Please wait a minute...
浙江大学学报(工学版)
J4  2012, Vol. 46 Issue (2): 232-236    DOI: 10.3785/j.issn.1008-973X.2012.02.008
化学工程     
Au/Al2O3催化剂上环己烷氧化
赵静, 朱明乔, 杨洋洋, 戴欢, 蔡贞玉, 陈新志
浙江大学 化学工程与生物工程学系, 浙江 杭州 310027
Study of cyclohexane oxidation over Au/Al2O3 catalyst
ZHAO Jing, ZHU Ming-qiao, YANG Yang-yang,
DAI Huan, CAI Zhen-yu, CHEN Xin-zhi
Department of Chemical and Biochemical Engineering, Zhejiang University, Hangzhou 310027, China
 全文: PDF 
摘要：

针对金催化剂制备过程的复杂性和氯离子残留问题,介绍一种负载型金催化剂Au/Al2O3的制备方法和考察该催化剂在环己烷氧化中的催化性能.采用浸渍氨洗法制备Au/Al2O3催化剂,并应用电感耦合等离子体原子发射光谱（ICP-AES）、X射线衍射（XRD）和透射电子显微镜（TEM）对其进行表征.以氧气氧化环己烷制备环己酮和环己醇为研究对象,考察金质量分数、反应温度、压力、时间等因素对催化活性的影响.结果表明,随着金质量分数增加,金颗粒增大,催化剂的活性降低，在150 ℃、1.5 MPa条件下反应3 h,Au实际质量分数为0.58%的Au/Al2O3催化剂上环己烷转化率为8.96%,环己酮、环己醇和环己基过氧化氢三者的总选择性为93.52%.此外,循环实验表明Au/Al2O3催化剂具有一定的稳定性.
关键词： 金催化剂;  氧化铝;  环己烷;  氧化    
Abstract:

According to the problems of complexity and chloride ion residue in the preparation of gold catalysts, a preparation method to obtain supported gold catalyst Au/Al2O3 was introduced and its catalytic performance was tested for cyclohexane oxidation. Au/Al2O3 catalysts were prepared by an impregnation-ammonia washing method. Inductively coupled plasma-atomic emission spectrometry (ICP-AES), X-ray diffraction (XRD) and transmission electron microscopy (TEM) were used to characterize these catalysts. The effects of gold loadings, reaction temperature, pressure and reaction time on the catalytic activity for the selective oxidation of cyclohexane to cyclohexanone and cyclohexanol using molecular oxygen as oxidant were studied. The results show that the higher the gold loading is, the bigger the size of the gold particles is and the lower the catalytic activity is. Under the reaction conditions of 150 ℃, 1.5 MPa and 3 h, using Au/Al2O3 catalyst with an actual gold loading of 0.58%, the cyclohexane conversion can reach 8.96% with 93.52% of total selectivity to cyclohexanone, cyclohexanol and cyclohexyl hydroperoxide. Moreover, according to the recycling test, the Au/Al2O3 catalyst exhibites good stability.
Key words:  gold catalyst    alumina    cyclohexane    oxidation
出版日期: 2012-03-02
:  TQ 231.14  
基金资助:

浙江省自然科学基金资助项目（Y4080247）；浙江省自然科学基金杰出青年团队资助项目（R40903580）；广西石化资源加工及过程强化技术重点实验室开放课题基金资助.
通讯作者: 朱明乔,男,副教授,     E-mail: zhumingqiao@zju.edu.cn
作者简介: 赵静(1987—),女,硕士生,从事绿色催化研究,E-mail: zhaojingzj@zju.edu.cn
服务　　
把本文推荐给朋友
加入引用管理器
E-mail Alert
RSS
作者相关文章　　

引用本文:

赵静, 朱明乔, 杨洋洋, 戴欢, 蔡贞玉, 陈新志. Au/Al2O3催化剂上环己烷氧化[J]. J4, 2012, 46(2): 232-236.

ZHAO Jing, ZHU Ming-qiao, YANG Yang-yang, DAI Huan, CAI Zhen-yu, CHEN Xin-zhi. Study of cyclohexane oxidation over Au/Al2O3 catalyst. J4, 2012, 46(2): 232-236.

