CO-CO2体系制备氘代甲醇催化剂的合成与改性

doi:10.16085/j.issn.1000-6613.2023-1252

摘要/Abstract

摘要：

作为一种重要的化工原料和氘代中间体，氘代甲醇（CD₃OD）广泛用于核磁共振试剂、氘代药物中间体和光电材料改性，但其在CO-CO₂体系的催化合成效率仍有待提高。本研究采用浸渍法掺杂稀土元素对CuO/ZnO/Al₂O₃（CZA）催化剂进行改性，评价了其在CO-CO₂体系加D₂制氘代甲醇的催化性能，并表征了催化剂。结果表明，稀土元素成功掺杂并均匀分散于CZA催化剂中，La和Ce的掺入能有效提高催化剂的比表面积和孔容，增加表面CuO的数量；而Pr的掺入降低了催化剂活性。其中，CZA-3%La催化剂具有最大的比表面积（46.69m²/g）和最大的孔容（0.26cm³/g），催化活性最好，其氘代甲醇时空产率相比CZA催化剂提高了7.96%。稀土掺杂改性的CZA催化剂对提升CO-CO₂体系合成氘代甲醇的反应效率有重要意义。

关键词: 催化剂, 合成, 活性, 氘代甲醇, 稀土元素改性

Abstract:

As an important chemical raw material and deuterated intermediate, deuterated methanol (CD₃OD) has been widely used in nuclear magnetic resonance reagents, deuterated drug intermediates and photoelectric material modification, but its catalytic synthesis efficiency in CO-CO₂ system is still not sufficiently high. In this study, rare earth elements were doped into CuO/ZnO/Al₂O₃ (CZA) catalyst by impregnation method. The catalytic performance of CZA catalysts in CO-CO₂ system with D₂ was tested and the catalysts were characterized. The results showed that the rare earth elements were uniformly dispersed in the CZA catalyst. The incorporation of La and Ce could effectively increase the specific surface area and pore volume of the catalyst and the amount of CuO on the surface of the catalyst as well. But the activity of the catalyst was reduced with the incorporation of Pr. CZA-3%La catalyst had the largest specific surface area of 46.69m²/g and the largest pore volume of 0.26cm³/g, therefore, giving the best catalytic activity with a deuterated methanol space-time yield of 7.96 %, higher than that of CZA catalyst. The CZA catalyst doped with rare earth elements was of great significance to improve the deuterated methanol synthesis efficiency in CO-CO₂ system.

Key words: catalyst, synthesis, activity, deuterated methanol, rare earth element modification

中图分类号:

TQ27

龙涛, 周锋, 张伟, 吴泓, 王建, 陈霖. CO-CO₂体系制备氘代甲醇催化剂的合成与改性[J]. 化工进展, 2024, 43(8): 4411-4420.

LONG Tao, ZHOU Feng, ZHANG Wei, WU Hong, WANG Jian, CHEN Lin. Synthesis and modification of deuterated methanol catalyst used in CO-CO₂ system[J]. Chemical Industry and Engineering Progress, 2024, 43(8): 4411-4420.

图/表 12

图1 催化剂反应装置① 气体钢瓶；② 质量流量计；③ 阀门；④反应器；⑤ 管式炉；⑥ 控温系统；⑦ 液阱；⑧ FL9790气相色谱仪；⑨ 计算机；⑩ FL9790Ⅱ气相色谱仪

表1 稀土改性CZA催化剂性能

催化剂	X(D₂)/%	X(CO)/%	X(CO₂)/%	STY(CD₃OD) /mg· $g c a t - 1$ ·h^-1
CZA	43.86	73.49	37.88	529.40
CZA-3%La	45.38	73.82	35.66	571.54
CZA-5%La	44.98	71.73	37.55	550.16
CZA-7%La	44.91	67.21	33.54	547.38
CZA-10%La	43.30	68.77	32.35	543.69
CZA-3%Ce	45.34	70.97	37.28	548.67
CZA-5%Ce	44.94	69.44	36.59	544.74
CZA-7%Ce	43.49	68.34	33.07	524.92
CZA-10%Ce	42.76	69.3	37.53	494.72
CZA-3%Pr	43.24	70.11	36.67	506.22
CZA-5%Pr	43.18	66.61	35.37	492.55
CZA-7%Pr	42.88	70.81	35.67	482.89

