2 195/O6 .chxb.cn No. THHPD3 w 32 2011 CN 21-1 ISSN 0253-9837 ISSN CODEN CODEN ol. http://ww V YSIS
AL OF CAT
中 国 化 学 会 催 化 学 会 会 刊 ransaction of the Catalysis Society of China ransaction of the Catalysis T
CHINESE JOURNAL CHINESE Editor-in-Chief LIN Liwu 主编 林励吾
报
学 化 催 CHINESE JOURNAL OF CATALYSIS February 2011 Vol. 32 No. 2 pages 207- 386
2011 年 2011 第 32 卷 第 2 期 CHINESE JOURNAL OF CATALYSIS Vol. 32 No. 2 In This Issue
封面: Menéndez 教授等综述了碳催化剂上 CH4 裂解及其与 CO2 的重
整反应, 见本期第 207~216 页. 碳催化剂上的 CH4 与 CO2 重整可看作是 CH4 裂解和沉积碳与 CO2 气化反应的组合. CH4 裂解生成 H2 和沉积碳, 而 后者堵塞了碳催化剂上的活性位. 随后, 至少这些具有高活性的沉积碳可
被 CO2 气化, 使得碳催化剂上的活性位得以原位和连续地再生. Cover: Prof. Menéndez and coworkers in their article on pages 207–216 reviewed the recent development of carbon catalysts for decomposition and CO2 reforming of methane. The dry reforming reaction over carbonaceous catalysts can be considered a combination of CH4 decomposition and CO2 gasification of carbon deposits. The decomposition of CH4 gives rise to hy- drogen and carbonaceous deposits, which block the active centers on the car- bon catalyst. Then, the deposits, at least those which are highly reactive, are gasified by the CO2, leading to an in situ and continuous regeneration of the active centers on the carbon catalyst.
About the Journal
Chinese Journal of Catalysis is published monthly by Chinese Chemical Society and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. The objective of the journal is to publish original, rigorous, and scholarly contributions in the fields of heteroge- neous and homogeneous catalysis. The journal accepts papers in Chinese and English.
Scope of the Journal Impact Factor z New trends in heterogeneous and homogeneous catalysis in relation to 0.786 (ISI) 0.755 (ISI, 5-Year Impact Factor) energy, environment, new materials, petroleum chemicals, and fine 0.940 (ISTIC) chemicals Abstracting and Indexing z Scientific bases for the preparation and activation of catalysts of com- Abstract Journals (VINITI) mercial interest or that are representative models Cambridge Scientific Abstracts (CIG) z Scientific methods for the characterization of heterogeneous catalysts, Catalysts & Catalysed Reactions (RSC) especially methods for in situ characterization Current Contents/Engineering, z New heterogeneous and homogeneous catalytic reactions of potential Computing and Technology (Thomson ISI) practical interest in environment, energy, and fine chemicals applica- Chemical Abstract Service/SciFinder (CAS) Chemistry Citation Index (Thomson ISI) tions Japan Information Center of Science and Technology z Relationship between homogeneous and heterogeneous catalysis Journal Citation Reports/Science Edition (Thomson ISI) z Theoretical studies on the structure and reactivity of catalysts Science Citation Index Expanded (Thomson ISI) z The journal also accepts contributions dealing with other issues related SCOPUS (Elsevier) to catalysis, such as photo-catalysis, bio-catalysis, surface science, and Web of Science (Thomson ISI) chemical kinetics. 国内数据库收录 Types of Contributions 《中文核心期刊要目总览》 《中国学术期刊文摘》(CSA) Reviews are surveys of recent progress on important topics of catalysis, 《中国科学引文数据库》(CSCD) with entire, systematic, and important information. Authors should have 《中国科技期刊精品数据库》 published articles in the field. More than 60 references are suggested. 《中国学术期刊综合评价数据库》(CAJCED) Communications rapidly report studies with significant innovation and 《中国期刊全文数据库》(CNKI) major academic value. They are limited to four Journal pages. After pub- 《万方数据资源系统》(ChinaInfor) lication, their full-text papers can also be submitted to this or other jour- 《中文科技期刊数据库》(VIP) nals. 《中文电子期刊服务数据库》(CEPS) Articles are original full-text reports on innovative, systematic, and 《中国化学文献数据库》(CCBD) complete results in catalysis. 《中国化学化工文摘》
2011年 2011 第32卷 第2期 CHINESE JOURNAL OF CATALYSIS Vol. 32 No. 2
《催化学报》第四届编辑委员会 月刊 SCI 收录 1980 年 3 月创刊 中国化学会催化学会会刊 The Fourth Editorial Board of Chinese Journal of Catalysis 2011年2月20日出版 顾问 (Advisors)
主管 中国科学院 蔡启瑞 (CAI Qirui) 胥诲熊 (XU Huixiong) Bernard DELMON (比利时) 主办 中国化学会 闵恩泽 (MIN Enze) Jürgen CARO (德国) Gerhard ERTL (德国) 中国科学院大连化学物理研究所 彭少逸 (PENG Shaoyi) Michel CHE (法国) Masaru ICHIKAWA (日本) 主编 林励吾 宋春山 (SONG Chunshan, 美国) 编辑 《催化学报》编辑委员会 出版 主编 (Editor-in-Chief)
林励吾 (LIN Liwu) 国内统一连续出版物号 CN 21-1195/O6 副主编 (Associate Editors-in-Chief) 国际标准连续出版物号 ISSN 0253-9837 CODEN THHPD3 包信和 (BAO Xinhe) 寇 元 (KOU Yuan) 张 涛 (ZHANG Tao) 广告经营许可证号 2102002008000002 高 滋 (GAO Zi) 刘宇新 (LIU Yuxin)
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Publication Monthly (12 issues) 伏义路 (FU Yilu) 沈之荃 (SHEN Zhiquan) 杨启华 (YANG Qihua) Started in March 1980 高 滋 (GAO Zi) 申文杰 (SHEN Wenjie) 杨维慎 (YANG Weishen) Transaction of the Catalysis Society of China 关乃佳 (GUAN Naijia) 苏宝连 (SU Baolian, 比利时) 杨向光 (YANG Xiangguang) Superintended by 郭新闻 (GUO Xinwen) 孙予罕 (SUN Yuhan) 余 林 (YU Lin) Chinese Academy of Sciences Sponsored by 何鸣元 (HE Mingyuan) 万惠霖 (WAN Huilin) 袁友珠 (YUAN Youzhu) Chinese Chemical Society and Dalian 贺鹤勇 (HE Heyong) 王德峥 (WANG Dezheng) 张 涛 (ZHANG Tao) Institute of Chemical Physics of CAS 胡友良 (HU Youliang) 王国祯 (WANG Guozhen) 赵进才 (ZHAO Jincai) Editor-in-Chief LIN Liwu Edited by Editorial Board of 贾继飞 (JIA Jifei, 美 国 ) 王建国 (WANG Jianguo) 郑小明 (ZHENG Xiaoming) Chinese Journal of Catalysis 寇 元 (KOU Yuan) 王祥生 (WANG Xiangsheng) 钟顺和 (ZHONG Shunhe) Published by Science Press 编辑部成员 (Editorial Office Staff)
