化工进展 ›› 2024, Vol. 43 ›› Issue (6): 3061-3079.DOI: 10.16085/j.issn.1000-6613.2023-1068
• 工业催化 • 上一篇
曾壮1(), 李柯志1, 苑志伟1, 杜金涛1, 李卓师2(
), 王悦2(
)
收稿日期:
2023-06-27
修回日期:
2023-08-15
出版日期:
2024-06-15
发布日期:
2024-07-02
通讯作者:
李卓师,王悦
作者简介:
曾壮(1993—),男,博士,工程师,研究方向为催化剂制备技术和清洁生产技术。E-mail:zengzh.chji@sinopec.com。
基金资助:
ZENG Zhuang1(), LI Kezhi1, YUAN Zhiwei1, DU Jintao1, LI Zhuoshi2(
), WANG Yue2(
)
Received:
2023-06-27
Revised:
2023-08-15
Online:
2024-06-15
Published:
2024-07-02
Contact:
LI Zhuoshi, WANG Yue
摘要:
一氧化碳/二氧化碳(CO/CO2)加氢制低碳醇(C2+OH)是碳一化学的重要组成部分,是将煤、天然气、生物质、CO2等非石油资源转化为液体燃料和高附加值化学品的重要途径。该过程具有工艺路线短、原子经济性高、操作可行性强等优点,是颇具前景的合成路线。改性的费托合成催化剂是该体系最具潜力的催化剂之一,但仍存在低碳醇时空收率不理想、反应网络复杂、产物分布难以调控及稳定性差等问题,高效稳定催化剂的开发极具挑战。本文首先从热力学上分析了CO/CO2加氢反应制低碳醇适宜的工艺条件;其次,对改性费托合成催化剂上CO/CO2加氢制低碳醇的反应路径进行了解析,并据此提出催化剂的设计思路。随后,介绍了铁基和钴基催化剂的研究现状,详细阐述了前体结构、助剂、金属-载体相互作用等因素对催化剂性能的影响机制,重点分析了高性能催化剂的构建策略。后续可借助于先进表征技术和理论计算进一步加深对反应机理的认识,并通过催化剂结构的精细调控,获取低碳醇时空收率和催化剂稳定性的提升策略。
中图分类号:
曾壮, 李柯志, 苑志伟, 杜金涛, 李卓师, 王悦. CO/CO2 加氢制低碳醇改性费托合成催化剂研究进展[J]. 化工进展, 2024, 43(6): 3061-3079.
ZENG Zhuang, LI Kezhi, YUAN Zhiwei, DU Jintao, LI Zhuoshi, WANG Yue. Advances in modified Fischer-Tropsch synthesis catalysts for CO/CO2 hydrogenation to higher alcohols[J]. Chemical Industry and Engineering Progress, 2024, 43(6): 3061-3079.
过程 | 反应 | ΔG⊖(25℃)/kJ·mol-1 | ΔH⊖(25℃)/kJ·mol-1 |
---|---|---|---|
甲醇合成 | -25.1 | -90.5 | |
3.5 | -49.3 | ||
乙醇合成 | -221.1 | -253.6 | |
-32.4 | -86.7 | ||
甲烷化 | -141.9 | -205.8 | |
-113.5 | -165.0 | ||
WGS反应 | -28.6 | -41.1 | |
RWGS反应 | 28.6 | 41.1 |
表1 CO/CO2加氢反应过程中重要反应的热力学数据[17-18]
过程 | 反应 | ΔG⊖(25℃)/kJ·mol-1 | ΔH⊖(25℃)/kJ·mol-1 |
---|---|---|---|
甲醇合成 | -25.1 | -90.5 | |
3.5 | -49.3 | ||
乙醇合成 | -221.1 | -253.6 | |
-32.4 | -86.7 | ||
甲烷化 | -141.9 | -205.8 | |
-113.5 | -165.0 | ||
WGS反应 | -28.6 | -41.1 | |
RWGS反应 | 28.6 | 41.1 |
催化剂 | 反应条件 | CO转化率 /% | 选择性/% | 收率/% | 时空收率③/g·g-1·h-1 | 参考文献 | |||||
---|---|---|---|---|---|---|---|---|---|---|---|
温度/℃ | 压力/MPa | H2/CO比 | 空速/h-1 | 总醇 | 低碳醇 | 低碳醇 | 总醇 | 低碳醇 | |||
CNF-2-0.005① | 275 | 5 | 1.5 | 32000② | 11 | 47 | 37 | 4.1 | 0.670 | 0.530 | [ |
