000);中国科学院战略先导(XDA21020600);中国科学院青年创新促进会

Tuning cobalt carbide wettability environment for Fischer-Tropsch to olefins with high carbon efficiency

Peigong Liu^a, Tiejun Lin^a^,^b^,^*(), Lei Guo^a, Xiaozhe Liu^b^,^c, Kun Gong^b^,^c, Taizhen Yao^b^,^c, Yunlei An^b, Liangshu Zhong^a^,^b^,^*()

^aSchool of Physical Science and Technology, ShanghaiTech University, Shanghai 201210, China
^bCAS Key Laboratory of Low-Carbon Conversion Science and Engineering, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai 201210, China
^cUniversity of Chinese Academy of Sciences, Beijing 100049, China

Received:2022-11-26 Accepted:2023-01-19 Online:2023-05-18 Published:2023-04-20
Contact: * E-mail: lintj@sari.ac.cn (T. Lin), zhongls@sari.ac.cn (L. Zhong).
Supported by:
National Natural Science Foundation of China(91945301);National Natural Science Foundation of China(U22B20136);National Natural Science Foundation of China(22072177);Natural Science Foundation of Shanghai(21ZR1471700);Natural Science Foundation of Shanghai(22JC1404200);Program of Shanghai Academic/Technology Research Leader(20XD1404000);“Transformational Technologies for Clean Energy and Demonstration”, Strategic Priority Research Program of the Chinese Academy of Sciences(XDA21020600);Youth Innovation Promotion Association of CAS

摘要/Abstract

摘要：

合成气转化是实现煤、天然气、生物质、固体废弃物及CO₂等非石油含碳资源清洁高效利用的关键过程, 可合成多种清洁液体燃料和高附加值化学品, 如汽油、柴油、航空煤油、固体石蜡、烯烃、芳烃和含氧化合物等. 其中, 合成气直接制烯烃(STO)具有流程短、能耗低和经济性高等优点, 备受学术界和工业界关注. 近年来, 合成气直接制烯烃取得了突破性进展, 发展了基于氧化物-分子筛的双功能路线法以及改性费托路线法. 然而, 由于目前STO体系所使用的氧化物或者碳化物活性相同时也是水煤气变换(WGS)活性位点, 导致反应过程产生30%-50%的CO₂副产物, 造成较低的碳原子利用效率和烯烃收率, 以及尾气产品分离能耗的增加. 如何通过催化剂界面和局域环境的调控, 创新反应路径, 提高烯烃选择性和收率, 降低C1副产物选择性已成为重大挑战.
本文提出通过发展界面浸润性调控策略, 将CoMnAl复合氧化物(CMA)衍生的Co₂C活性相与疏水SiO₂进行一定尺度的物理耦合, 能够将CO₂选择性从47.8%降到16.8%, 同时催化剂的活性提高30%, 总产物中烯烃选择性也提高了~65%, 体现出较高的碳效. FI-IR光谱和接触角测试结果表明, 疏水基团成功引入到SiO₂载体上, 并且通过粉末混合的方式获得了同样具备疏水特性的CoMnAl复合催化剂(CMASc). 热重(TG-DTG)结果表明, 即使样品经过300 °C的高温处理, 其疏水性仍然能得到保持. X射线衍射(XRD)和高分辨率透射电镜(HRTEM)表征结果表明, 复合氧化物的活性中心仍是棱柱状Co₂C. 进一步表征和探针实验解释了催化剂浸润性调变对Co₂C基催化剂FTO性能的影响. CO/H₂O-TPSR-MS实验表明, 往体系中引入H₂O蒸气, CMASc催化剂产生的CO₂信号强度远低于单独CMA催化剂的. CO/H₂-TPSR-MS实验结果表明, 在相同的温度下, CMASc催化剂上产生的H₂O信号强度高于CMA, 而相应的CO₂信号强度则要低很多. 在250-400 °C, 将产生的CO₂信号峰面积进行积分, 发现CMA产生的CO₂浓度是CMASc的2.3倍. 利用固定床开展CO/H₂和CO/H₂O探针切换实验, 结果表明, 在典型FTO反应条件下引入水蒸气到CMA催化剂体系后, CO转化率和尾气H₂/CO比大幅度提高, 而CMASc上则出现相反趋势. 这些实验证实了H₂O分子容易吸附在CMA上发生WGS反应, 而在Co₂C活性位界面构建局域疏水环境有利于水分子快速转移, 并防止其再次吸附.
利用CO-DRIFTS和烯烃-H₂脉冲实验研究活性和烯烃选择性提高的原因. 相比于CMA, CO更容易吸附在疏水CMASc上. H₂O的引入会导致CO在两个催化剂的强度变弱, 但CMASc上吸附的CO强度仍要高于CMA. 这说明活性位点存在水会阻碍CO的吸附, 而CMASc上相对干燥的表面更有利于CO吸附及后续活化. 调控H₂O分压探针实验也在宏观层面上验证了该结论, 说明活性中心吸附的H₂O会抑制催化活性. 丙烯加氢脉冲实验发现, 浸润环境可以极大地影响烯烃的吸附和加氢能力. 在H₂O存在的情况下, 丙烯更容易在CMA上发生加氢生成丙烷, 而疏水CMASc上丙烯更容易直接脱落, 从而提高了烯烃选择性.
综上, 通过调控Co₂C活性位局域疏水环境, 可以降低表面H₂O的吸附, 抑制CO₂副产物生成, 同时强化CO吸附和烯烃脱附, 提高烯烃选择性和收率, 这为高碳效Co₂C基催化剂的理性设计提供借鉴.

