新型Ru基催化剂的制备及其2-乙基蒽醌加氢性能

doi:10.16085/j.issn.1000-6613.2020-0599

摘要/Abstract

摘要：

通过等体积浸渍法和多元醇法制备了负载型钌氧化铝催化剂（Ru/Al₂O₃-IMP和Ru/Al₂O₃-CRP），并首次探究了其在2-乙基蒽醌（2-eAQ）加氢催化反应中的性能。实验发现，在不同的反应条件（温度、压力、时间）下，Ru/Al₂O₃-CRP催化剂催化2-eAQ加氢反应的活性均高于Ru/Al₂O₃-IMP催化剂。采用电感耦合等离子体原子发射光谱（ICP-AES）、X射线衍射（XRD）、透射电镜（TEM）、光电子能谱（XPS）等分析技术对两种催化剂进行了结构表征。XRD和TEM表征结果发现，Ru/Al₂O₃-CRP催化剂表面的Ru金属颗粒具有高分散性且颗粒尺寸分布较窄。此外，XPS表征结果证实Ru/Al₂O₃-CRP催化剂上钌的电子云密度低，这使得它对2-eAQ上氧孤对电子有着强的吸引力，有利于活化2-eAQ，进而表现出强的加氢反应活性。

关键词: 钌/氧化铝, 加氢, 多元醇法

Abstract:

The aluminum oxide supported ruthenium catalysts were prepared by impregnation and polyol method (i.e., Ru/Al₂O₃-IMP and Ru/Al₂O₃-CRP), and their performance in the hydrogenation of 2-ethylanthraquinone (2-eAQ) was investigated. It was found that the catalysts prepared by different methods were all active and the Ru/Al₂O₃-CRP catalyst exhibited relatively high catalytic activity and stability. The catalysts were characterized by inductively coupled plasma atomic emission spectrometry (ICP-AES), X-ray diffraction (XRD), transmission electron microscopy (TEM) and photoelectron spectroscopy (XPS). The XRD and TEM results suggested that Ru particles were highly dispersed on the surface of the support. In addition, the Ru/Al₂O₃-CRP catalyst exhibited a low electron cloud density of Ru according to the XPS results, which made the Ru active sites more attractive to the lone pair electrons on the oxygen of 2-eAQ, and hence was conducive to activation of 2-eAQ.

Key words: Ru/Al₂O₃, hydrogenation, polyol method

中图分类号:

O643.36

谢继阳, 王红琴, 杨杰, 唐春, 戴云生, 安霓虹. 新型Ru基催化剂的制备及其2-乙基蒽醌加氢性能[J]. 化工进展, 2021, 40(2): 901-907.

Jiyang XIE, Hongqin WANG, Jie YANG, Chun TANG, Yunsheng DAI, Nihong AN. Preparation of a novel Ru-based catalyst and its performance in the hydrogenation of 2-ethylanthraquinone[J]. Chemical Industry and Engineering Progress, 2021, 40(2): 901-907.

图/表 10

图1 Ru/Al2O3-IMP催化剂和Ru/Al2O3-CRP催化剂催化性能与反应压力的关系

图2 Ru/Al2O3-IMP催化剂和Ru/Al2O3-CRP催化剂催化性能与反应温度的关系

图3 Ru/Al2O3-IMP催化剂和Ru/Al2O3-CRP催化剂催化性能与反应时间的关系

图4 Ru/Al2O3-IMP催化剂和Ru/Al2O3-CRP催化剂的稳定性实验

图5 Al2O3、Ru/Al2O3-IMP催化剂和Ru/Al2O3-CRP催化剂的N2吸附-脱附等温曲线

表1 Al2O3载体、Ru/Al2O3-IMP催化剂和Ru/Al2O3-CRP催化剂的结构参数

样品名称	比表面积^①/m²·g^-1	平均孔径^①/nm	孔容^①/cm³·g^-1	Ru质量分数^②/%	Ru粒径^③/nm	TOF^④/s^-1
Al₂O₃	100.7	17.6	0.46	—	—	—
Ru/Al₂O₃-IMP	97.3	16.5	0.44	0.99	4.8	1.78
Ru/Al₂O₃-CRP	97.8	16.7	0.45	0.99	2.3	2.86