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(CUIHUA XUEBAO) CHINESE JOURNAL OF CATALYSIS 中国科学院科学出版基金资助出版 月刊 SCI 收录 2011 年 2 月 第 32 卷 第 2 期 目 次
综 述 Viswanathan BALASUBRAMANIAN 286 207 (国际版/封面文章) Si 掺杂对 TiO2 空心微球微结构和光催化性能的影响 用于甲烷分解和甲烷二氧化碳重整的碳材料催化剂研究 李纲, 刘昉, 阳启华, 张昭 进展 Beatriz FIDALGO, J. Ángel MENÉNDEZ 293 SSZ-13 和 RUB-50 分子筛上甲醇制烯烃的对比研究 李鹏 张维萍 韩秀文 包信和 研究快讯 , , , 299 217 (国际版) 新型双膦配体的合成及其在 2-丁烯氢甲酰化反应中的应 动态水热合成 b 轴取向 MFI 型分子筛膜 用 李显明, 王正宝, 郑洁, 邵世群, 王胤超, 严玉山 张林, 李春, 付海燕, 袁茂林, 李瑞祥, 陈华 224 (国际版) 303 单层分散型 Ru-Zn 催化剂及其催化苯选择加氢制环己烯 载体焙烧温度对稀燃天然气汽车尾气净化
的性能 Pd/Zr0.5Al0.5O1.75 催化剂性能的影响 孙海杰, 张旭东, 陈志浩, 周小莉, 郭伟, 刘仲毅, 刘寿长 王云, 唐石云, 龙恩艳, 林之恩, 龚茂初, 陈耀强 231 (国际版) 309 胶束催化体系中的对映选择性环醚化反应 La 和 Mn 助剂对完全液相法制备的 CuZr 浆状催化剂结构 Bhupesh S. SAMANT, Sunil S. BHAGWAT 和性能的影响 235 (国际版) 高志华, 黄伟, 阴丽华, 谢克昌 用 Dawson 型聚氧钨酸乳液催化氧化燃油超深度脱硫 315 张永娜, 王璐, 张玉良, 蒋宗轩, 李灿 柠檬酸改性对掺 Ba 纳米 MgO 及其担载的 Ru 氨合成催化
剂性能的影响 研究论文 霍超, 夏庆华, 潘美华, 杨霞珍, 骆燕, 刘化章
240 (国际版) 321 炭气凝胶孔结构对其负载的 TiO2 光催化降解甲基橙性能 Al2O3 性质对加氢脱硫催化剂 Co-Mo/Al2O3 活性相形成的 影响 的影响 齐和日玛, 李会峰, 袁蕙, 张韫宏, 徐广通 崔华楠, 赵振华, 梁业如, 石建英, 吴丁财, 刘鸿, 符若文 250 (国际版) 325 载体对负载型 Ni-B 催化剂催化 2-乙基蒽醌加氢制 H2O2 反 高负载量 LaMnOx/SBA-15 的制备及其催化甲苯燃烧性能 张泽凯, 梁一微, 任倩茹, 刘华彦, 陈银飞 应性能的影响 陈雪莹, 乔明华, 贺鹤勇 258 (国际版) 333 纳米孔碳负载 Fe3O4 催化剂上苯直接羟基化制苯酚 Pezhman ARAB, Alireza BADIEI, Amir KOOLIVAND, Ti-MWW 催化氯丙烯环氧化反应动力学行为 Ghodsi MOHAMMADI ZIARANI 方向青, 王钰宁, 邓秀娟, 吴海虹, 吴鹏, 刘月明, 何鸣元 264 (国际版) 340
碱促进的钴酸镁催化剂上的氧化亚氮分解 冷等离子体喷射流对甲烷二氧化碳重整用 Ni/Al2O3 催化 Bahaa M. ABU-ZIED 剂的还原机制 胡诗婧, 龙华丽, 徐艳, 尚书勇, 印永祥 273 (国际版) 用于甲烷水蒸气重整的镍基催化剂的失活和再生 345 Seyed Meysam HASHEMNEJAD, Matin PARVARI 铜基催化剂上甘油脱水制备羟基丙酮 牛莎莎, 朱玉雷, 郑洪岩, 张维, 李永旺 280 (国际版) 聚合物负载的钯-咪唑催化烯烃加氢 352 Udayakumar VELU, Alexander STANISLAUS, Bi 添加对 MoVO/AlPO4 催化剂异丁烯选择氧化反应性能 Gayathri VIRUPAIAH, Shivakumaraiah, 的影响
王希涛, 王芬, 蒋实, 钟顺和 374
357 吸附柱色谱法制备负载型纳米金催化剂 翟新磊, 徐金光, 徐秀峰, 邹旭华, 齐世学, 祁彩霞, 核苷中 2'-位取代基对 Burkholderia cepacia 脂肪酶选择性 安立敦 酰化核苷的影响 王朝宇, 宗敏华 379 362 介孔氧化铝的制备及其在甲醇脱水制二甲醚反应中的应 用 无第二模板剂法合成多级结构 ZSM-5 分子筛微球及其在 聂仁峰, 王军华, 费金华, 侯昭胤, 郑小明 甲烷无氧芳构化反应中的应用
杨建华, 于素霞, 胡慧晔, 初乃波, 鲁金明, 殷德宏,
王金渠 相关信息
368 320 第七届全国环境催化与环境材料学术会议 制备方法对双介孔钴基催化剂结构及其费-托反应性能的 385 作者索引 影响
王俊刚, 李德宝, 侯博, 贾丽涛, 贾利宏, 孙志强, 刘斌, 郭金刚, 任润厚, 孙予罕 www.chxb.cn
(CUIHUA XUEBAO)
Supported by the Science Publication CHINESE JOURNAL OF CATALYSIS Foundation of the CAS Monthly Vol. 32 No. 2 February 2011 Contents
Review
Chin. J. Catal., 2011, 32: 207–216 doi: 10.1016/S1872-2067(10)60166-0
Carbon Materials as Catalysts for Decomposition and CO2 Reforming of Methane: A Review
Beatriz FIDALGO, J. Ángel MENÉNDEZ* Instituto Nacional del Carbón (CSIC), Spain
2H2 CH4
CO2 2CO Methane CO 2 C decomposition C gasification
DRY REFORMING CH + CO = 2H + 2CO 4 2 2
Decomposition and CO2 reforming of methane over carbon catalysts are reviewed. The focus was on the relationship between the physicochemical properties of the carbon catalysts and their catalytic activity and why they get deactivated.
Communications
Chin. J. Catal., 2011, 32: 217–223 doi: 10.1016/S1872-2067(10)60167-2
Dynamic Hydrothermal Synthesis of a b-Oriented MFI Zeolite Film
LI Xianming, WANG Zhengbao*, ZHENG Jie, SHAO Shiqun, WANG Yinchao, YAN Yushan Zhejiang University, China; University of California, Riverside, USA
Continuous b-oriented MFI zeolite films were prepared using a rotating convection oven. The advantages of this dynamic method include a shorter synthesis time, a more uniform particle size distribution, and better film orientation. Chin. J. Catal., 2011, 32: 224–230 doi: 10.1016/S1872-2067(10)60168-4
Monolayer Dispersed Ru-Zn Catalyst and Its Performance in the Selective Hydrogenation of Benzene to Cyclohexene
SUN Haijie, ZHANG Xudong, Chen Zhihao, ZHOU Xiaoli, GUO Wei, LIU Zhongyi*, LIU Shouchang Zhengzhou University
Cyclohexene yield: 58.9% ZnO
ZnSO4·3Zn(OH)2·7H2O
ZnSO4 + H2O Ru Ru
Ru-Zn(8.6%) catalyst Monolayer dispersed Ru-Zn catalyst
A monolayer dispersed Ru-Zn catalyst showed excellent catalytic performance in the selective hydrogenation of benzene to cyclohexene. A maximum cyclohexene yield of 58.9% was achieved over this catalyst.
Chin. J. Catal., 2011, 32: 231–234 doi: 10.1016/S1872-2067(10)60169-6
O O OH PhLi, THF, Enantioselective Cycloetherification in a Micellar Catalysis 1 1 R o R System -78 C to rt COPh
Bhupesh S. SAMANT*, Sunil S. BHAGWAT Rhodes University, South Africa
Institute of Chemical Technology, India - H2O2 R Ni+I , Toluene + H O, + - 4 2 R4N I H2O2 SDS, rt + - The cycloetherification of substituted keto phenols into Hydrophobic [R4N] [IO] Hydrophilic enantioselective dihydrobenzofuran derivatives was carried out core bulk using hydrogen peroxide and tetrabutyl ammonium iodide in O micellar media. This approach increased the conversion rate and R1 COPh widens the scope of the cycloetherification reaction.