Au-Fe-10 | 260 | 3 | 1 | 4800 | 20.0 | 52.5 | 31.7 | 6.3 | 0.268 | 0.195 | [ |
Co1Fe2 | 260 | 3 | 1 | 9600② | 9.9 | 51.2 | 38.5 | 3.8 | 0.206 | 0.143 | [ |
CoFe-300-0.25 | 260 | 3 | 2 | 10800② | 24.3 | 34.0 | 31.0 | 7.5 | 0.281 | 0.243 | [ |
S2-CuFeMg-cat | 300 | 4 | 2 | 2000 | 56.9 | 49.1 | 32.8 | 18.7 | 0.280 | 0.187 | [ |
CuFe@HHSS① | 300 | 3 | 2 | 5000 | 65.1 | 46.6 | 约27.7 | 18.0 | 0.118 | 0.070 | [ |
Cu4Fe1 | 260 | 1 | 2 | 2400② | 53.2 | 29.8 | 27.1 | 14.4 | 0.201 | 0.183 | [ |
3DOM Cu2Fe1 | 200 | 4.8 | 1 | 2000 | 12.9 | 47.6 | 45.0 | 5.8 | 0.230 | 0.218 | [ |
Cu5.2Fe4.8 | 350 | 5.5 | 2 | 6000 | 70.5 | 12.4 | 7.2 | 5.1 | 0.177 | 0.102 | [ |
CF0.5 | 260 | 4 | 2 | 5000 | 18.0 | 20.8 | 10.0 | 1.8 | 0.050 | 0.024 | [ |
Cu-Fe/SiO2 (WI) | 250 | 3 | 2 | 6000② | 14.0 | 26.8 | 8.47 | 1.2 | 0.104 | 0.033 | [ |
2Ca-Fe | 190 | 4 | 2 | 1800② | 22.2 | 37.8 | — | — | 0.039 | — | [ |
表2 CO加氢制低碳醇Fe基催化剂的性能汇总
催化剂 | 反应条件 | CO转化率 /% | 选择性/% | 收率/% | 时空收率③/g·g-1·h-1 | 参考文献 | |||||
---|---|---|---|---|---|---|---|---|---|---|---|
温度/℃ | 压力/MPa | H2/CO比 | 空速/h-1 | 总醇 | 低碳醇 | 低碳醇 | 总醇 | 低碳醇 | |||
CNF-2-0.005① | 275 | 5 | 1.5 | 32000② | 11 | 47 | 37 | 4.1 | 0.670 | 0.530 | [ |
Au-Fe-10 | 260 | 3 | 1 | 4800 | 20.0 | 52.5 | 31.7 | 6.3 | 0.268 | 0.195 | [ |
Co1Fe2 | 260 | 3 | 1 | 9600② | 9.9 | 51.2 | 38.5 | 3.8 | 0.206 | 0.143 | [ |
CoFe-300-0.25 | 260 | 3 | 2 | 10800② | 24.3 | 34.0 | 31.0 | 7.5 | 0.281 | 0.243 | [ |
S2-CuFeMg-cat | 300 | 4 | 2 | 2000 | 56.9 | 49.1 | 32.8 | 18.7 | 0.280 | 0.187 | [ |
CuFe@HHSS① | 300 | 3 | 2 | 5000 | 65.1 | 46.6 | 约27.7 | 18.0 | 0.118 | 0.070 | [ |
Cu4Fe1 | 260 | 1 | 2 | 2400② | 53.2 | 29.8 | 27.1 | 14.4 | 0.201 | 0.183 | [ |
3DOM Cu2Fe1 | 200 | 4.8 | 1 | 2000 | 12.9 | 47.6 | 45.0 | 5.8 | 0.230 | 0.218 | [ |
Cu5.2Fe4.8 | 350 | 5.5 | 2 | 6000 | 70.5 | 12.4 | 7.2 | 5.1 | 0.177 | 0.102 | [ |
CF0.5 | 260 | 4 | 2 | 5000 | 18.0 | 20.8 | 10.0 | 1.8 | 0.050 | 0.024 | [ |
Cu-Fe/SiO2 (WI) | 250 | 3 | 2 | 6000② | 14.0 | 26.8 | 8.47 | 1.2 | 0.104 | 0.033 | [ |
2Ca-Fe | 190 | 4 | 2 | 1800② | 22.2 | 37.8 | — | — | 0.039 | — | [ |
