氧化/还原预处理对Cu<sub>2</sub>O/AC催化甲醇氧化羰基化的影响

王瑞玉; 白思雨; 郑传月; 李忠

氧化/还原预处理对Cu₂O/AC催化甲醇氧化羰基化的影响

1.
中国矿业大学江苏省煤基CO₂捕集与地质储存重点实验室, 江苏徐州 221006;
2.
太原理工大学煤科学与技术教育部及山西省重点实验室, 山西太原 030024

基金项目: 国家自然科学基金(21506249),江苏省博士后基金(1401096c)和中央高校基本科研业务费(中国矿业大学,2014QNA19)资助项目

详细信息

通讯作者:
李忠,Tel:0516-83883501,E-mail:wangruiyu0694@163.com.

中图分类号: O643
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出版历程
- 收稿日期: 2015-03-24
- 修回日期: 2015-06-09
- 刊出日期: 2015-10-31

Effect of oxidative/reductive pretreatment on the performance of Cu₂O/AC catalyst for oxidative carbonylation of methnol

1.
Key Laboratory of Coal-based CO₂ Capture and Geological Storage of Jiangsu province, China University of Mining and Technology, Xuzhou 221006, China;
2.
Key Laboratory of Coal Science and Technology, Ministry of Education and Shanxi Province, Taiyuan University of Technology, Taiyuan 030024, China

Funds: The project was supported by the National Natural Science Foundation of China (21506249), the Jiangsu Postdoctoral Sustentantion Fund (1401096c) and the Fundamental Research Funds for the Central Universities (China University of Mining and Technology, 2014QNA19).

摘要

摘要: 将醋酸铜热解制备的Cu₂O/AC(活性炭)催化剂,在氧化(O₂/N₂)和还原(H₂/N₂、CO/N₂)气氛下进行预处理。350 ℃下预处理4 h,氧化气氛中Cu₂O完全被氧化为CuO,还原气氛中Cu₂O被还原为单质铜。经CO/N₂预处理的催化剂表面Cu⁰分散性好,催化活性显著升高。在常压固定床微型反应装置上测试,在140 ℃的反应温度下,碳酸二甲酯的时空收率和选择性分别达到了261.9 mg/(g·h)和74.7%。反应后,还原气氛(H₂/N₂、CO/N₂)预处理的催化剂与Cu₂O/AC催化剂中铜物种价态组成趋于一致,催化活性亦趋于一致。关联反应前后催化剂表面铜物种的变化和催化活性的差异,可以认为Cu⁰具有较高的初始催化活性,Cu₂O活性和价态均较为稳定,CuO活性较低。
- 铜基催化剂 /
- 活性炭 /
- 预处理 /
- 氧化羰基化 /
- 碳酸二甲酯 /
- 非均相催化
Abstract: The Cu₂O/AC catalyst prepared by pyrolysis of copper acetate supported on activatede carbon was pretreated under oxidative (O₂/N₂) or reductive (H₂/N₂ and CO/N₂) atmospheres. The oxidation/reduction of Cu₂O was completed through pretreatment at 350 ℃ for 4 h, the Cu₂O in catalyst could be completely oxidized to CuO by oxidative atmosphere, or reduced to metallic copper by reductive atmosphere. The catalyst activities were evaluated in a continuous fixed-bed tubular micro reactor under atmospheric pressure at 140 ℃. The catalyst pretreated by CO/N₂ had good Cu⁰ dispersion on its surface and exhibited the highest activity. The space-time yield and selectivity of DMC reached 261.9 mg/(g·h) and 74.7%, respectively. After 58 h reaction, the valence state of copper species and the catalytic activity of catalysts pretreated by reductive atmosphere were found to be close to that of the Cu₂O/AC catalyst. Comparing the catalytic performance, the characterization of surface and bulk copper species before and after reaction, it was obvious that metallic copper exhibited a high initial activity, while Cu₂O was stable in catalytic activity and valence state, and CuO was low in activity.
- copper based catalyst /
- activated carbon /
- pretreatment /
- oxidative carbonylation /
- dimethyl carbonate /
- heterogeneous catalysis

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参考文献(28)

KELLER N, REBMANN G, KELLER V. Catalysts, mechanisms and industrial processes for the dimethyl carbonate synthesis[J]. J Mol Catal A: Chem, 2010, 317(1/2): 1-18.

宋一兵, 罗爱国, 杜玉海, 方奕文. 甲醇直接气相氧化羰基化合成碳酸二甲酯[J]. 化学进展, 2008, 20(2/3): 221-226. (SONG Yi-bin, LUO Ai-guo, DU Yu-hai, FANG Yi-wen. Synthesis of dimethyl carbonate by direct vapor-phase oxycarbonylation of methanol[J]. Prog Chem, 2008, 20(2/3): 221-226.)