Chin. J. Catal., 2011, 32: 235–239 doi: 10.1016/S1872-2067(10)60170-2
Ultra-deep Oxidative Desulfurization of Fuel Oil Catalyzed by Dawson-type Polyoxotungstate Emulsion Catalysts
ZHANG Yongna, WANG Lu, ZHANG Yuliang, JIANG Zongxuan*, LI Can* Dalian Institute of Chemical Physics, Chinese Academy of Sciences
100
80 18 O Q P2W 12 O s DBT s
60 s
+
+
N
N
N
N
N N
+ +
+ + 4,6-DMDBT
N
N 40 + + O
2 W 1 BT M)W O N P 2 N PO +
+ (
20 +
N
+ S
N
N O
N
N
2,5-DMT +
N
+
+ O +
N
+ N O
Conversion (%) Conversion 0 + W O W 12 POM) S P 2 S ( O N
N 0 20 40 60 80 100 120 +
+
+
N
N
Reaction time (min) + +
N N
N
+ S +
N O
+ O
N S O
)W +
N POM O P + ( 2W12 +N O N 2 + S
H2 H O2 N
2 + +
N S
N
N
+ +
+ O
N O O
N
+ (POM)W N
P O +
2W
1 N S 2 + +N N S + lin n eca Decali D
18 The lacunary Dawson-type emulsion catalyst Q P2W12, which can transform into an active polyperoxometalate in the presence of H2O2 showed very high activity for the oxidation of sulfur-containing compounds under mild conditions.
Articles
Chin. J. Catal., 2011, 32: 240–249 doi: 10.1016/S1872-2067(10)60171-4
Effect of Alumina Supports on the Formation of Active Phase of Selective Hydrodesulfurization Catalysts Co-Mo/Al2O3
Qiherima, LI Huifeng, YUAN Hui, ZHANG Yunhong, XU Guangtong* Beijing Institute of Technology; Research Institute of Petroleum Processing, SINOPEC; Inner Mongolia Medical College
CoMoS Al2O 3‐1 Co‐Mo/Al2O 3‐1 H H MoS2 O O 0.01 H H H S/H O O Mo 2 2 CoMoS O O O O Strong MoS 2 OH Al O interaction 3+ 2 3 Al
Al2O 3‐2 Absorbance Co-Mo/Al2O3-2 Co‐Mo/Al2O 3‐2 H O H O H 2S/H2 O Mo CoMoS Co-Mo/Al2O3-1 O O O MoS Weak 2 2250 2200 2150 2100 2050 2000 1950 1900 Al O interaction Wavenumber (cm−1) 2 3
An Al2O3 support with higher crystallinity and fewer hydroxyl groups has a moderate metal-support interaction that increased the slab
length and stacking number of MoS2, which gave more formation of the active CoMoS phase and an increase in Hydrodesulfurization activity and selectivity.
Chin. J. Catal., 2011, 32: 250–257 doi: 10.1016/S1872-2067(10)60172-6
Preparation of Highly Loaded LaMnOx/SBA-15 Catalyst and Its Toluene Combustion Performance
ZHANG Zekai, LIANG Yiwei, REN Qianru, Liu Huayan, CHEN Yinfei* Zhejiang University of Technology
100 1 time 2 times 80 3 times 6 times
Mn3O4 60
40
Conversion (%) 20 VIH 0 160 200 240 280 320 360 Temperature (oC)
A step coating NH3/water vapor-induced internal hydrolysis (VIH) method was used to prepare the highly loaded LaMnOx/SBA-15
catalyst. The LaMnOx species was scattered in the pores much better.
Chin. J. Catal., 2011, 32: 258–263 doi: 10.1016/S1872-2067(10)60173-8
Direct Hydroxylation of Benzene to Phenol over Fe3O4 Supported on Nanoporous Carbon
Pezhman ARAB, Alireza BADIEI*, Amir KOOLIVAND, Ghodsi MOHAMMADI ZIARANI University of Tehran, Iran; Alzahra University, Irant
We investigated the direct hydroxylation of benzene to phenol
using hydrogen peroxide as an oxidant and Fe3O4/CMK-3 as a
catalyst. Fe3O4/CMK-3 showed good catalytic activity and 18%
benzene conversion was achieved with a 92% selectivity for phenol. Chin. J. Catal., 2011, 32: 264–272 doi: 10.1016/S1872-2067(10)60174-X
Nitrous Oxide Decomposition over Alkali-Promoted Magnesium 100
Cobaltite Catalysts 500 oC 80 475 oC Bahaa M. ABU-ZIED* 60 o Assiut University, Egypt 450 C 425 oC 40 400 oC
N2O decomposition was studied over a series of MgxCo1-xCo2O4 (0.0 ≤ x ≤ (%) Conversion 275 o C 375 oC 1.0) catalysts as well as over alkali-doped MgCo2O4 catalysts. The 20 o o dependence of the activity on the K/Co ratio revealed that the catalyst with 250 C 350 C 325 oC a K/Co ratio of 0.05 had the highest activity. 300 oC 0 0.00 0.05 0.10 0.15 0.20 K/Co ratio
Chin. J. Catal., 2011, 32: 273–279 doi: 10.1016/S1872-2067(10)60175-1
Deactivation and Regeneration of Nickel-Based Catalysts for Steam-Methane Reforming
Seyed Meysam HASHEMNEJAD, Matin PARVARI* Iran University of Science and Technology, Iran
DEACTIVATION OF NICKEL CATALYSTS
Sintering Phase Transformation
Sulfur poisoning Coke formation
Deactivation of nickel catalyst used in Arak and Razi petrochemical complexes followed by catalyst regeneration was evaluated.
Promising results in redispersion of coalescent nickel particles along with desulfurization of industrial Ni/CaAlmOn catalyst were achieved.
Chin. J. Catal., 2011, 32: 280–285 doi: 10.1016/S1872-2067(10)60176-3
Hydrogenation of Olefins Catalyzed by Polymer-Supported Palladium-Imidazole
Udayakumar VELU, Alexander STANISLAUS, Gayathri VIRUPAIAH*, Shivakumaraiah, Viswanathan BALASUBRAMANIAN Bangalore University, India; Siddaganga Institute of Technology, India; National Centre for Catalysis Research, India
H H C C C C
Alkene Alkane H 2
CH2 N S N U Cl P P Pd O N R CH N Cl T 2
Polymer-bound palladium-imidazole complex
The hydrogenation of various olefins using a reusable polymer-supported palladium-imidazole catalyst under mild conditions was studied. The solvent used and structure of the olefins played a dominant role on the reactivity.
Chin. J. Catal., 2011, 32: 286–292 doi: 10.3724/SP.J.1088.2011.00819
Effect of Si Doping on the Microstructure and Photocatalytic Performance of TiO2 Hollow Microspheres
LI Gang, LIU Fang, YANG Qihua, ZHANG Zhao* Sichuan University
Si-TiO2 hollow microsphere samples were fabricated by a simple one-pot hydrothermal method. The effect of Si doping on the microstructure and photocatalytic activity of the hollow microspheres was investigated.
Chin. J. Catal., 2011, 32: 293–298 doi: 10.3724/SP.J.1088.2011.00902
A Comparative Study of Methanol to Olefins over SSZ-13 and RUB-50 Zeolites
LI Peng, ZHANG Weiping*, HAN Xiuwen, BAO Xinhe* Dalian Institute of Chemical Physics, Chinese Academy of Sciences
SSZ-13 with CHA structure and RUB-50 with LEV structure were comparatively investigated in methanol-to-olefin reaction. SSZ-13 with larger cage size exhibits higher propylene selectivity, while RUB-50 with smaller cage size exhibits higher ethylene selectivity.
Chin. J. Catal., 2011, 32: 299–302 doi: 10.3724/SP.J.1088.2011.00833
Synthesis of a New Biphophorus Ligand and Its Application in Hydroformylation of 2-Butene
ZHANG Lin, LI Chun, FU Haiyan, YUAN Maolin, LI Ruixiang, CHEN Hua* Sichuan University
CO-H2 catalyst
CO-H2 Ligand catalyst
A new biphosphorus ligand has been developed and applied in the rhodium-catalyzed regioselective hydroformylation of 2-butene, and higher activity and regioselectivity are obtained. Chin. J. Catal., 2011, 32: 303–308 doi: 10.3724/SP.J.1088.2011.00910
Influence of Support Calcination Temperature on the Performance of Pd/Zr0.5Al0.5O1.75 Catalyst Used in Lean-Burn Natural Gas Vehicles
WANG Yun, TANG Shiyun, LONG Enyan, LIN Zhien, GONG Maochu, CHEN Yaoqiang∗ Sichuan University
CO, CH 4 100 CO2,H2O CO2,O2
) 90 %
( 80 Cat-1050 70 Cat-1000 Cat-950 60 Cat-900 conversion conversion 4 50 Cat-800 CH Cat-700 40 30 Zr Al O 250 300 350 400 450 500 550 0.5 0.5 1.75 Temperture (οC)
Over the Pd/Zr0.5Al0.5O1.75 catalyst with the support calcined at 950 °C, the complete conversion temperature of methane was 315 °C, which indicated that the catalyst has excellent catalytic activity at low temperature.
