低温深度脱除液相丙烯中微量CO的CuO(y)/CuxCe1-xOδ催化剂表征分析及性能实验

doi:10.16085/j.issn.1000-6613.2020-0315

化工进展 ›› 2020, Vol. 39 ›› Issue (12): 5104-5111.DOI: 10.16085/j.issn.1000-6613.2020-0315

低温深度脱除液相丙烯中微量CO的CuO(y)/Cu_xCe_1-_xO_δ催化剂表征分析及性能实验

顾慧劼¹^,²(), 李磊³^,⁴, 叶丽萍¹^,²^,⁴(), 黄河³^,⁴, 罗勇¹^,²^,⁴, 金政伟³^,⁴

^1.聚烯烃催化技术与高性能材料国家重点实验室，上海 200062
^2.上海化工研究院有限公司，上海 200062
^3.国家能源集团宁夏煤业有限责任公司煤炭化学工业技术研究院，宁夏银川 750411
^4.宁夏煤基合成树脂高值化产业技术协同创新中心，宁夏银川 750411

出版日期:2020-12-05 发布日期:2020-12-02
通讯作者: 叶丽萍
作者简介:顾慧劼（1990—），女，硕士，研究方向为工业催化净化。E-mail：ghjmianyang@126.com。
基金资助:
上海人才发展资金(2018019);宁夏煤基合成树脂高值化产业技术协同创新中心(2017DC57)

Characterization of CuO(y)/Cu_xCe_1-_xO_δ mixed-oxide catalysts and their performance in deep removal of trace amount of CO in liquid-phase propylene

Huijie GU¹^,²(), Lei LI³^,⁴, Liping YE¹^,²^,⁴(), He HUANG³^,⁴, Yong LUO¹^,²^,⁴, Zhengwei JIN³^,⁴

^1.State Key Laboratory of Polyolefins and Catalysis, Shanghai 200062, China
^2.Shanghai Research Institute of Chemical Industry Co. , Ltd. , Shanghai 200062, China
^3.Institute of Coal Chemical Industry Technology, Ningxia Coal Industry Co. , Ltd. , CHN Energy Group, Yinchuan 750411, Ningxia, China
^4.Innovation Centre of Synergetic Technology of Coal-based Value-added Synthetic Resin Industry, Yinchuan 750411, Ningxia, China

Online:2020-12-05 Published:2020-12-02
Contact: Liping YE

摘要/Abstract

摘要：

采用柠檬酸络合-浸渍的方法制备了CuO(y)/Cu_xCe_1-_xO_δ催化剂，重点研究了CuO的载体掺杂和表面负载对催化剂结构性质、氧化还原性能、吸附性能及CO净化性能等的影响，旨在指导催化剂进一步改性，实现低温下深度脱除液相丙烯中微量CO的工业化应用。采用X射线衍射（XRD）、透射电镜（TEM）、X射线光电子能谱分析仪（XPS）、拉曼光谱仪（Raman）和程序升温化学吸附仪（H₂-TPR、CO-TPD）等手段表征了催化剂的结构和性质，结果显示，CuO掺杂的载体，Cu进入CeO₂晶体形成固溶体，有利于催化剂氧化还原性能；浸渍法负载CuO制得的催化剂，表面具有更多的还原态、高分散的Cu物种，有利于表面对CO吸附性能；两者协同作用共同促进了CO催化氧化性能的提升。CuO(0.40)/Cu_0.1Ce_0.9O_δ催化剂具有优异的CO净化性能，在50℃、3.0MPa的工况条件下，可将液相丙烯中CO体积分数从1×10^-5脱除至2.65±0.27×10^-8，达到聚合级烯烃对CO脱除深度的要求，稳定性能良好。

关键词: 催化剂, 载体, 吸附作用, 一氧化碳, 深度脱除, 液相丙烯

Abstract:

Three CuO(y)/Cu_xCe_1-_xO_δcatalysts with different compositions were prepared and evaluated for the removal of trace CO in liquid-phase propylene at low temperature. The effects of the surface Cu species and Cu_xCe_1-_xO_δsolid solution on the structure, redox ability, surface state and CO oxidation activity were investigated, aiming to gain guide for further modification of the catalysts and finally to realize the industrial application. The catalysts were characterized by XRD, TEM, XPS, H₂-TPR, CO-TPD, etc. which showed that in the carrier Cu_xCe_1-_xO_δprepared by citric acid complexation, the copper particles could enter into the crystal lattice of cerium oxide, which enhanced the reducibility of the catalyst for oxygen activation. And the catalyst improved by impregnation method on this carrier, had more reduced and highly dispersed Cu species on the surface, which was beneficial to the chemisorption of CO. Therefore, the CO oxidation was promoted by the synergistic interaction. CuO(0.40)/Cu_0.1Ce_0.9O_δ_{exhibited the highest activity for CO conversion. Under the conditions of 50℃, LHSV=8h^-1 and 3.0MPa, the volume fraction of CO in liquid propylene decreased from 1.0×10^-5 to 2.65±0.27×10^-8 with good stability, which met the requirements of "polymer grade" propylene.}

Key words: catalyst, support, adsorption, carbon monoxide, deep removal, liquid propylene

中图分类号:

TQ032.41

顾慧劼, 李磊, 叶丽萍, 黄河, 罗勇, 金政伟. 低温深度脱除液相丙烯中微量CO的CuO(y)/Cu_xCe_1-_xO_δ催化剂表征分析及性能实验[J]. 化工进展, 2020, 39(12): 5104-5111.

Huijie GU, Lei LI, Liping YE, He HUANG, Yong LUO, Zhengwei JIN. Characterization of CuO(y)/Cu_xCe_1-_xO_δ mixed-oxide catalysts and their performance in deep removal of trace amount of CO in liquid-phase propylene[J]. Chemical Industry and Engineering Progress, 2020, 39(12): 5104-5111.