RICHTER M, FAIT M J G, ECKELT R, SCHNEIDER M, RADNIK J, HEIDEMANN D, FRICKE R. Gas-phase carbonylation of methanol to dimethyl carbonate on chloride-free Cu-precipitated zeolite Y at normal pressure[J]. J Catal, 2007, 245(1): 11-24.

RICHTER M, FAIT M J G, ECKELT R, SCHREIER E, SCHNEIDER M, POHL M-M, FRICKE R. Oxidative gas phase carbonylation of methanol to dimethyl carbonate over chloride-free Cu-impregnated zeolite Y catalysts at elevated pressure[J]. Appl Catal B: Environ, 2007, 73(3/4): 269-281.

张海涛, 王淑芳, 赵新强, 王延吉. 负载型CuO催化剂上甲醇气相氧化羰基化合成碳酸二甲酯反应研究[J]. 河北工业大学学报, 2004, 33(4): 36-40. (ZHANG Hai-tao,WANG Shu-fang,ZHAO Xin-qiang,WANG Yan-ji. Study of synthesis of dimethyl carbonate by gas-phase oxidative carbonylation of methanol over supported copper catalysts[J]. J Hebei Univ Techol, 2004, 33(4): 36-40.)

李忠, 文春梅, 王瑞玉, 郑华艳, 谢克昌. 醋酸铜热解制备无氯Cu₂O/AC催化剂及其催化氧化羰基化[J]. 高等学校化学学报, 2009, 30(10): 2024-2031. (LI Zhong,WEN Chun-mei, WANG Rui-yu, ZHENG Hua-yan, XIE Ke-chang. Chloride-free Cu₂O/AC catalyst prepared by pyrolysis of copper acetate and catalytic oxycarbonylation[J]. Chem J Chin Univ, 2009, 30(10): 2024-2031.)

李忠, 文春梅, 郑华艳, 谢克昌. 载体表面性质对Cu₂O/AC催化剂结构和活性的影响[J]. 高等学校化学学报, 2010, 31(1): 145-152. (LI Zhong, WEN Chun-mei, ZHENG Hua-yan, XIE Ke-chang. Effects of the active carbon surface properties on the structure and catalytic activity of Cu₂O/AC catalyst[J]. Chem J Chin Univ, 2010, 31(1): 145-152.)

章日光, 郑华艳, 王宝俊, 李忠. CO和CH₃O在Cu₂O (Ш)表面吸附特性及共吸附的理论研究[J]. 高等学校化学学报, 2010, 31(6): 1246-1251. (ZHANG Ri-guang, ZHENG Hua-yan, WANG Bao-jun, LI Zhong. Theoretical study on the properties of CO and CH₃O adsorption on Cu₂O(111) surface and co-adsorption[J]. Chem J Chin Univ, 2010, 31(6): 1246-1251.)

YAN B, HUANG S Y, WANG S P, MA X B. Catalytic oxidative carbonylation over Cu₂O nanoclusters supported on carbon materials: The role of the carbon support[J]. Chem Cat Chem, 2014, 6(9): 2671-2679.

王瑞玉, 李忠, 郑华艳, 谢克昌. 无氯Cu/AC催化剂的制备及其催化气相甲醇氧化羰基化反应性能[J]. 催化学报, 2010, 31(7): 851-856. (WANG Rui-yu, LI Zhong, ZHENG Hua-yan, XIE Ke-chang. Preparation of chlorine-free Cu/AC catalyst and its catalytic properties for vapor phase oxidative carbonylation of methanol[J]. Chin J Catal, 2010, 31(7): 851-856.)

任军, 郭长江, 杨雷雷, 李忠. 淀粉基炭负载纳米铜催化合成碳酸二甲酯[J]. 催化学报, 2013, 34(9): 1734-1744. (REN Jun, GUO Chang-jiang, YANG Lei-lei, LI Zhong. Synthesis of dimethyl carbonate over starch-based carbon-supported Cu nanoparticles catalysts[J]. Chin J Catal, 2013, 34(9): 1734-1744.)

REN J, WANG W, WANG D l, ZUO Z J, LIN J Y, LI Z. A theoretical investigation on the mechanism of dimethyl carbonate formation on Cu/AC catalyst[J]. Appl Catal A: Gen, 2014, 472: 47-52.

WANG L C, HE L, LIU Y M, CAO Y, HE H Y, FAN K N, ZHUANG J H. Effect of pretreatment atmosphere on CO oxidation over α-Mn₂O₃ supported gold catalysts[J]. J Catal, 2009, 264(2): 145-157.