Chin. J. Catal., 2011, 32: 309–314 doi: 10.3724/SP.J.1088.2011.00909
Effect of La and Mn Promoters on Structure and Performance of CuZr Catalyst Prepared by Complete Liquid-Phase Technology
GAO Zhihua, HUANG Wei*, YIN Lihua, XIE Kechang Taiyuan University of Technology
30 100 CuZr La Mn H O C 25 LaMn-CuZr 90 20 80 15 CuZr slurry catalyst 10 70
5 60 CO conversion(%) + 0 (%) selectivity DME 50 480 500 520 540 560 Temperature (K) The CuZr slurry catalyst prepared by complete liquid-phase technology can catalyze syngas to dimethyl ether and the addition of La and Mn promoters enhanced the interaction between Cu and Zr and obviously improved the CO conversion.
Chin. J. Catal., 2011, 32: 315–320 doi: 10.3724/SP.J.1088.2011.00934
Effects of Citric Acid Modification on the Performance of Nano-Ba-MgO Supports and Its Ru-Based Catalysts for Ammonia Synthesis
HUO Chao*, XIA Qinhua, PAN Meihua, YANG Xiazhen, LUO Yan, LIU Huazhang Zhejiang University of Technology
Stern Diffuse Stern Diffuse Stern Diffuse Stern Diffuse double layer double layer double layer double layer - 2+ 2+ - - - Ba Ba - - - NO NO3 2+ 2+ NO - 3 - Ba Ba - O 3 - - NO 2+ - NO3 3 Ba - - - - NO 2+ - 3 - NO3 Ba - - NO3 - H C C O - 2+ - - 2 - O NO Ba 2+ 2 3 - - 2 2 - Ba C CH2 NO - - O O O 3 - 2 C CH2 - O C C OH - NO - O 2+ 3 - - O - - - Ba O OH C C O - NO3 - - C C OH - H C C O 2+ NO3 O O NO3 2 Ba Mg(OH)
- Mg(OH) - C CH Mg(OH) - NO3 - NO O 2 - NO - 3 2+ - 3 Mg(OH) O 2+ C CH2 O Ba - 2+ - Ba - O - Ba - - 2+ - - NO - - 2+ NO 3 - Ba - Ba - 3 2+ NO - - 3 2+ NO3 - NO3 Ba Ba - - NO - NO NO3 3 NO3 - 3 - -
Slip Slip Slip Slip - Potential + - Potential - Potential+ - Potential + - Potential + No addition of citric acid Small addition of citric acid Appropriate addition of citric acid Excessive addition of citric acid
Citric acid can change the electric type and density of surface charges of Mg(OH)2. Therefore the Ba doping amount in the MgO support can be controlled by changing the adding amount of citric acid.
Chin. J. Catal., 2011, 32: 321–324 doi: 10.3724/SP.J.1088.2011.00932
mesopore Influence of Carbon Aerogel (CA) Pore Structure on
(C H 3 ) 2 N Photodegradation of Methyl Orange over TiO2/CA
N
N (CH 3)2N
N N (CH S 3)2N O S 3 N O3N a a * N N
S CUI Huanan, ZHAO Zhenhua, LIANG Yeru, SHI Jianying , O3N a WU Dingcai*, LIU Hong, FU Ruowen
(C Sun Yat-sen University H 3 ) 2 N
a N (C 3 H O 3)2N N S
N N N
SO 3Na
N S TiO /CA125 with a large amount of mesopores displays the higher O 2 N 3 N Na a SO3
N N ) 2 N 3 H photocatalytic activity than TiO2/CA500. The favorable adsorption and (C
) 2N H 3 micropore (C suitable confinement effect of mesopore structure are beneficial to the macropore photodegradation of methyl orange. carbon TiO (CH3)2N N N SO3Na methyl orange 2
Chin. J. Catal., 2011, 32: 325–332 doi: 10.3724/SP.J.1088.2011.00941
Effects of Supports on Catalytic Properties of the Supported Ni-B Catalysts for Selective Hydrogenation of 2-Ethylanthraquinone
to H2O2
CHEN Xueying*, QIAO Minghua, HE Heyong Fudan University
O Et 100 Ni-B/SiO 2 O 80 eAQ H2O2 60
Cat. H O )/%
2 2 2 Ni-B/SiO2
O 2 40 Ni-B/γ-Al2O3 (H
OH Y Ni-B/AC Raney Ni Et 20 Ultrafine Ni-B 50 nm 0 OH 0 60 120 180 240 300 360 420 Reaction time (min) eAQH2
The catalytic properties of the supported Ni-B catalysts with SiO2, γ-Al2O3, and active carbon (AC) as supports in selective hydrogenation
of 2-ethylanthraquinone to H2O2 were strongly affected by the pore structure and surface properties of the supports.
Chin. J. Catal., 2011, 32: 333–339 doi: 10.3724/SP.J.1088.2011.00820
Reaction Dynamics Behavior of Epoxidation of Allyl Chloride with Hydrogen Peroxide Catalyzed by Ti-MWW
FANG Xiangqing,WANG Yuning, DENG Xiujuan, WU Haihong, WU Peng, LIU Yueming*, HE Mingyuan East China Normal University
Different parameters affecting the epoxidation of allyl chloride with H2O2 catalyzed by Ti-MWW and the reaction dynamics behavior are described. The epoxidation reaction rate is an S-type curve when the Ti content in Ti-MWW increases. Chin. J. Catal., 2011, 32: 340–344 doi: 10.3724/SP.J.1088.2011.00818
Reduction Mechanism of Ni/Al2O3 Catalyst Reduced by Cold Plasma Jet for Carbon Dioxide Reforming of Methane
HU Shijing, LONG Huali, XU Yan, SHANG Shuyong, YIN Yongxiang* Sichuan University
e H H H H O H H O O O Ni Ni Ni O ONi Ni Ni Ni(NO3)2 O Ni Ni Ni Ni Ni Al2O3 Ni Al2O3
The reduction mechanism of Ni/Al2O3 catalyst by Ar-H2 cold plasma jet (CPJ) is hydrogen atom action. CPJ brings energetic electrons,
which impact H2 molecules, to generate enough H atoms.
Chin. J. Catal., 2011, 32: 345–351 doi: 10.3724/SP.J.1088.2011.00914
Dehydration of Glycerol to Acetol over Copper-Based Catalysts
NIU Shasha, ZHU Yulei*, ZHENG Hongyan, ZHANG Wei, LI Yongwang Shanxi Institute of Coal Chemistry, Chinese Academy of Sciences; Graduate University of Chinese Academy of Sciences; Synfuels China Co. Ltd
Glycerol Glycerol 100 Acetol Cu/SiO -H 2O-H2 2 1,2-PDO 80 +H2 1,2-PDO Acerol 1,3-dihydroacetone 60 40
Glyceraldehyde 20
Target product (%) selectivity and Conversion 0 N H N /H 2 2 2 2
The Cu/SiO2 catalyst exhibited significantly higher activity and selectivity for acetol under the mixed atmosphere of H2/N2. That is
because the catalyst deactivation was restrained compared with pure N2 atmosphere, and the excessive hydrogenation of acetol was also
restrained compared with pure H2 atmosphere.
Chin. J. Catal., 2011, 32: 352–356 doi: 10.3724/SP.J.1088.2011.01009
Effects of Bi on the Catalytic Performance of MoVO/AlPO4 Catalyst for Selective Oxidation of Isobutene
WANG Xitao, WANG Fen, JIANG Shi, ZHONG Shunhe* Tianjin University
CHO CH2 – = O CH C(CH )=CH O CH =C(CH )CHO H33C–C–3CH3 2 H2C2 =C–CH3 3 +O ++H H OO + O22 V O Bi O Mo 22 O O O O O O O
AlPO4
5+ 4+ The addition of Bi can promote the dispersion of crystalline MoO3 and V2O5, modify the surface V /V ratio, enhance the activity of the
lattice oxygen species, and obviously improve the catalytic performance of MoVO/AlPO4 for selective oxidation of isobutene.