表1 稀土改性CZA催化剂性能

催化剂	X(D₂)/%	X(CO)/%	X(CO₂)/%	STY(CD₃OD) /mg· $g c a t - 1$ ·h^-1
CZA	43.86	73.49	37.88	529.40
CZA-3%La	45.38	73.82	35.66	571.54
CZA-5%La	44.98	71.73	37.55	550.16
CZA-7%La	44.91	67.21	33.54	547.38
CZA-10%La	43.30	68.77	32.35	543.69
CZA-3%Ce	45.34	70.97	37.28	548.67
CZA-5%Ce	44.94	69.44	36.59	544.74
CZA-7%Ce	43.49	68.34	33.07	524.92
CZA-10%Ce	42.76	69.3	37.53	494.72
CZA-3%Pr	43.24	70.11	36.67	506.22
CZA-5%Pr	43.18	66.61	35.37	492.55
CZA-7%Pr	42.88	70.81	35.67	482.89

图2 催化剂焙烧样的N2等温吸附-解吸附曲线与孔径分布曲线

表2 稀土（La、Ce）改性后的CZA催化剂样品孔结构性质

催化剂	比表面积/m²·g^-1	孔容/cm³·g^-1	平均孔径/nm
CZA	38.59	0.19	12.67
CZA-3%La	46.49	0.26	10.88
CZA-3%Ce	41.77	0.23	10.89

图3 催化剂XRD图谱

表3 各催化剂焙烧样及还原样中晶粒尺寸

催化剂	焙烧样CuO晶粒尺寸/nm	还原样Cu晶粒尺寸/nm
CZA	8.21	16.52
CZA-3%La	7.88	14.19
CZA-5%La	6.67	11.73
CZA-7%La	7.32	12.00
CZA-10%La	7.8	12.57
CZA-3%Ce	8.06	13.13
CZA-5%Ce	7.40	10.55
CZA-7%Ce	7.79	11.75
CZA-10%Ce	9.24	13.13

图4 部分催化剂的H2-TPR图谱

表4 部分催化剂焙烧样的H2消耗量

催化剂	α峰/mmol·g^-1	β峰/mmol·g^-1	γ峰/mmol·g^-1
CZA	0.18	0.11	—
CZA-3%La	—	—	0.33
CZA-3%Ce	—	—	0.31