催化剂 | 反应条件 | CO转化率 /% | 选择性/% | 收率/% | 时空收率 /g·g-1·h-1 | 参考文献 | |||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|---|
温度/℃ | 压力/MPa | H2/CO比 | 空速/h-1 | 甲醇 | 低碳醇 | 烃类 | CO2 | 低碳醇 | 总醇 | 低碳醇 | |||
Co1Ga0.6-ZnAl-LDO/γ-Al2O3 | 260 | 3 | 2 | 2000 | 43.5 | 4.2 | 54.8 | 39.9 | 0.61 | 23.8 | — | — | [ |
0.6Na-Co/AC | 220 | 3 | 2 | 2000② | 12.8 | 3.8 | 27.0 | 56.6 | 12.6 | 3.5 | — | — | [ |
Co1Mn/AC | 220 | 3 | 2 | 2000 | 29.1 | 1.6 | 19.8 | 76.2 | 2.4 | 5.8 | 0.047 | 0.043 | [ |
Co/MnOx@quasi-MOF-74 | 230 | 3 | 2 | 15000② | 10.5 | 3.8 | 33.9 | 62.4 | 0.0 | 3.6 | 0.206③ | 0.185 | [ |
Co4.7Mo@C | 275 | 3 | 2 | 15000② | 48 | 2.3 | 9.6 | 67.0 | 21.1 | 4.6 | 0.123 | 0.099 | [ |
(Cu1Co2)2Al/CNT | 230 | 3 | 2 | 3900② | 45.4 | 2.1 | 60.8 | 35.3 | 1.8 | 27.6 | 0.149 | 0.137 | [ |
Co3Cu-11%CNT(h型) | 300 | 5 | 1 | 7200② | 38.5 | 5.0 | 57.9 | 20.7 | 5.0 | 22.3 | 0.683 | 0.611 | [ |
CoCu/5%GE-LFO① | 300 | 3 | 2 | 3900② | 49.7 | 9.7 | 47.2 | 35.2 | 7.9 | 23.5 | — | — | [ |
(Cu1Co2)2Al-Red① | 250 | 3 | 2 | 3900② | 51.8 | 1.7 | 44.1 | 51.3 | 2.9 | 22.8 | — | — | [ |
Co3Cu1/KIT-6 | 270 | 3 | 2 | 14400② | 62.9 | 15.6 | 30.6 | 53.1 | 0.8 | 19.2 | — | — | [ |
Co2.5Cu1-773 | 270 | 3 | 1 | 4800② | 45.3 | 9.8 | 31.8 | 55.5 | 2.9 | 14.4 | — | — | [ |
CuCoMn | 270 | 2.5 | 2 | 7500 | 29.7 | 13.7 | 32.5 | 51.9 | 0.4 | 9.7 | — | — | [ |
15Cu5Co@MCN① | 220 | 2 | 1 | 4000② | 20.4 | 20.2 | 29.8 | 38.3 | 11.7 | 6.1 | 0.080 | 0.048 | [ |
Cu0.25Co0.75 | 250 | 3 | 2 | 3900 | 71.3 | 2.6 | 11.2 | 86.2 | — | 8.0 | 0.148 | 0.121 | [ |
表3 CO加氢制低碳醇Co基催化剂的性能汇总
催化剂 | 反应条件 | CO转化率 /% | 选择性/% | 收率/% | 时空收率 /g·g-1·h-1 | 参考文献 | |||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|---|
温度/℃ | 压力/MPa | H2/CO比 | 空速/h-1 | 甲醇 | 低碳醇 | 烃类 | CO2 | 低碳醇 | 总醇 | 低碳醇 | |||
Co1Ga0.6-ZnAl-LDO/γ-Al2O3 | 260 | 3 | 2 | 2000 | 43.5 | 4.2 | 54.8 | 39.9 | 0.61 | 23.8 | — | — | [ |
0.6Na-Co/AC | 220 | 3 | 2 | 2000② | 12.8 | 3.8 | 27.0 | 56.6 | 12.6 | 3.5 | — | — | [ |
Co1Mn/AC | 220 | 3 | 2 | 2000 | 29.1 | 1.6 | 19.8 | 76.2 | 2.4 | 5.8 | 0.047 | 0.043 | [ |