Chin. J. Catal., 2011, 32: 357–361 doi: 10.3724/SP.J.1088.2011.00901
Influence of 2'-Substituent in the Nucleosides on Burkholderia cepacia Lipase-Catalyzed Regioselective Acylation
WANG Zhaoyu*, ZONG Minhua Huaiyin Institute of Technology; South China University of Technology
3'-Regioselective enzymatic acylations of unprotected nucleosides bearing different substituents in 2'-position with acyl donors were investigated to reveal the substrate specificity of the Burkholderia cepacia lipase.
Chin. J. Catal., 2011, 32: 362–367 doi: 10.3724/SP.J.1088.2011.00937
Synthesis of Herarchical HZSM-5 Microspheres without Second Template and Their Application in Methane Dehydroaromatization
YANG Jianhua, YU Suxia, HU Huiye, CHU Naibo, LU Jinming, YIN Dehong, WANG Jinqu* Dalian University of Technology
CH4 No secondary C6H6+H2 template
12
8
4 Mo/HZSM-5-HW
Benzene (%) yield Mo/HZSM-5-HT Mo/HZSM-5 TPABr+NaOH+ 0 H O+AIP+TEOS 04812162024 2 Time (h)
Hierarchical ZSM-5(ZSM-5-HW) microspheres with a diameter range of 10–15 μm were synthesized by controlling the hydrothermal
conditions without any secondary template. The Mo/HZSM-5-HW catalyst exhibited higher activity and stability in CH4 dehydroaromatization.
Chin. J. Catal., 2011, 32: 368–373 doi: 10.3724/SP.J.1088.2011.01003
Influence of Preparation Methods on Catalytic Performance of Double Mesoporous Co-Based Catalyst for Fischer-Tropsch Synthesis
WANG Jungang, LI Debao*, HOU Bo, JIA Litao, JIA Lihong, SUN Zhiqiang, LIU Bin, GUO Jingang, REN Runhou, SUN Yuhan* Institute of Coal Chemistry, Chinese Academy of Sciences; Lu’an Coal to Synfuel Co. Ltd; Shanxi Lu’an (Mining) Group Co. Ltd; Shanghai Advanced Research Institute, Chinese Academy of Sciences.
incipient-wetness impregnation Co/DM-MCM41(IWI) excessive Double impregnation Mesoporous MCM-41 Co/DM-MCM41(EI) vapor-induced hydrolysis Co/DM-MCM41(VIH)
The CH4 selectivity and C5+ selectivity over double mesoporous Co-based catalyst in Fischer-Tropsch synthesis were obvious different because of the different preparation methods. Chin. J. Catal., 2011, 32: 374–378 doi: 10.3724/SP.J.1088.2011.01004
Preparation of Supported Nano-gold Catalyst by Adsorption Column Chromatography
ZHAI Xinlei, XU Jinguang*, XU Xiufeng, ZOU Xuhua, QI Shixue, QI Caixia, AN Lidun Yantai University
NH ·H O H O HAuCl4 3 2 2 solution Au/Al2O3
Dried at 110 oC
Al2O3 Reduced by o H2 at 300 C
Adsorption column chromatography was used to prepare an Al2O3-supported nano-gold catalyst. This method can improve the utilization ratio of gold and effectively remove toxic chlorine ions.
Chin. J. Catal., 2011, 32: 379–384 doi: 10.3724/SP.J.1088.2011.01008
Preparation of Mesoporous Alumina and Its Application in Dehydration of Methanol to Dimethyl Ether
NIE Renfeng, WANG Junhua, FEI Jinhua, HOU Zhaoyin*, ZHENG Xiaoming Zhejiang University
Channels HMTM OH¯ DME =
Boehmite/CTAB CH3OH Mesoporous CTAB/Al3+ alumina + CTAB Al3 A novel homogeneous precipitation method was reported for the preparation of mesoporous alumina with framework pore walls made of
crystalline, tubelike Al2O3 nanoparticles. The mesoporous alumina exhibits higher activity for dehydration of methanol to dimethyl ether.
2011 Chinese Journal of Catalysis Vol. 32 No. 2
文章编号: 0253-9837(2011)02-0315-06 DOI: 10.3724/SP.J.1088.2011.00934 研究论文: 315~320
柠檬酸改性对掺 Ba 纳米 MgO 及其担载的 Ru 氨合成 催化剂性能的影响
霍 超, 夏庆华, 潘美华, 杨霞珍, 骆 燕, 刘化章 浙江工业大学化学工程与材料学院 , 浙江杭州 310032
摘要: 采用超声-静电吸附法制备了一系列经柠檬酸改性的掺 Ba 纳米 MgO 及其负载的氨合成 Ru 催化剂. 并采用场发射扫描
电镜、X 射线粉末衍射、N2 物理吸附-脱附、电感耦合等离子体发射光谱及红外光谱等手段对样品进行了表征. 结果表明, 适 量添加柠檬酸可有效调控 Ba 的掺杂量, 从而使 Ba-MgO 结构与化学性质发生变化, 其表面性能得到极大改善, 最终导致相应 Ru/Ba-MgO 催化剂氨合成的低温活性显著提高. 在 10 MPa, 400 °C, 10 000 h−1 的条件下, 柠檬酸浓度为 2.0 mmol/L 时制得的 Ru/Ba-MgO 催化剂出口氨生成速率达 63.2 mmol/(g·h), 较未经柠檬酸改性的 Ru/Ba-MgO 催化剂活性提高了 21%. 关键词: 柠檬酸; 改性; 掺钡; 纳米氧化镁; 钌; 氨合成; 超声制备 中图分类号: O643 文献标识码: A
Effects of Citric Acid Modification on the Performance of Nano-Ba-MgO Support and Its Ru-Based Catalysts for Ammonia Synthesis
HUO Chao*, XIA Qinhua, PAN Meihua, YANG Xiazhen, LUO Yan, LIU Huazhang College of Chemical Engineering and Materials Science, Zhejiang University of Technology, Hangzhou 310032, Zhejiang, China