参考文献

1	LUO Zhenghong, CAO Zhikai, SU Yaotang, et al. Monte carlo simulation of propylene polymerization (Ⅰ) effects of impurity on propylene polymerization[J]. Chinese Journal of Chemical Engineering, 2006, 14: 194-199.
2	马晶, 夏先知,张天一, 等. 微量杂质对丙烯聚合性能的影响[J]. 石油化工, 2013, 42(7): 767- 770.
2	MA Jing, XIA Xianzhi, ZHANG Tianyi, et al. Effect of trace impurities on propylene polymerization[J]. Petrochemical Technology, 2013, 42(7): 767-770.
3	王树立. 采用固定床催化剂技术脱除炼厂丙烯中的一氧化碳[J]. 石化技术与应用, 2009, 27(2): 159-161.
3	WANG Shuli. Application of fixed bed catalyst technique in removing carbon monoxide from refinery propylene[J]. Petrochemical Technology & Application, 2009, 27(2): 159-161.
4	HENZE G, KARRER L, ARTRIP D J, et al. Process for the activation of a copper-, zinc- and zirconium oxide-comprising adsorption composition: US 8637723B2[P]. 2011-09-07.
5	王育, 马天石, 刘海江, 等. 液相丙烯脱CO催化剂的研究[J]. 石油化工, 2015, 44(7): 798-803.
5	WANG Yu, MA Tianshi, LIU Haijiang, et al. CuO/ZnO/ZrO₂ catalyst used in deep removal of carbon monoxide in liquid propylene[J]. Petrochemical Technology, 2015, 44(7):798-803.
6	XIE Y C, BU N Y, LIU J, et al. Adsorbents for use in the separation of carbon monoxide and/or unsaturated hydrocarbons from mixed gases: US 4917711[P]. 1990-04-17.
7	DONG L, YAO X, CHEN Y. Chem-inform abstract: interactions among supported copper-based catalyst components and their effects on performance: a review[J]. Chinese Journal of Catalysis, 2013, 34(5):851-864.
8	顾慧劼, 叶丽萍, 李帅, 等. CuO含量对yCuO/Cu_xCe_1-_xO_δ催化剂脱除微量CO性能的影响[J]. 精细化工, 2015, 32(4): 999- 1003, 1008.
8	GU Huijie, YE Liping, LI Shuai, et al. The influences of CuO content on yCuO/Cu_xCe_1-_xO_δ catalysts in deep removal of trace amount of CO[J]. Fine Chemicals, 2015, 32(4):999-1003, 1008.
9	HE C, YU Y, YUE L, et al. Low temperature removal of toluene and propanal over highly active mesoporous CuCeO_x catalysts synthesized via a simple self-precipitation protocol[J]. Applied Catalysis B: Environmental, 2014, 147: 156-166.
10	ELIAS J S, ARTRITH N, BUGNET M, et al. Elucidating the nature of the active phase in copper/ceria catalysts for CO oxidation[J]. ACS Catalysis, 2016, 6: 1675-1679.
11	LUO M F, MA J M, LU J Q, et al. High-surface area CuO-CeO₂ catalysts prepared by a surfactant-templated method for low- temperature CO oxidation[J]. Journal of Catalysis, 2007, 246: 52-59.
12	AMIT S, MITAL G S. Ce_1-_xO_?Cu_x nanoparticles: synthesis, characterization and catalytic activity for phenol degradation[J]. Journal of Nanoscience and Nanotechnology, 2019, 19(8): 5220-5226.
13	QI L, YU Q, DAI Y, et al. Influence of cerium precursors on the structure and reducibility of mesoporous CuO-CeO₂ catalysts for CO oxidation[J]. Applied Catalysis B: Environmental, 2012, 119: 308-320.
14	XIE Y, YIN Y L, ZENG S H, et al. Coexistence of Cu⁺ and Cu²⁺ in star-shaped CeO₂/Cu_xO catalyst for preferential CO oxidation[J]. Catalysis Communications, 2017, 99: 110-114.
15	HUANG B, KOBAYASHI H, YAMAMOTO T, et al. A CO adsorption site change induced by copper substitution in a ruthenium catalyst for enhanced CO oxidation activity[J]. Angewandte Chemie (International ed. in English), 2019, 58(8): 2230-2235.
16	JIA A P, HU G S, GE L, et al. CO oxidation over CuO/Ce_1-_xCu_xO_2-_δ and Ce_1-_xCu_xO_2-_δcatalysts: synergetic effects and kinetic study[J]. Journal of Catalysis, 2012, 289: 199-209.
17	FIRSOVA A A, MOROZOVA O S, VOROB’EVA G A, et al. Mechanochemical activation of Cu-CeO₂ mixture as a promising technique for the solid-state synthesis of catalysts for the selective oxidation of CO in the presence of H₂[J]. Kinetics and Catalysis, 2018, 59(2): 160-173.
18	LEE D S, CHEN Y W. Au/CuO-CeO₂ catalyst for preferential oxidation of CO in hydrogen-rich stream: effect of CuO content[J]. International Journal of Hydrogen Energy, 2016, 41: 3605-3612.
19	CHAGAS C A, SOUZA E F, MANFRO R L, et al. Copper as promoter of the NiO-CeO₂ catalyst in the preferential CO oxidation[J]. Applied Catalysis B: Environmental, 2016, 38: 750-755.
20	MOCK S A, SHARP S E, STONER T R, et al. CeO₂ nanorods- supported transition metal catalysts for CO oxidation[J]. Journal of Colloid and Interface Science, 2016, 466: 261-267.
21	CHEN J, LI W, SHEN R. CO hydrogenation to higher alcohols over Ni- and Mo-modified Cu/CeO₂ catalyst [J]. Korean Journal of Chemical Engineering, 2016, 33: 500-506.
22	WAN Y Y, YANG G P, XIANG J Y, et al. Promoting effects of water on the NH₃-SCR reaction over Cu-SAPO-34 catalysts: transient and permanent influences on Cu species[J]. Dalton Transactions (Cambridge, England), 2019, 49: 764-773.