图6 Ru/Al2O3-IMP催化剂和Ru/Al2O3-CRP催化剂的XRD谱图

图7 Ru/Al2O3-IMP催化剂和Ru/Al2O3-CRP催化剂的TEM图和粒径分布

图8 Ru/Al2O3-IMP催化剂和Ru/Al2O3-CRP催化剂的XPS谱图

表2 Ru/Al2O3-IMP催化剂和Ru/Al2O3-CRP催化剂的XPS表征结果

样品	Ru 3p_3/2/eV		Ru 3p_1/2/eV
样品	Ru⁰	Ru^δ⁺	Ru⁰	Ru^δ⁺
Ru/Al₂O₃-IMP	462.1	465.1	484.3	487.0
Ru/Al₂O₃-CRP	463.5	466.7	485.7	488.6

参考文献 27

1	王伟建, 潘智勇, 李文林, 等. 蒽醌法流化床与固定床的发展趋势[J]. 化工进展, 2016, 35(6): 1766-1773.
	WANG W J, PAN Z Y, LI W L, et al. Recent advances in development of the fluidized bed and fixed bed in the anthraquinoneroute[J]. Chemical Industry and Engineering Progress, 2016, 35(6): 1766-1773.
2	GUO Y Y, DAI C N, LEI Z G, et al. Synthesis of hydrogen peroxide over Pd/SiO₂/COR monolith catalysts by anthraquinone method[J]. Catalysis Today, 2016, 276: 36-45.
3	GUO Y Y, DAI C N, LEI Z G, et al. Hydrogenation of 2-ethylanthraquinone on Pd-La/SiO₂/cordierite and Pd-Zn/SiO₂/cordierite bimetallic monolithic catalysts[J]. Chemical Engineering and Processing Process Intensification, 2019, 136: 211-225.
4	SANTACESARIA E, FERRO R, RICCI S, et al. Kinetic aspects in the oxidation of hydrogenate 2-ethyltetrahydroanthraquinone[J]. Industrial & Engineering Chemistry Research, 1987, 26: 155-159.
5	SHEIKH J, KERSHENBAUM J, ALPAY E. Analytical basis for separation enhanced reaction in continuous flow processes[J]. Chemical Engineering Science, 1988, 53: 2933-2939.
6	严润华, 蔡卫权, 卓俊琳, 等. 一锅溶剂蒸发诱导自组装法制备助剂体相分布的Pd-Ba-Zn/γ-Al₂O₃催化剂及其蒽醌加氢性能[J]. 化工进展, 2018, 37(3): 1014-1020.
	YAN R H, CAI W Q, ZHUO J L, et al. One-pot solvent evaporation induced self-assembly synthesis of Pd-Ba-Zn/γ-Al₂O₃ catalyst with homogeneous distribution of the promoters and its hydrogenation performance of anthraquinone [J]. Chemical Industry and Engineering Progress, 2018, 37(3): 1014-1020.
7	FENG J T, WANG H Y, XUE D, et al. Catalytic hydrogenation of ethylanthraquinone over highly dispersed eggshell Pd/SiO₂-Al₂O₃ spherical catalysts[J]. Applied Catalysis A: General, 2010, 382: 240-245.
8	ZHANG D, LUO J J, XIAO X, et al. Ru/FeO_x catalyst performance design: highly dispersed Ru species for selective carbon dioxide hydrogenation[J]. Chinese Journal of Catalysis, 2018, 39: 157-166.
9	GUO X, WANG X C, XIAN M, et al. Selective hydrogenation of D-glucose to D-sorbitol over Ru/ZSM-5 catalysts[J]. Chinese Journal of Catalysis, 2014, 35: 733-740.
10	MICHELLE F, ANTONIO J. Influence of the support nature and morphology on the performance of ruthenium catalysts for partial hydrogenation of benzene in liquid phase[J]. Catalysis Today, 2010, 149: 321-325.
11	HUANG B, KIOBAYASHI H, YAMAMOTO T, et al. Solid-solution alloying immiscible Ru and Cu with enhanced CO oxidation activity[J]. Journal of the American Chemical society, 2017, 139: 4643-4646.
12	KATARZYNA B, JANINA O, WLODZIMIERZ T. Microwave-assisted polyol synthesis of bimetallic RuRe nanoparticles stabilized by PVP or oxide supports (alumina and silica) [J]. Applied Catalysis A: General, 2015, 511: 117-130.