Abstract: A series of citric acid-modified Ba-MgO supports (Ba-MgO(CA)) were prepared by ultrasound electrostatic adsorption (UEA), and the corresponding Ru catalysts for ammonia synthesis were then prepared by the impregnation method. Their physical and chemical properties were characterized by scanning electronic microscopy, X-ray diffraction, nitrogen physical adsorption, inductively coupled plasma-atomic emission spectrometry, and infrared spectroscopy. The results showed that the introduction of citric acid during the prepara- tion of the support changed not only the chemical and textural properties of the nano-Ba-MgO support but also the doping amount of Ba in the Ba-MgO(CA) support. When the concentration of citric acid was 2.0 mmol/L, the Ru/Ba-MgO(CA) catalyst exhibited the highest cata- lytic activity for ammonia synthesis with a reaction rate of 63.20 mmol/(g·h) at 400 oC, 10 MPa, and 10 000 h−1, which is 21% higher than that of unmodified Ru/Ba-MgO. Key words: citric acid; modification; barium doping; nano-magnesia; ruthenium; ammonia synthesis; ultrasonic preparation
Ru 基催化剂因在低温低压下具有高活性而被 为了克服传统浸渍法的这一弊病, 本课题组[7,8]曾利 认为是继熔铁催化剂以来的第二代氨合成催化剂, 用超声-静电吸附法 (UEA) 成功地制备了高活性的 是当今国内外学者研究的热点之一[1]. 目前, 用于负 Ru/Ba-MgO 催化剂. 结果表明, Ba 在 MgO 中的掺 [2] [3] [4] 载 Ru 的载体包括活性炭 、MgO 、Al2O3 和铈酸 杂量及其掺杂形式既是影响催化剂性能的关键因 钡[5]等. 其中 MgO 具有机械强度高、稳定性好和碱 素, 又与所制得载体的表面性能关系密切. 性高等优点, 被认为是最具开发潜力的载体之一[3,6]. 研究表明[9,10], 柠檬酸等有机分子作为金属及 但是, 用传统浸渍法制备的 Ba-Ru/MgO 氨合成活性 氧化物胶体粒子的稳定剂, 极易吸附在胶体粒子表 都不高[6], 主要原因是活性组分 Ru 的分散度较低. 面, 可以有效地改变胶体的带电性及带电量, 提高胶
收稿日期: 2010-10-04. 接收日期: 2010-11-02. 联系人: 霍 超. Tel/Fax: (0571)88320815; E-mail: [email protected] 基金来源: 国家自然科学基金 (20203016); 浙江省自然科学基金 (Y406294). 316 催 化 学 报 Chin. J. Catal., 2011, 32: 315–320
体粒子之间的静电及空间排斥力, 从而极大地改善 1.3 催化剂的评价 纳米粒子的表面性能及团聚情况. 因此, 本文采用 氨合成反应在内径为 14 mm 的不锈钢连续流 UEA 法制备载体的同时, 尝试添加柠檬酸进行改性 动反应器上进行. 取 2 ml 催化剂 (14~20 目) 置于反
修饰, 考察其对载体表面性能的影响以及 MgO 中 应器等温区, 用 75% H2-25% N2 混合气对催化剂进 Ba 掺杂量的调控能力, 旨在更大幅度地提高 行还原活化, 在 10 MPa, 10 000 h−1 和 375~450 °C
Ru/Ba-MgO 催化剂的低温氨合成活性. 条件下, 测定反应器出口气体中的 NH3 浓度, 由此 计算出氨生成速率 r (mmol/(g·h)), 作为催化剂活性 1 实验部分 评价的依据. 1.1 催化剂的制备 2 结果与讨论 将一定量的 Mg(NO3)2·6H2O (AR, 上海泗联化
工厂) 和 Ba(NO3)2 (AR, 上海化工高等专科学校实 2.1 柠檬酸改性对 Ba-MgO 载体表面织构的影响 验工厂) 分别与不同摩尔比例的柠檬酸混合溶解在 图 1 为经不同浓度柠檬酸改性后的 Ba-MgO 样
蒸馏水中, 按化学计量比加入氨水 (NH3 浓度为 品前驱体的 XRD 谱. 由图可见, 各样品的主要特征
25%, 杭州长征化工厂), 同时施以超声作用 50 min 衍射峰位置十分相似, 其中 Mg 以 Mg(OH)2 的形式
(宁波科生仪器厂, 超声频率 25 kHz, 功率 300 W). 存在, Ba 则主要以 Ba(NO3)2 的形式存在. 随着柠檬
待反应完成后, 将反应液静置老化 24 h, 再经抽滤、 酸浓度的增加, 载体中 Ba(NO3)2 的衍射峰先变弱,
乙醇洗涤后, 将得到的 Mg(OH)2 在 110 °C 干燥 12 后变强. 同时还出现了柠檬酸钡 Ba3(C6H6O7)2 的衍 h, 600 °C 焙烧 5 h, 即得一系列不同柠檬酸用量改性 射峰. 经 2 mmol/L 柠檬酸改性的载体前驱体, 经不 的 Ba-MgO 样品, 球磨筛分后备用. 同温度焙烧后所得载体的 XRD 谱见图 2. 由图可
采用浸渍法制备 Ru/Ba-MgO 催化剂. 见, 随着焙烧温度的升高, 载体前驱体中 Mg(OH)2
Ru3(CO)12 的合成参见文献[11]. 将制得的 Ba-MgO 逐渐向 MgO 转变, 而 Ba(NO3)2 和 Ba3(C6H6O7)2 逐
载体用一定量的 Ru3(CO)12 四氢呋喃 (AR, 浙江杭州 渐向 BaCO3 的形式转变. 这是因为载体中的
双林化工试剂厂) 溶液等体积浸渍 12 h. 水浴蒸干 Ba(NO3)2 及 Ba3(C6H6O7)2 在高温焙烧时均会分解为
溶剂后, 于 60 °C 烘干, 再在 450 °C 真空分解后用 BaO, 并再吸收了空气中的 CO2 形成 BaCO3.
H2 还原, 经压片、破碎、筛分后, 即得 Ru/Ba-MgO 催 ■ Mg(OH) 化剂, Ru 负载量为 2%. 2 ▼ Ba(NO3)2 1.2 催化剂的表征 ● Ba3(C6H5O7)2
Ba-MgO 样品表面形貌在 Hitachi S-4700(II) 型 (5) 场发射扫描电镜 (FE-SEM) 上观察, 加速电压为 15 (4)
kV. 催化剂的物相结构采用 Thermo ARL SCINTAG Intensity (3) (2) X′TRA 型 X 射线衍射仪 (XRD) 进行表征, Cu Kα 辐 射, 固体探测器, 电压 45 kV, 电流 40 mA, 扫描速率 5°/min, 扫描范围 2θ = 10°~80°. 催化剂比表面积及 (1)
孔容在 Quantachrome NOVA-1000e 型物理吸附仪 10 20 30 40 50 60 70 80 上测定, 称取一定量样品经 250 °C 真空脱气处理 3 2θ/( o ) h 后, 在液 N2 温度下进行 N2 吸附-脱附测定. 图 1 添加不同柠檬酸浓度的 Ba-MgO 前驱体的 XRD 谱 Fig. 1. XRD patterns of Ba-MgO precursors modified with different 将载体和催化剂用 HNO3 溶解配制成一定浓度 concentration of citric acid (CA). (1) 0 mmol/L; (2) 1.0 mmol/L; (3) 的溶液, 在 ICP-AES 仪器上测定其 Ba, Mg 及 Ru 含 2.0 mmol/L; (4) 3.0 mmol/L; (5) 4.0 mmol/L. 量. 红外吸收光谱 (FT-IR) 实验在 Nicolet Nexus 型 红外光谱仪 上进行, MCT 检测器, 扫描次数 64, 分 表 1 为添加不同柠檬酸浓度所制 Ba-MgO 样品 辨率 2 cm−1, 样品分别与 KBr 混合后压片用于测定. 的织构性质. 由表可见, 随着柠檬酸浓度的增加, 载 www.chxb.cn 霍 超 等: 柠檬酸改性对掺 Ba 纳米 MgO 及其担载的 Ru 氨合成催化剂性能的影响 317
见, 各样品均为纳米级颗粒, 但适量柠檬酸的添加使
● BaCO3 ▼ Ba(NO3)2 得样品初级粒子明显细化 (见图 3 (b)~(d)), 这与表 1 ■ MgO ★ Mg(OH)2 结果一致. 另外, 经柠檬酸修饰的 Ba-MgO 颗粒趋 于规则的球形, 且分布较为均匀, 团聚变少. 这是因 为适量柠檬酸的添加可使得 Ba-MgO 颗粒的表面极
性减弱, 表面能降低, 从而使颗粒处于较为稳定的状 Intensity (3) 态, 颗粒间的团聚现象随之减少. 但柠檬酸的过量 (2) 添加将会导致颗粒重新团聚且呈片状 (见图 3(e), (1) (f)), 这可能是由于 Ba 的架桥作用引起的[12]. 柠檬酸改性对 中 掺杂量的影响 10 20 30 40 50 60 70 80 2.3 Ba-MgO Ba 2θ/( o ) 图 4 为柠檬酸添加量对 MgO 中 Ba 掺杂量的 图 2 经不同温度焙烧的 Ba-MgO 的 XRD 谱 影响. 由图可见, MgO 中 Ba 的掺杂量随柠檬酸添 Fig. 2. XRD patterns of Ba-MgO samples with 2 mmol/L citric acid 加浓度的增加呈先减少后增加的趋势. 结合胶体化 calcined at different temperatures. (1) 450 °C; (2) 500 °C; (3) 600 °C. [13] 学知识 , 上述现象是由胶体的带电性、带电量 (主 表 1 Ba-MgO 与 Ba-MgO(CA) 的表面织构 7 Table 1 Textural parameters of Ba-MgO and Ba-MgO (CA) 6 Citric acid concentration ABET Pore volume Pore size 2 3 (mmol/L) (m /g) (cm /g) (nm) 5 0 44.7 0.16 14.7 4 1 47.7 0.24 20.1 3 2 52.2 0.38 29.2 3 58.2 0.29 25.4 2 4 44.0 0.17 15.3 Ba doping amount (%) Ba doping amount 1 7 36.2 0.23 26.3 0 体比表面积和孔容先增大后减小, 孔径也发生了相 012345 Citric acid concentration (mmol/L) 应的变化. 这与文献[9]结果类似. 图 4 不同柠檬酸浓度对 MgO 中 Ba 掺入量的影响 2.2 FE-SEM 结果 Fig. 4. Effects of citric acid concentration on the amount of Ba 图 3 为各 Ba-MgO 样品的 SEM 照片. 由图可 doped in MgO.