Co/MnOx@quasi-MOF-74 | 230 | 3 | 2 | 15000② | 10.5 | 3.8 | 33.9 | 62.4 | 0.0 | 3.6 | 0.206③ | 0.185 | [ |
Co4.7Mo@C | 275 | 3 | 2 | 15000② | 48 | 2.3 | 9.6 | 67.0 | 21.1 | 4.6 | 0.123 | 0.099 | [ |
(Cu1Co2)2Al/CNT | 230 | 3 | 2 | 3900② | 45.4 | 2.1 | 60.8 | 35.3 | 1.8 | 27.6 | 0.149 | 0.137 | [ |
Co3Cu-11%CNT(h型) | 300 | 5 | 1 | 7200② | 38.5 | 5.0 | 57.9 | 20.7 | 5.0 | 22.3 | 0.683 | 0.611 | [ |
CoCu/5%GE-LFO① | 300 | 3 | 2 | 3900② | 49.7 | 9.7 | 47.2 | 35.2 | 7.9 | 23.5 | — | — | [ |
(Cu1Co2)2Al-Red① | 250 | 3 | 2 | 3900② | 51.8 | 1.7 | 44.1 | 51.3 | 2.9 | 22.8 | — | — | [ |
Co3Cu1/KIT-6 | 270 | 3 | 2 | 14400② | 62.9 | 15.6 | 30.6 | 53.1 | 0.8 | 19.2 | — | — | [ |
Co2.5Cu1-773 | 270 | 3 | 1 | 4800② | 45.3 | 9.8 | 31.8 | 55.5 | 2.9 | 14.4 | — | — | [ |
CuCoMn | 270 | 2.5 | 2 | 7500 | 29.7 | 13.7 | 32.5 | 51.9 | 0.4 | 9.7 | — | — | [ |
15Cu5Co@MCN① | 220 | 2 | 1 | 4000② | 20.4 | 20.2 | 29.8 | 38.3 | 11.7 | 6.1 | 0.080 | 0.048 | [ |
Cu0.25Co0.75 | 250 | 3 | 2 | 3900 | 71.3 | 2.6 | 11.2 | 86.2 | — | 8.0 | 0.148 | 0.121 | [ |
催化剂 | 反应条件 | CO2转化率 /% | 选择性/% | 收率/% | 参考文献 | |||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|
温度/℃ | 压力/MPa | H2/CO2比 | 空速/h-1 | 甲醇 | 低碳醇 | 甲烷 | C2+烃 | CO | 低碳醇 | |||
(K2O)5%CuZnFeZrO2 | 320 | 3 | 3 | 3600 | 25.5 | 12.3 | 11.0 | 23.6(所有烃) | 53.1 | 2.81 | [ | |
FeNaS-0.6① | 320 | 3 | 3 | 8000② | 32.0 | 0.2 | 12.6 | 10.3 | 56.2 | 20.7 | 4.03 | [ |
4.6K-CuMgZnFe | 320 | 5 | 3 | 6000② | 30.4 | 1.3 | 15.9 | 9.7 | 42.7 | 30.6 | 4.83 | [ |
Cs-Cu0.8Fe1.0Zn1.0 | 330 | 5 | 3 | 4500② | 36.6 | 0.9 | 19.8 | 11.8 | 46.9 | 20.6 | 7.25 | [ |
K/Cu-Fe-Zn | 300 | 7 | 3 | 5000③ | 44.2 | 2.0 | 26.9 | 46.1(所有烃) | 5.9 | 11.9 | [ | |
RhFeLi/TiO2NRs-500℃① | 250 | 3 | 3 | 6000 | 15.7 | 2.2 | 31.4 | 53.9 | 0 | 12.5 | 4.93 | [ |
CuZnFe0.5K0.15 | 300 | 6 | 3 | 5000 | 42.3 | 4.7 | 32.0 | 56.4(所有烃) | 6.9 | 13.5 | [ | |
Cr(1%)-CuFe | 320 | 4 | 3 | 6000② | 38.4 | — | 29.2 | — | 14.8 | 11.2 | [ | |
CZA(1)/K-CMZF(1) | 320 | 5 | 3 | 6000② | 42.3 | 1.3 | 17.4 | 67.6(所有烃) | 13.8 | 7.4 | [ | |
Co@Co3O4/C-N | 220 | 2 | 3 | 6000② | 18.6 | 18.3 | 1.2 | 79.5 | 0.7 | 0 | 0.22 | [ |