[1]	张明焱, 刘燕, 张雪婷, 刘亚科, 李从举, 张秀玲. 非贵金属双功能催化剂在锌空气电池研究进展[J]. 化工进展, 2023, 42(S1): 276-286.
[2]	时永兴, 林刚, 孙晓航, 蒋韦庚, 乔大伟, 颜彬航. 二氧化碳加氢制甲醇过程中铜基催化剂活性位点研究进展[J]. 化工进展, 2023, 42(S1): 287-298.
[3]	谢璐垚, 陈崧哲, 王来军, 张平. 用于SO₂去极化电解制氢的铂基催化剂[J]. 化工进展, 2023, 42(S1): 299-309.
[4]	杨霞珍, 彭伊凡, 刘化章, 霍超. 熔铁催化剂活性相的调控及其费托反应性能[J]. 化工进展, 2023, 42(S1): 310-318.
[5]	王乐乐, 杨万荣, 姚燕, 刘涛, 何川, 刘逍, 苏胜, 孔凡海, 朱仓海, 向军. SCR脱硝催化剂掺废特性及性能影响[J]. 化工进展, 2023, 42(S1): 489-497.
[6]	邓丽萍, 时好雨, 刘霄龙, 陈瑶姬, 严晶颖. 非贵金属改性钒钛基催化剂NH₃-SCR脱硝协同控制VOCs[J]. 化工进展, 2023, 42(S1): 542-548.
[7]	程涛, 崔瑞利, 宋俊男, 张天琪, 张耘赫, 梁世杰, 朴实. 渣油加氢装置杂质沉积规律与压降升高机理分析[J]. 化工进展, 2023, 42(9): 4616-4627.
[8]	王鹏, 史会兵, 赵德明, 冯保林, 陈倩, 杨妲. 过渡金属催化氯代物的羰基化反应研究进展[J]. 化工进展, 2023, 42(9): 4649-4666.
[9]	高彦静. 单原子催化技术国际研究态势分析[J]. 化工进展, 2023, 42(9): 4667-4676.
[10]	张启, 赵红, 荣峻峰. 质子交换膜燃料电池中氧还原反应抗毒性电催化剂研究进展[J]. 化工进展, 2023, 42(9): 4677-4691.
[11]	王伟涛, 鲍婷玉, 姜旭禄, 何珍红, 王宽, 杨阳, 刘昭铁. 醛酮树脂基非金属催化剂催化氧气氧化苯制备苯酚[J]. 化工进展, 2023, 42(9): 4706-4715.
[12]	葛亚粉, 孙宇, 肖鹏, 刘琦, 刘波, 孙成蓥, 巩雁军. 分子筛去除VOCs的研究进展[J]. 化工进展, 2023, 42(9): 4716-4730.
[13]	李东泽, 张祥, 田键, 胡攀, 姚杰, 朱林, 卜昌盛, 王昕晔. 基于水泥窑脱硝的碳基还原NO _x 研究进展[J]. 化工进展, 2023, 42(9): 4882-4893.
[14]	吴海波, 王希仑, 方岩雄, 纪红兵. 3D打印催化材料开发与应用进展[J]. 化工进展, 2023, 42(8): 3956-3964.
[15]	王报英, 王皝莹, 闫军营, 汪耀明, 徐铜文. 聚合物包覆膜在金属分离回收中的研究进展[J]. 化工进展, 2023, 42(8): 3990-4004.

低温深度脱除液相丙烯中微量CO的CuO(y)/Cu_xCe_1-_xO_δ催化剂表征分析及性能实验

Characterization of CuO(y)/Cu_xCe_1-_xO_δ mixed-oxide catalysts and their performance in deep removal of trace amount of CO in liquid-phase propylene

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

编辑推荐

Metrics

本文评价

低温深度脱除液相丙烯中微量CO的CuO(y)/CuxCe1-xOδ催化剂表征分析及性能实验

Characterization of CuO(y)/CuxCe1-xOδ mixed-oxide catalysts and their performance in deep removal of trace amount of CO in liquid-phase propylene

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

编辑推荐

Metrics

本文评价

低温深度脱除液相丙烯中微量CO的CuO(y)/Cu_xCe_1-_xO_δ催化剂表征分析及性能实验

Characterization of CuO(y)/Cu_xCe_1-_xO_δ mixed-oxide catalysts and their performance in deep removal of trace amount of CO in liquid-phase propylene