(a) (b) (c)
(d) (e) (f)
图 3 Ba-MgO 和柠檬酸改性的 Ba-MgO 载体的 FE-SEM 照片 Fig. 3. FE-SEM images of the Ba-MgO supports modified with different concentration of citric acid. (a) 0 mmol/L; (b) 1 mmol/L; (c) 2 mmol/L; (d) 3 mmol/L; (e) 4 mmol/L; (f) 5 mmol/L. 318 催 化 学 报 Chin. J. Catal., 2011, 32: 315–320
要受溶液 pH、离子的强度及反离子等因素影响) 及 及带电量, 且对金属离子具有不同的吸附机理. 由
柠檬酸本身特有的物理化学性质所引起的, 即物理 于 Mg(OH)2 胶体在水溶液中的等电点为 pH = 吸附及化学吸附作用对 Ba 的掺杂量起着决定性的 12[15], 因此在本实验条件下 (氨水为沉淀剂, 反应最
影响. 可见, 柠檬酸添加量可用于调控 MgO 中 Ba 终 pH = 10 左右), Mg(OH)2 胶体将带正电. 当不添 − 的掺杂量. 加柠檬酸时, Mg(OH)2 表面极易先吸附一层 NO3 , 2.4 柠檬酸修饰的作用机理 随后吸附少量的 Ba2+(见图 5(a))[7]; 当添加柠檬酸 −12 −4 − 由 Mg 和 Ba 溶度积 (Ksp = 10 , 10 ) 与氨水 时, 由于柠檬酸根为三价阴离子, 极易与 NO3 产生 −5 的解离常数 (NH4OH: Kb = 1.7 × 10 ) 可知, Ba 在 竞争吸附, 从而改变胶体的带电性与带电量, 最终影 反应溶液中会以 Ba2+或 Ba(OH)+的形式存在. 而柠 响了 Ba2+的吸附量. 当柠檬酸浓度较低时 (低于 1
檬酸的各级解离常数分别为 pKa1 = 3.11, pKa2 = mmol/L), 三个羧基头极易同时吸附在 Mg(OH)2 表 2+ − 4.77, pKa3 = 6.40, 所以当溶液呈微酸性时, 柠檬酸主 面上, 此时化学吸附的 Ba 极少, 同时对 NO3 的吸 要以 HA2−及 HA−的形式存在, 此时柠檬酸可与 Mg 附位也随之减少, 导致物理吸附的 Ba2+量减少 (见 络合[14]. 在实验过程中随着氨水的迅速加入, 溶液 图 5(b)); 随着柠檬酸根量的增加 (1~3 mmol/L), 它 2+ − pH 值升高, 溶液中游离的 Mg 与 OH 反应即生成 在 Mg(OH)2 表面上的竞争吸附将导致三个羧基头 2+ 了 Mg(OH)2 晶核. 随着溶液中 Mg 的不断消耗, 柠 在颗粒表面与溶液中重新分配, 最终使得溶液中羧 檬酸-镁络合物将逐渐解离为柠檬酸根离子与 Mg 基头与 Ba2+结合, 即发生化学吸附 Ba2+. 此外, 由于 − 离子, 从而促进了 Mg(OH)2 晶核的均匀成长, 所得 柠檬酸根的离子半径比 NO3 的大, 将使紧密层 颗粒均匀性好. 与此同时, 柠檬酸根离子将吸附在 (stern 层) 厚度扩大, 导致物理吸附的 Ba2+也同时增
Mg(OH)2 颗粒上, 阻止 Mg(OH)2 的进一步增长. 包 加 . 这样, 物理吸附与化学吸附的共同作用使得 2+ 覆 Mg(OH)2 的柠檬酸根越多, Mg(OH)2 的生长阻力 Ba 的吸附量增多 (见图 5 (c), (d)); 而随着柠檬酸 就越大, 相应的颗粒就越小, 这可由 Ba-MgO 的 根的继续增加 (过量), 吸附在颗粒表面过量的柠檬 SEM 照片和织构性质得到证实. 酸根则会因为 Ba 的架桥作用[12], 使颗粒之间重新 另一方面, 在水溶液中胶体具有不同的带电性 团聚, 且为多层吸附.
Stern Diffuse Stern Diffuse Stern Diffuse Stern Diffuse double layer double layer double layer double layer - 2+ 2+ - - - Ba Ba - - NO - NO3 2+ 2+ NO - 3 - Ba Ba - O 3 - - NO 2+ - NO3 3 Ba - - - - NO 2+ - 3 - NO3 Ba - - NO3 - H C C O - 2+ - - 2 - O NO Ba 2+ 2 3 - - 2 2 - Ba C CH2 NO - - O O O 3 - 2 C CH2 - O C C OH - NO - O 2+ 3 - - O - - - Ba O OH C C O - NO3 - - C C OH - H C C O 2+ NO3 O O NO3 2 Ba Mg(OH)
- Mg(OH) - C CH Mg(OH) NO3 - O 2 - - - NO 2+ NO 3 - 3 Mg(OH) O 2+ C CH2 O Ba - 2+ - Ba - O - Ba - - 2+ - - NO - - 2+ NO 3 - Ba - Ba - 3 2+ NO - - 3 2+ NO3 - NO3 Ba Ba - - NO - NO NO3 3 NO3 - 3 - -
Slip Slip Slip Slip - Potential + - Potential + - Potential + - Potential - Potential + - Potential (a) (b) (c) (d) 图 5 不同柠檬酸量改性 Ba-MgO 前驱体的相互作用 Fig. 5. Schematic presentation of the interaction of citric acid-modified Ba-MgO precursors. (a) No addition of CA; (b) Small addition of CA; (c) Appropriate addition of CA; (d) Excessive addition of CA.
图 6 是经不同用量的柠檬酸改性后的 峰对应于 H–O 键的对称伸缩振动和不对称伸缩振
Ba-Mg(OH)2 的 FT-IR 谱. 由图可见, 未经柠檬酸改 动, 它可归因于 Ba-MgO 表面的羟基和吸附水的存 −1 − 性的 Ba-Mg(OH)2 在 3 650, 3 420, 1 480 和 700~800 在. 1 480 cm 附近有一强吸收峰, 归属于 NO3 中 cm−1 处存在特征吸收峰. 其中 3 650 cm−1 的宽吸收 N=O 键的对称伸缩振动, 1 000 cm−1 以下的峰归属 www.chxb.cn 霍 超 等: 柠檬酸改性对掺 Ba 纳米 MgO 及其担载的 Ru 氨合成催化剂性能的影响 319
70
(5) 60 )) h
⋅ 50
(4) g ( 40 (3) mmol/
( 30 3 (2) NH 20 Absorbance (1) 10 3420
1630 012345678 1480 3650 Citric acid concentration (mmol/L)
3500 3000 2500 2000 1500 1000 图 7 400 °C 时 Ru/Ba-MgO 催化剂氨合成活性随载体制 Wavenumber (cm−1) 备时柠檬酸浓度的变化 图 6 Ba-MgO(CA) 前驱体的 FT-IR 谱 Fig. 7. Rate of export ammonia over Ru/Ba-MgO catalysts with Fig. 6. IR spectra of Ba-MgO(CA) samples modified with different citric acid-modification at 400 °C, 10 MPa, and 10000 h−1. amounts of citric acid. (1) 0 mmol/L; (2) 1.0 mmol/L; (3) 2.0 mmol/L; (4) 3.0 mmol/L; (5) 4.0 mmol/L. 应催化剂活性开始下降.