图5 催化剂的H2-TPD曲线

图6 催化剂的SEM图谱

图7 CZA-3%La还原样及CZA-3%Ce还原样SEM-Mapping图谱

图8 CZA-3%La催化剂的TEM图谱

参考文献 21

1	刘晓林, 代伟娜, 许东海, 等. 一种氘代甲醇的制备方法: CN111116313B[P]. 2023-04-14.
	LIU Xiaolin, DAI Weina, XU Donghai. A preparation method of deuterated methanol: CN111116313B[P]. 2023-04-14.
2	王建国, 邵方君, 王萧剑. 一种制备氘代甲醇的催化剂及其制备方法: CN112675875A[P]. 2021-04-20.
	WANG Jianguo, SHAO Fangjun, WANG Xiaojian. A catalyst for preparing deuterated methanol and its preparation method: CN112675875A[P]. 2021-04-20.
3	张文池, 王亚东. 一种合成氘代甲醇的催化剂及其制备方法: CN109078638A[P]. 2018-12-25.
	ZHANG Wenchi, WANG Yadong. A catalyst for the synthesis of deuterated methanol and its preparation method: CN109078638A[P]. 2018-12-25.
4	SONG Hyun-tae, FAZELI Ali, KIM Hyun Dong, et al. Effect of lanthanum group promoters on Cu/(mixture of ZnO and Zn-Al spinnel-oxides) catalyst for methanol synthesis by hydrogenation of CO and CO₂ mixtures[J]. Fuel, 2021, 283: 118987-119002.
5	YOSHIHARA Jun, CAMPBELL Charles T. Methanol synthesis and reverse water-gas shift kinetics over Cu(110) model catalysts: structural sensitivity[J]. Journal of Catalysis, 1996, 161(2): 776-782.
6	FISHER Ian A, BELL Alexis T. In-situ infrared study of methanol synthesis from H₂/CO₂ over Cu/SiO₂and Cu/ZrO₂/SiO₂ [J]. Journal of Catalysis, 1997, 172: 222-237.
7	贾晨喜, 邵敬爱, 白小薇, 等. 二氧化碳加氢制甲醇铜基催化剂性能的研究进展[J]. 化工进展, 2020, 39(9): 3658-3668.
	JIA Chenxi, SHAO Jing’ai, BAI Xiaowei, et al. Review on Cu-based catalysts for CO₂hydrogenation to methanol[J]. Chemical Industry and Engineering Progress, 2020, 39(9): 3658-3668.
8	BAN Hongyan, LI Congming, ASAMI Kenji, et al. Influence of rare-earth elements (La, Ce, Nd and Pr) on the performance of Cu/Zn/Zr catalyst for CH₃OH synthesis from CO₂ [J]. Catalysis Communications, 2014, 54: 50-54.
9	TURSUNOV Obid, KUSTOV Leonid, TILYABAEV Zaid. Methanol synthesis from the catalytic hydrogenation of CO₂ over CuO-ZnO supported on aluminum and silicon oxides[J]. Journal of the Taiwan Institute of Chemical Engineers, 2017, 78: 416-422.
10	KOURTELESIS Marios, KOUSI Kalliopi, KONDARIDES Dimitris I. CO₂ hydrogenation to methanol over La₂O₃-promoted CuO/ZnO/Al₂O₃ catalysts: A kinetic and mechanistic study[J]. Catalysts, 2020, 10: 183-201.
11	张鲁湘. CO₂催化加氢合成甲醇催化剂CuO-ZnO-Al₂O₃改性的研究[D]. 大连: 大连理工大学, 2012.
	ZHANG Luxiang. Investigation of modification of catalyst CuO-ZnO-Al₂O₃ for methanol synthesis from CO₂ catalytic hydrogenation[D]. Dalian: Dalian University of Technology, 2012.
12	Stefanie KÜHL, SCHUMANN Julia, KASATKIN Igor, et al. Ternary and quaternary Cr or Ga-containing ex-LDH catalysts — Influence of the additional oxides onto the microstructure and activity of Cu/ZnAl₂O₄ catalysts[J]. Catalysis Today, 2015, 246: 92-100.
13	季生福, 张谦温, 赵彬侠. 催化剂基础及应用[M]. 北京: 化学工业出版社, 2011.
	JI Shengfu, ZHANG Qianwen, ZHAO Binxia. Catalyst foundation and application[M]. Beijing: Chemical Industry Press, 2011.
14	JIANG Xiao. Palladium-copper bimetallic catalysts for selective carbon dioxide hydrogenation to methanol[D]. Commonwealth of Pennsylvania: The Pennsylvania State University, 2015.
15	ARENA Francesco, MEZZATESTA Giovanni, ZAFARANA Giovanni, et al. How oxide carriers control the catalytic functionality of the Cu-ZnO system in the hydrogenation of CO₂ to methanol[J]. Catalysis Today, 2013, 210: 39-46.
16	何迈, 方萍, 谢冠群, 等. CuO/CeO₂-Al₂O₃催化剂中CuO物种的原位XRD、Raman和TPR表征[J]. 物理化学学报, 2005, 21(9): 997-1000.
	HE Mai, FANG Ping, XIE Guanqun, et al. Characterization of CuO species in CuO/CeO₂-Al₂O₃ catalysts by in-situ XRD, Raman spectroscopy and TPR[J]. Acta Physico-Chimica Sinica, 2005, 21(9): 997-1000.
17	高琪. 碱性助剂对铜基催化剂结构及CO₂加氢合成甲醇催化活性的影响[D]. 银川: 宁夏大学, 2019.
	GAO Qi. Effects of alkaline promoter on the structure of copper-based catalysts and the activity of CO₂ hydrogenation to methanol[D]. Yinchuan: Ningxia University, 2019.
18	LONG Yi, CHU Wei, YE Yanghbng H, et al. Hydrogenolysis of methyl formate to methanol on copper-based catalysts and TPR characterization[J]. Studies in Surface Science and Catalysis, 2004, 147: 613-618.
19	DONG Xin, ZHANG Hongbin, LIN Guodong, et al. Highly active CNT-promoted Cu-ZnO-Al₂O₃ catalyst for methanol synthesis from H₂/CO/CO₂ [J]. Catalysis Letters, 2003, 85: 237-246.
20	丁洁莲, 金秋, 曾崇余, 等. 不同沉淀剂对制备邻苯基苯酚的Cu-Mg催化剂性能的影响[J]. 工业催化, 2008, 16(5): 11-15.
	DING Jielian, JIN Qiu, ZENG Chongyu, et al. Effect of precipitants on Cu-Mg catalyst for synthesis of o-phenylphenol[J]. Industrial Catalysis, 2008, 16(5): 11-15.
21	GRAAF Geert H, STAMHUIS Eize J, BEENACKERS Anthonius A C M. Kinetics of low-pressure methanol synthesis[J]. Chemical Engineering Science, 1988, 43(12): 3185-3195.