邹汉波, 陈胜洲, 林维明. Cu₁Zr₁Ce₉Oδ催化剂选择性氧化CO性能的研究[J]. 工业催化, 2008, 16(2): 23-27. (ZOU Han-bo, CHEN Sheng-zhou, LIN Wei-ming. Effect of reaction conditions on the performance of Cu₁Zr₁Ce₉Oδ catalyst for selective oxidation of CO[J]. Ind Catal, 2008, 16(2): 23-27.)

张丽萍, 万海勤, 朱捷, 宋春燕, 刘斌, 李丹, 董林. CO预处理对CuO/γ-Al ₂O₃催化剂性能的影响[J]. 无机化学学报, 2007, 23(3): 427-431. (ZHANG Li-ping, WAN Hai-qin, ZHU Jie, SONG Chun-yan, LIU Bin, LI Dan, DONG Lin. Effect of CO pretreatment on properties of CuO/γ-Al ₂O₃ catalyst[J]. Chin J Inorg Chem, 2007, 23(3): 427-431.)

WAN H Q, LI D, DAI Y, HU Y H, ZHANG Y H, LIU L J, ZHAO B, LIU B, SUN K Q, DONG L, CHEN Y. Effect of CO pretreatment on the performance of CuO/CeO₂/γ-Al₂O₃ catalysts in CO+O₂ reactions[J]. Appl Catal A: Gen, 2009, 360(1): 26-32.

BUKUR D B, LANG X S, DING Y J. Pretreatment effect studies with a precipitated iron Fischer-Tropsch catalyst in a slurry reactor[J]. Appl Catal A: Gen, 1999, 186(1/2): 255-275.

ZHANG Y C, TANG J Y, WANG G L, ZHANG M, HU X Y. Facile synthesis of submicron Cu₂O and CuO crystallites from a solid metalorganic molecular precursor[J]. J Cryst Growth, 2006, 294(2): 278-282.

HUANG L, PENG F, YU H, WANG H J. Preparation of cuprous oxides with different sizes and their behaviors of adsorption, visible-light driven photocatalysis and photocorrosion[J]. Solid State Sci, 2009, 11(1): 129-138.

CHEN A P, LONG H, LI X C, LI Y H, YANG G, LU P X. Controlled growth and characteristics of single-phase Cu₂O and CuO films by pulsed laser deposition[J]. Vacuum, 2009, 83(6): 927-930.

WANG L C, LIU Y M, CHEN M, CAO Y, HE H Y, WU G S, DAI W L, FAN K N. Production of hydrogen by steam reforming of methanol over Cu/ZnO catalysts prepared via a practical soft reactive grinding route based on dry oxalate-precursor synthesis[J]. J Catal, 2007, 246(1): 193-204.

GVNTER M M, RESSLER T, JENTOFT R E, BEMS B.Redox behavior of copper oxide/zinc oxide catalysts in the steam reforming of methanol studied by in situ X-ray diffraction and adsorption spectroscopy[J]. J Catal, 2001, 203(1): 133-149.

LUO M F, FANG P, HE M, XIE Y L. In situ XRD, Raman, and TPR studies of CuO/Al₂O₃ catalysts for CO oxidation[J]. J Mol Catal A: Chem, 2005, 239(1/2): 243-248.

李忠, 黄海彬, 谢克昌. Cu(I)/SO₄^2-/ZnO和Cu(I)/S₂₈O^2-/ZnO催化剂的制备与表征[J]. 高等学校化学学报, 2008, 29(8): 1609-1615. (LI Zhong, HUANG Hai-bin, XIE Ke-chang. Preparation and characterization of Cu(I)/SO₄^2-/ZnO and Cu(I)/S₂₈O^2-/ZnO catalysts[J]. Chem J Chin Univ, 2008, 29(8): 1609-1615.)

LEE C Y, HA B H. Reduction behavior of copper oxide in copper/mordenites[J]. Stud Surf Sci Catal, 1994, 84: 1563-1570.

WAN Y, MA J X, WANG Z, ZHOU W, KALIAGUINE S. Selective catalytic reduction of NO over Cu-Al-MCM-41[J]. J Catal, 2004, 227(1): 242-252.

YANG P, CAO Y, DAI W L, DENG J F, FAN K N. Effect of chemical treatment of activated carbon as a support for promoted dimethyl carbonate synthesis by vapor phase oxidative carbonylation of methanol over Wacker-type catalysts[J]. Appl Catal A: Gen, 2003, 243(2): 323-331.

姜瑞霞, 宋兴涛, 陈大伟, 畅延青, 谢在库. 高温氢气处理对活性炭及钯炭催化剂性能的影响[J]. 化学反应工程与技术, 2007, 23(4): 375-379. (JIANG Rui-xia, SONG Xing-tao, CHEN Da-wei, CHANG Yan-qing, XIE Zai-ku. Effects of hydrogen treatment on the properties of activated carbon and Pd/C catalysts[J]. Chem React Eng Technol, 2007, 23(4): 375-379.)

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