13	ALAYOGLU S, ZAVAIJ P, ERICHHOM B, et al. Structural and architectural evaluation of bimetallic nanoparticles: a case study of Pt-Ru core-shell and alloy nanoparticles[J]. ACS Nano, 2009, 3: 3127-3137.
14	FILIP M, CHRISTOPHER M, KAREL H. Protein unfolding, amyloid fibril formation and configurational energy landscapes under high pressure conditions[J]. Chemical Society Reviews, 2006, 108: 845-904.
15	ALAYOGLU S, ERICHHOMM B, NILEKAR A, et al. Ru-Pt core-shell nanoparticles for preferential oxidation of carbon monoxide in hydrogen[J]. Nature Materials, 2008, 7: 333-338.
16	AKANE M, IOAN B, YOSHIO N, et al. Preparation of Ru nanoparticles supported on γ-Al₂O₃ and its novel catalytic activity for ammonia synthesis[J]. Journal of Catalysis, 2001, 204: 364-371.
17	陈纪兴. 蒽醌法双氧水生产中加氢反应原理及其控制[J]. 无机盐工业, 2000, 32(2):36-40.
	CHEN J X. The principle and control of hydrogenation in the production process of hydrogen peroxide with 2-EAQ as working medium[J]. Inorganic Chemicals Industry, 2000, 32(2): 36-40.
18	ZHANG J L, GAO K G, WANG S L, et al. Performance of bimetallic PdRu catalysts supported on gamma alumina for 2-ethylanthraquinone hydrogenation[J]. RSC Advances, 2017, 7: 6447-6456.
19	YU J F, GE J, FANG W, et al. Influences of calcination temperature on the efficiency of CaO promotion over CaO modified Pt/γ-Al₂O₃ catalyst[J]. Applied Catalysis A: General, 2011, 395: 114-119.
20	SHI Y, LI X R, RONG X, et al. Influence of support on the catalytic properties of Pt-Sn-K/θ-Al₂O₃ for propane dehydrogenation[J]. RSC Advances, 2017, 7: 19841-19848.
21	OKAL J, ZAWADZKI M, TYLUS W. Microstructure characterization and propane oxidation over supported Ru nanoparticles synthesized by the microwave-polyol method[J]. Applied Catalysis B: Environmental, 2011, 101: 548-559.
22	STEFANOV P, TODOROVA, NAYDENOV A, et al. On the development of active and stable Pd-Co/γ-Al₂O₃, catalyst for complete oxidation of methane[J]. Chemical Engineering Journal, 2015, 266(8):329-338.
23	LI Y, FENG J, HE Y, et al. Controllable synthesis, structure, and catalytic activity of highly dispersed Pd catalyst supported on whisker-modified spherical alumina[J]. Industrial & Engineering Chemistry Research, 2015, 51(34): 11083-11090.
24	ZAWADZKI M, OKAL J. Synthesis and structure characterization of Ru nanoparticles stabilized by PVP or γ-Al₂O₃[J]. Materials Research Bulletin, 2008, 43: 3111-3121.
25	YUAN E, WU C, HOU X, et al. Synergistic effects of second metals on performance of (Co, Ag, Cu)-doped Pd/ Al₂O₃, catalysts for 2-ethyl-anthraquinone hydrogenation[J]. Journal of Catalysis, 2017, 347(10):79-88.
26	何志远. 蒽醌加氢反应钯基催化剂的研究[D]. 天津:天津大学, 2015.
	HE Z Y. Study on Pd-based catalyst for anthraquinone hydrogenation reaction[D]. Tianjin: Tianjin University, 2015.
27	MOHAMMAD N, TURN S. Characterization of Ru/Q10 catalysts containing Zr or Mn and their activity for Fischer-Tropsch synthesis[J]. Fuel Processing Technology, 2015, 5: 1-10.