链接本文:

http://www.zjujournals.com/xueshu/eng/CN/10.3785/j.issn.1008-973X.2012.02.008    或    http://www.zjujournals.com/xueshu/eng/CN/Y2012/V46/I2/232

［1］ 郭志武,靳海波,佟泽民.环己酮、环己醇制备技术进展［J］.化工进展,2006,25(8): 852-858.
GUO Zhiwu, JIN Haibo, TONG Zemin. Advances in techniques for production of cyclohexanone and cyclohexanol ［J］. Chemical Industry and Engineering Progress, 2006, 25(8): 852-858.
［2］ SCHUCHARDT U, CARDOSO D, SERCHELI R, et al. Cyclohexane oxidation continues to be a challenge ［J］. Applied Catalysis A: General, 2001, 211(1): 1-17.
［3］ HARUTA M, KOBAYASHI T, SANO H, et al. Novel gold catalysts for the oxidation of carbon monoxide at a temperature far below 0℃ ［J］. Chemistry Letters, 1987, 16(2): 405-408.
［4］ HARUTA M, YAMADA N, KOBAYASHI T, et al. Gold catalysts prepared by coprecipitation for lowtemperature oxidation of hydrogen and of carbon monoxide ［J］. Journal of Catalysis, 1989, 115(2): 301-309.
［5］ HASHMI A S K, HUTCHINGS G J. Gold Catalysis ［J］. Angewandte Chemie International Edition, 2006, 45(47): 7896-7936.
［6］ PINA C D, FALLETTA E, PRATI L, et al. Selective oxidation using gold ［J］. Chemical Society Reviews, 2008, 37(9): 2077-2095.
［7］ ZHAO R, JI D, LV G M, et al. A highly efficient oxidation of cyclohexane over Au/ZSM5 molecular sieve catalyst with oxygen as oxidant ［J］. Chemical Communications, 2004, (7): 904-905.
［8］ LI L, JIN C, WANG X C, et al. Cyclohexane oxidation over sizeuniform Au nanoparticles (SBA15 hosted) in a continuously stirred tank reactor under mild conditions ［J］. Catalysis Letters, 2009, 129(3/4): 303-311.
［9］ ZHU K K, HU J C, RICHARDS R. Aerobic oxidation of cyclohexane by gold nanoparticles immobilized upon mesoporous silica ［J］. Catalysis Letters, 2005, 100 (3/4): 195-199.
［10］ XIE J, WANG Y J, WEI Y. Immobilization of manganese tetraphenylporphyrin on Au/SiO2 as new catalyst for cyclohexane oxidation with air ［J］. Catalysis Communications, 2009, 11(2): 110-113.
［11］ XU L X, HE C H, ZHU M Q, et al. Silicasupported gold catalyst modified by doping with titania for cyclohexane oxidation ［J］. Catalysis Letters, 2007, 118(3/4): 248-253.
［12］ XU L X, HE C H, ZHU M Q, et al. A highly active Au/Al2O3 catalyst for cyclohexane oxidation using molecular oxygen ［J］. Catalysis Letters, 2007, 114(3/4): 202-205.
［13］ XU L X, HE C H, ZHU M Q, et al. Surface stabilization of gold by solgel postmodification of alumina support with silica for cyclohexane oxidation ［J］. Catalysis Communications, 2008, 9(5): 816-820.