关键词: 费托合成制烯烃, 合成气转化, 碳化钴, 疏水性, 低CO₂选择性

Abstract:

Fischer-Tropsch synthesis to olefins (FTO) with high carbon efficiency is an important but challenging research target. Current routes for direct syngas conversion to olefins suffer from high CO₂ selectivity and low olefin yields due to the inevitable water-gas shift (WGS) reaction. Herein, we report that product selectivity can be controlled by tuning the wettability of the environment around the active center through simple physical mixing of cobalt carbide (Co₂C) with a hydrophobic SiO₂ component. The suppressed WGS reactivity results in a greatly improved catalytic performance of Co₂C, significantly decreased CO₂ selectivity (from 47.8% to 16.8%), and increased olefin selectivity (by ~65%) and activity (by 30%). The local hydrophobic environment favors the rapid diffusion of water away from the Co₂C active center, thus remarkably enhancing the linear adsorption of CO and suppressing the production of CO₂ via WGS. This work provides a simple yet effective strategy to modulate the product selectivity and improve the carbon efficiency of the FTO process.

Key words: Fischer-Tropsch to olefins, Syngas conversion, Cobalt carbide, Hydrophobic, Low CO₂ selectivity

刘培功, 林铁军, 郭磊, 刘晓哲, 龚坤, 尧泰真, 安芸蕾, 钟良枢. 调控Co₂C局域浸润环境实现高碳效合成气直接制烯烃[J]. 催化学报, 2023, 48: 150-163.

Peigong Liu, Tiejun Lin, Lei Guo, Xiaozhe Liu, Kun Gong, Taizhen Yao, Yunlei An, Liangshu Zhong. Tuning cobalt carbide wettability environment for Fischer-Tropsch to olefins with high carbon efficiency[J]. Chinese Journal of Catalysis, 2023, 48: 150-163.

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图/表 12

Fig. 1. Catalytic performance of various catalysts. (a) CO conversion and product selectivity of CMA and CMASc composite oxides with different mixing ratios. (b) Comparison of the catalytic activity and CO2 formation rate calculated based on the total molar CO consumption. (c) Space-time yield of olefins and olefin formation rate. (d) Stability test over the CMASc-1/1 catalyst. Reaction conditions: H2/CO = 0.5, 260 °C, 10 bar, 4000 mL·g-1·h-1.

Fig. 2. CO hydrogenation performance over composite catalysts with different proximity. (a) CO conversion and product selectivity (including CO2) over varied catalysts. (b) Granule mixing of 40-60 mesh CMA and 40-60 mesh hydrophobic SiO2. (c) Powder mixture of CMA and hydrophobic SiO2. (d) Core-shell structured CMA@SiO2-c. ROH denotes oxygenates. Reaction conditions: H2/CO = 0.5, 260 °C, 10 bar, 4000 mL·g-1·h-1.

Fig. 3. (a) FTIR spectra of SiO2. Water droplet contact angle of SiO2 (b) and SiO2-c (c). (d) TG-DTG curves of hydrophobic SiO2-c.

Fig. 4. FTIR spectra of various fresh (a) and reduced (b) samples. Water droplet contact angles of fresh (c) and reduced (d) CMASc-1/1 composite catalysts.

Fig. 5. XRD patterns of various fresh (a), reduced (b), and spent (c) catalysts. (d) H2-TPR profile of various catalysts.

Fig. 6. (HR)TEM images of various spent catalysts. (a) CMA; (b) CMASc-1/1; (c) CMASc-1/5.

Fig. 7. CO/H2O-TPSR-MS of spent CMA and CMASc-1/1 samples.

Fig. 8. CO/H2-TPSR-MS of the spent CMA and CMASc-1/1 samples. (a) Signal of H2O (m/z = 18). (b) Signal of CO2 (m/z = 44).

Fig. 9. WGS probe reaction over the working CMA (a) and CMASc-1/1 (b) samples.

Fig. 10. DRIFTS spectra of CO adsorption. Spent CMA (a) and CMASc-1/1 (b) in the absence of H2O. Spent CMA (c) and CMASc-1/1 (d) in the presence of H2O.

Fig. 11. Effect of H2O partial pressure on CO conversion and CO2 selectivity over working CMA and CMASc-1/1 (a) and its partial enlarged detail (b).

Fig. 12. Transient response curves obtained from propene hydrogenation pulse experiments without (a,c) and with (b,d) the water vapor over the spent CMA and CMASc-1/1 catalyst. R: peak area ratio of C3H6/C3H8.

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调控Co₂C局域浸润环境实现高碳效合成气直接制烯烃

Tuning cobalt carbide wettability environment for Fischer-Tropsch to olefins with high carbon efficiency

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