[1]	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.
[2]	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.
[3]	毛善俊, 王哲, 王勇. 基团辨识加氢：从概念到应用[J]. 化工进展, 2023, 42(8): 3917-3922.
[4]	王兰江, 梁瑜, 汤琼, 唐明兴, 李学宽, 刘雷, 董晋湘. 快速热解铂前体合成高分散的Pt/HY催化剂及其萘深度加氢性能[J]. 化工进展, 2023, 42(8): 4159-4166.
[5]	王晓晗, 周亚松, 于志庆, 魏强, 孙劲晓, 姜鹏. 不同晶粒尺寸Y分子筛的合成及其加氢裂化反应性能[J]. 化工进展, 2023, 42(8): 4283-4295.
[6]	于志庆, 黄文斌, 王晓晗, 邓开鑫, 魏强, 周亚松, 姜鹏. B掺杂Al₂O₃@C负载CoMo型加氢脱硫催化剂性能[J]. 化工进展, 2023, 42(7): 3550-3560.
[7]	李栋先, 王佳, 蒋剑春. 皂脚热解-催化气态加氢制备生物燃料[J]. 化工进展, 2023, 42(6): 2874-2883.
[8]	陈怡欣, 甄摇摇, 陈瑞浩, 吴继伟, 潘丽美, 姚翀, 罗杰, 卢春山, 丰枫, 王清涛, 张群峰, 李小年. 铂基纳米催化剂的制备及在加氢领域的进展[J]. 化工进展, 2023, 42(6): 2904-2915.
[9]	徐贤, 崔楼伟, 刘杰, 施俊合, 朱永红, 刘姣姣, 刘涛, 郑化安, 李冬. 原料组成对半焦中间相结构发展的影响[J]. 化工进展, 2023, 42(5): 2343-2352.
[10]	王嘉, 彭冲, 唐磊, 陆安慧. 渣油加氢催化剂活性相结构调控及对反应性能影响[J]. 化工进展, 2023, 42(4): 1811-1821.
[11]	李玲, 马超峰, 卢春山, 于万金, 石能富, 金佳敏, 张建君, 刘武灿, 李小年. 新型含氟替代品1,1,2-三氟乙烯的合成工艺与催化剂研究进展[J]. 化工进展, 2023, 42(4): 1822-1831.
[12]	葛伟童, 廖亚龙, 李明原, 嵇广雄, 郗家俊. Pd-Fe/MWCNTs双金属催化剂制备及其脱氯动力学[J]. 化工进展, 2023, 42(4): 1885-1894.
[13]	萧垚鑫, 张军, 胡升, 单锐, 袁浩然, 陈勇. 甲醇供氢体系铜锌双金属催化糠醛加氢转化[J]. 化工进展, 2023, 42(3): 1341-1352.
[14]	李乃珍, 孙瑞洁, 秦志峰, 苗茂谦, 吴琼笑, 常丽萍, 孙鹏程, 曾剑, 刘毅. 焦炉煤气常量含碳气氛对加氢脱硫催化剂活性、选择性和积炭的影响[J]. 化工进展, 2023, 42(2): 783-793.
[15]	崔瑞利, 程涛, 宋俊男, 牛贵峰, 刘圆元, 张涛, 赵愉生, 王路海. 固定床渣油加氢脱残炭催化剂的再生表征及性能评价[J]. 化工进展, 2023, 42(10): 5200-5204.