［14］ 许立信,何潮洪,朱明乔,等.锆改性氧化铝负载的纳米金催化剂上环己烷氧化研究［J］.高校化学工程学报,2009,23(2): 309-313.
XU Lixin, HE Chaohong, ZHU Mingqiao, et al. Cyclohexane oxidation over nano gold catalysts supported on zirconiamodified alumina ［J］. Journal of Chemical Engineering of Chinese Universities, 2009, 23(2): 309-313.
［15］ MOREAU F, BOND G C, TAYLOR A O. Gold on titania catalysts for the oxidation of carbon monoxide: control of pH during preparation with various gold contents ［J］. Journal of Catalysis, 2005, 231(1): 105-114.
［16］ 王东辉,程代云,郝郑平,等.纳米金催化剂及其应用［M］.北京:国防工业出版社,2006: 22.
［17］ XU Q, KHARAS K C C, DATYE A K. The preparation of highly dispersed Au/Al2O3 by aqueous impregnation ［J］. Catalysis Letters, 2003, 85(3/4): 229-235.
［18］ DELANNOY L, HASSAN N E, MUSI A, et al. Preparation of supported gold nanoparticles by a modified incipient wetness impregnation method ［J］. Journal of Physical Chemistry B, 2006, 110(45): 22471-22478.
［19］ ZHOU L P, XU J, MIAO H, et al. Catalytic oxidation of cyclohexane to cyclohexanol and cyclohexanone over Co3O4 nanocrystals with molecular oxygen ［J］. Applied Catalysis A: General, 2005, 292: 223-228.
［20］ CHANG C K, CHEN Y J, YEH C T. Characterization of aluminasupported gold with temperatureprogrammed reduction ［J］. Applied Catalysis A: General, 1998, 174(1/2): 13-23.
[1] 曹伟波, 王丽军, 李希. 壁流蜂窝式微填充床制备及变压吸附中的应用[J]. 浙江大学学报(工学版), 2017, 51(4): 777-783.
[2] 韩磊,祝培旺,程乐鸣,王勤辉,施正伦,骆仲泱. 煤灰酸浸渣烧结反应试验[J]. 浙江大学学报(工学版), 2016, 50(5): 955-960.
[3] 王涛, 王亮, 林贵平, 柏立战, 刘向阳, 卜雪琴, 谢广辉. TiO2纳米流体在液冷服上的应用实验研究[J]. 浙江大学学报(工学版), 2016, 50(4): 681-690.
[4] 李媛, 尹雪峰, 张志磊. 负钛铜基载氧体在煤化学链燃烧中多环芳烃的生成[J]. 浙江大学学报(工学版), 2016, 50(2): 360-368.
[5] 徐辉, 蔡忆昔, 李小华, 施蕴曦, 李伟俊 . 低温等离子体降低柴油机微粒和NOx排放试验研究[J]. 浙江大学学报(工学版), 2016, 50(12): 2418-2423.
[6] 朱燕群, 杨业, 黄建鹏, 林法伟, 马强, 徐超群, 王智化, 岑可法. 橡胶厂60000 m3/h炭黑干燥炉烟气臭氧脱硝试验研究[J]. 浙江大学学报(工学版), 2016, 50(10): 1865-1870.
[7] 黄志义, 武斌, 康诚, 朱凯, 吴珂. 复合氢氧化物改性沥青阻燃和路用性能[J]. 浙江大学学报(工学版), 2016, 50(1): 27-32.
[8] 蒋伟, 柳景青, 叶萍, 李杭加. 氧化还原电位作为铁释放监测参数的中试研究[J]. 浙江大学学报(工学版), 2015, 49(4): 769-775.
[9] 邓凤霞,邱珊,岳秀丽,徐善文,陈聪,丁晓,马放. 非均相催化臭氧氧化深度处理炼油废水[J]. 浙江大学学报(工学版), 2015, 49(3): 555-563.
[10] 黄龙, 梁海莲, 顾晓峰, 董树荣, 毕秀文, 魏志芬. 多晶硅栅对LDMOS-SCR器件ESD防护性能的影响[J]. 浙江大学学报(工学版), 2015, 49(2): 366-370.
[11] 张莉, 王俏丽, 李伟, 李素静. 电力行业温室气体排放情景分析[J]. 浙江大学学报(工学版), 2015, 49(12): 2244-2251.
[12] 俞晋频,邱坤赞,宋浩,高翔,周劲松. Cr/TiO2催化剂汞氧化的实验[J]. 浙江大学学报(工学版), 2015, 49(11): 2186-2192.
[13] 方奕栋, 楼狄明, 胡志远, 谭丕强. 连续再生颗粒捕集器对生物柴油发动机颗粒及NOx排放的影响[J]. 浙江大学学报(工学版), 2015, 49(10): 1836-1841.
[14] 王晓,姚晓莉,候鉴峰,范利武,徐旭,俞自涛,胡亚才. 氧化石墨烯水悬浮液的非等温结晶过程[J]. 浙江大学学报(工学版), 2014, 48(7): 1272-1277.
[15] 唐月, 朱明乔, 黄霖, 王萌, 陈新志. Au/TS-1催化剂上葡萄糖氧化[J]. J4, 2013, 47(6): 1114-1119.