[1]	胡婷霞, 赵立欣, 姚宗路, 霍丽丽, 贾吉秀, 谢腾. 双金属催化剂在生物质焦油催化蒸汽重整领域的研究进展[J]. 化工进展, 2024, 43(8): 4354-4365.
[2]	张叶素, 权燕红, 丁欣欣, 任军. 链状MFI型分子筛的合成与应用[J]. 化工进展, 2024, 43(8): 4382-4392.
[3]	王嘉, 李文翠, 吴凡, 高新芊, 陆安慧. NiMo/Al₂O₃催化剂活性组分分布调控及其加氢脱硫应用[J]. 化工进展, 2024, 43(8): 4393-4402.
[4]	张子杭, 王树荣. 生物质热解转化与产物低碳利用研究进展[J]. 化工进展, 2024, 43(7): 3692-3708.
[5]	龚德成, 沈倩, 朱贤青, 黄云, 夏奡, 张敬苗, 朱恂, 廖强. 微藻超临界水气化制取富氢合成气的研究进展[J]. 化工进展, 2024, 43(7): 3709-3728.
[6]	郭鹏, 李红伟, 李贵贤, 季东, 王东亮, 赵新红. 直接甲醇燃料电池阳极催化剂的失活机制及应对策略[J]. 化工进展, 2024, 43(7): 3812-3823.
[7]	王丽娜, 武金升. 共价有机框架材料的合成与应用研究进展[J]. 化工进展, 2024, 43(7): 3834-3856.
[8]	罗丛佳, 豆义波, 卫敏. 水滑石光催化剂结构调控用于二氧化碳还原的研究进展[J]. 化工进展, 2024, 43(7): 3891-3909.
[9]	何弈雪, 秦先超, 马伟芳. 过硫酸盐高级氧化原位修复地下水中卤代烃污染研究进展[J]. 化工进展, 2024, 43(7): 4072-4088.
[10]	蓝瑞嵩, 刘丽华, 张倩, 陈博彦, 洪俊明. 硫掺杂石墨烯作为MFC阴极性能和生物毒性检测[J]. 化工进展, 2024, 43(6): 3430-3439.
[11]	李亚男, 郭凯, 王嘉琪, 武亚宁. 煤气化渣活化过二硫酸盐和过一硫酸盐降解苯酚的比较[J]. 化工进展, 2024, 43(6): 3503-3512.
[12]	张真, 张凡, 云祉婷. 绿氢在石化和化工行业的减碳经济性分析[J]. 化工进展, 2024, 43(6): 3021-3028.
[13]	何世坤, 张文豪, 冯君锋, 潘晖. 负载金属型固体酸催化木质纤维生物质定向转化为乙酰丙酸甲酯[J]. 化工进展, 2024, 43(6): 3042-3050.
[14]	陈富强, 仲兆平, 戚仁志. 铜基催化剂电还原二氧化碳为甲酸研究进展[J]. 化工进展, 2024, 43(6): 3051-3060.
[15]	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.

CO-CO₂体系制备氘代甲醇催化剂的合成与改性

Synthesis and modification of deuterated methanol catalyst used in CO-CO₂ system

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 12

参考文献 21

相关文章 15

编辑推荐

Metrics

本文评价