为 Mg-O 及 N=O 的反振动伸缩峰. 经柠檬酸改性 3 结论 −1 后, Ba-Mg(OH)2 样品在 1 630 cm 处出现新的吸收 采用 UEA 法制备掺 Ba 的 MgO 过程中, 适量 峰, 可归属为−COO 中 C=O 键的特征吸收峰[16]. 此 柠檬酸的添加可有效改变 Mg(OH)2 胶体的带电性 外, 3 650 cm−1 的宽吸收峰是由于柠檬酸分子中的 及带电量, 促使 Ba-MgO(CA) 载体的初级粒子明显 H−O 键对称伸缩振动和不对称伸缩振动所产生的. 细化, 颗粒间的团聚现象减少. 同时通过改变柠檬 据此我们认为, 柠檬酸与 Ba-Mg(OH)2 表面羟基发 酸的添加浓度可调控 Ba 在 MgO 中的掺杂量, 可明 生了类似于有机酸和醇的反应, 形成了 (RCOO)2Mg 显提高 Ru/Ba-MgO 催化剂的低温合成氨活性. 或 (RCOO)2Ba 难溶盐, 可能的反应为: Mg(OH)x + 2+ 参 考 文 献 yHOOCR + Ba = MgBa(OH)x-y[OOCR]y + yH2O. 其
可能的作用过程如下: 首先, 柠檬酸分子从液相主 1 Liang C H, Wei Zh B, Xin Q, Li C. Appl Catal A, 2001, 208: 193 体迁移到 Ba-Mg(OH)2 粒子表面, 生成难溶盐前驱 2 Kowalczyk Z, Jodzis S, Rarog W, Zielinski J, Pielaszek J, 体; 然后, 柠檬酸分子和纳米 Ba-Mg(OH) 粒子表面 2 Presz A. Appl Catal A, 1999, 184: 95 2+ 的 Mg 离子反应生成难溶盐, 同时液相主体的难溶 3 Wu Sh, Chen J X, Zheng X F, Zeng H Sh, Zheng Ch M, Guan N J. Chem Commun, 2003: 2488 盐 (RCOO)2Ba 前驱体迁移到 Mg(OH)2 粒子的表面; 4 Murata S, Aika K. J Catal, 1992, 136: 118 最后, 液相主体中的难溶盐在 Ba-Mg(OH) 粒子表 2 5 杨晓龙, 夏春谷, 熊绪茂, 慕新元, 胡斌. 催化学报 面吸附、生长, 把 Ba-Mg(OH)2 粒子包覆起来 (参见 (Yang X L, Xia Ch G, Xiong X M, Mu X Y, Hu B. Chin J 图 5 的示意图). Catal), 2010, 31: 377 6 Xu Q C, Lin J D, Fu X Z, Liao D W. Catal Commun, 2008, 2.5 柠檬酸改性对钌基催化剂活性的影响 9: 1214 图 7 为添加不同柠檬酸量制得的 Ba-MgO 负载 7 霍超, 张学辉, 夏庆华, 杨霞珍, 骆燕, 刘化章. 催化学 的 Ru 催化剂上氨合成活性. 可以看出, 随着柠檬酸 报 (Huo Ch, Zhang X H, Xia Q H, Yang X Zh, Luo Y, Liu 浓度的增加, 对应的 Ru/Ba-MgO 催化剂在 400 °C H Zh. Chin J Catal), 2010, 31: 360 8 霍超, 夏庆华, 杨霞珍, 骆燕, 刘化章. 催化学报 (Huo 时氨合成活性先降低后增加, 至 2.0 mmol/L 时, 即 Ch, Xia Q H, Yang X Zh, Luo Y, Liu H Zh. Chin J Catal), Ba/Ru ≈ 1:1 时 , 催化剂活性最高, 在 10 MPa, 400 2009, 30: 218 °C, 10 000 h−1 反应条件下, 出口氨生成速率可达 9 Vega E D, Narda G E, Ferretti F H. J Colloid Interface Sci, 2003, 268: 37 63.20 mmol/(g·h), 较未经柠檬酸改性的 Ru/Ba-MgO 10 Lackovic K, Angove M J, Wells J D, Johnson B B. J 催化剂活性提高了 21%, 继续增加柠檬酸用量的相 Colloid Interface Sci, 2004, 269: 37 320 催 化 学 报 Chin. J. Catal., 2011, 32: 315–320
11 霍超, 晏刚, 郑遗凡, 于凤文, 刘化章. 催化学报 (Huo Chemistry. Beijing: Chem Ind Press), 1996. 247 Ch, Yan G, Zheng Y F, Yu F W, Liu H Zh. Chin J Catal), 14 Kabra K, Chaudhary R, Sawhney R L. J Hazard Mater, 2007, 28: 484 2008, 155: 424 12 Lackovic K, Johnson B B, Angove M J, Wells J D. J Col- 15 Larson T E, Buswell A M. Ind Eng Chem, 1940, 32: 132 loid Interface Sci, 2003, 267: 49 16 章正熙, 华幼卿, 陈建峰, 王玉红. 北京化工大学学报 13 朱步瑶, 赵振国. 界面化学基础. 北京: 化学工业出版 (Zhang Zh X, Hua Y Q, Chen J F, Wang Y H. J Beijing 社 (Zhu B Y, Zhao Zh G. The Foundation of Interface Univ Chem Technol (Natur Sci)), 2002, 29: 49
第七届全国环境催化与环境材料学术会议 时间: 2011 年 8 月 12～15 日 地点: 北京昌平 承办单位: 中国石油大学 (北京) 协办单位: 北京工业大学 大连理工大学
环境保护在社会与经济可持续发展战略中占有重要 稿. 也可从邮箱 ([email protected], [email protected]) 的地位. 环境催化是环境保护和绿色化学最重要的科学 投稿. 与技术基础, 也是催化领域发展最为迅速的学科方向之一. 4. 根据在线投稿的说明, 选择稿件主题与投稿类别 经中国化学会催化专业委员会批准, 第七届全国环境催化 (口头报告或墙报). 与环境材料学术会议由中国石油大学 (北京) 承办, 北京工 5. 论文提交截止日期为 2011 年 4 月 30 日. 业大学和大连理工大学协办, 拟定于 2011 年 8 月 12~15 日 三、大会组织委员会 在北京的后花园——北京昌平召开. 本届会议将充分展示 顾问委员: 沈师孔, 潘惠芳, 徐春明, 高金森, 鲍晓军, 和交流近年来我国广大科技工作者在环境催化与环境材 郭绍辉, 刘晨光 料领域所取得的新成果、新进展, 为同行专家和产、学、 主席: 赵震 研单位间提供相互交流、切磋学习与深入讨论的机会, 促 共同主席: 何洪, 王新平 进相互了解与合作. 现面向全国从事环境催化与环境材 委员: 阎子峰, 戴洪兴, 窦涛, 申宝剑, 刘百军, 刘植昌, 料研究的同行和相关领域的企业征集会议论文或技术展 陈胜利, 赵锁奇, 巩雁军, 周亚松, 陈玉, 孙乾耀, 余长春, 张 示. 鑫 一、征文范围 秘书: 刘坚, 段爱军, 姜桂元, 张瑛, 王虹, 张桂臻, 邓积 气态污染物的催化消除; 温室气体减排技术; 废水/污 光 水催化净化; 清洁能源中的催化脱硫、脱氮、脱氯等技术; 四、联系方式 资源转化中的催化科学与技术; 绿色有机合成; 绿色反应 联系人: 赵震, 刘坚 介质与绿色过程工程研究; 生物催化及其在环境保护、资 通讯地址: 北京市昌平区中国石油大学 (北京) 重质 源节约中的作用; 光、电、磁、微波等条件下的催化技术 油国家重点实验室 (邮编 102249) 与环境保护; 环境催化材料的合成与表征; 环境催化剂设 会议网址: http://www.7ncec.org 计新概念、新理论与新材料; 理论化学和分子模拟在环境 联系电话: 010-89731586; 传真: 010-69724721 催化中的应用. 电子邮件: [email protected], [email protected] 二、征文要求 五、会议重要日期 1. 论文内容符合主题范围, 符合国家及各单位保密 2010-11-20 第一轮通知 (稿件征集) 规定, 文责自负. 2011-04-30 网站投稿结束 2. 论文模板及编排规则可在会议网站下载. 论文详 2011-05-25 第二轮通知 (论文录用通知及安排) 细摘要以 A4 纸不超过 2 页为宜. 要求上空 3 cm, 下空 2.8 2011-06-30 第三轮通知 (会议详细安排) cm, 左右各空 3 cm, 标题用三号黑体, 摘要用小五, 正文用 2011-08-12~2011-08-15 会期 五号宋体, 英文用 Times New Roman, 单倍行距. 3. 论文通过会议网站(http://www.7ncec.org)在线投 第七届全国环境催化与环境材料学术会议筹备组