Ir/Co(A)-Na2O/SiO2 | 220 | 2.1 | 3 | 2000 | 7.6 | 7.8 | 7.9 | 35.7 | 9.6 | 38.5 | 0.60 | [ |
Na-Co/SiO2 | 250 | 5 | 3 | 4000 | 18.8 | ~1.2 | ~8.3 | 38.7 | 22.7 | 29.1 | 1.45 | [ |
Co3O4-m① | 200 | 2 | 3 | 6000② | 28.9 | 10.2 | 9.0 | 53.6 | 27.2 | 0 | 2.60 | [ |
Cu/Co3O4-2h | 250 | 3 | 3 | 36000② | 13.9 | 2.4 | 15.2 | 37.9 | 19.9 | 6.5 | 2.11 | [ |
Pt/Co3O4-m① | 200 | 2 | 3 | 6000② | 10.7 | 23.6 | 23.6 | 14.9 | 9.6 | 28.3 | 2.53 | [ |
表4 CO2加氢制低碳醇改性FTS催化剂的性能汇总
催化剂 | 反应条件 | CO2转化率 /% | 选择性/% | 收率/% | 参考文献 | |||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|
温度/℃ | 压力/MPa | H2/CO2比 | 空速/h-1 | 甲醇 | 低碳醇 | 甲烷 | C2+烃 | CO | 低碳醇 | |||
(K2O)5%CuZnFeZrO2 | 320 | 3 | 3 | 3600 | 25.5 | 12.3 | 11.0 | 23.6(所有烃) | 53.1 | 2.81 | [ | |
FeNaS-0.6① | 320 | 3 | 3 | 8000② | 32.0 | 0.2 | 12.6 | 10.3 | 56.2 | 20.7 | 4.03 | [ |
4.6K-CuMgZnFe | 320 | 5 | 3 | 6000② | 30.4 | 1.3 | 15.9 | 9.7 | 42.7 | 30.6 | 4.83 | [ |
Cs-Cu0.8Fe1.0Zn1.0 | 330 | 5 | 3 | 4500② | 36.6 | 0.9 | 19.8 | 11.8 | 46.9 | 20.6 | 7.25 | [ |
K/Cu-Fe-Zn | 300 | 7 | 3 | 5000③ | 44.2 | 2.0 | 26.9 | 46.1(所有烃) | 5.9 | 11.9 | [ | |
RhFeLi/TiO2NRs-500℃① | 250 | 3 | 3 | 6000 | 15.7 | 2.2 | 31.4 | 53.9 | 0 | 12.5 | 4.93 | [ |
CuZnFe0.5K0.15 | 300 | 6 | 3 | 5000 | 42.3 | 4.7 | 32.0 | 56.4(所有烃) | 6.9 | 13.5 | [ | |
Cr(1%)-CuFe | 320 | 4 | 3 | 6000② | 38.4 | — | 29.2 | — | 14.8 | 11.2 | [ | |
CZA(1)/K-CMZF(1) | 320 | 5 | 3 | 6000② | 42.3 | 1.3 | 17.4 | 67.6(所有烃) | 13.8 | 7.4 | [ | |
Co@Co3O4/C-N | 220 | 2 | 3 | 6000② | 18.6 | 18.3 | 1.2 | 79.5 | 0.7 | 0 | 0.22 | [ |
Ir/Co(A)-Na2O/SiO2 | 220 | 2.1 | 3 | 2000 | 7.6 | 7.8 | 7.9 | 35.7 | 9.6 | 38.5 | 0.60 | [ |
Na-Co/SiO2 | 250 | 5 | 3 | 4000 | 18.8 | ~1.2 | ~8.3 | 38.7 | 22.7 | 29.1 | 1.45 | [ |
Co3O4-m① | 200 | 2 | 3 | 6000② | 28.9 | 10.2 | 9.0 | 53.6 | 27.2 | 0 | 2.60 | [ |
Cu/Co3O4-2h | 250 | 3 | 3 | 36000② | 13.9 | 2.4 | 15.2 | 37.9 | 19.9 | 6.5 | 2.11 | [ |
Pt/Co3O4-m① | 200 | 2 | 3 | 6000② | 10.7 | 23.6 | 23.6 | 14.9 | 9.6 | 28.3 | 2.53 | [ |
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