李彦辰,吕喜蕾,陈旭杰,魏茜文,蒋雨希,田鹏辉,吕秀阳

• 1:浙江大学生物质化工教育部重点实验室，浙江大学 化学工程与生物工程学院，浙江 杭州 310027

摘要(Abstract)：

酮基化反应是生物质基有机酸高值化利用的途径之一，能同时实现碳链增长和脱氧。针对生物质基有机酸很多情况下与水共存的现状，本研究提出了近临界水中有机酸直接液相酮基化制备长链酮的思路。以丙酸为模型物质，开展了铈（Ce）、锆（Zr）、锰（Mn）复合氧化物的筛选，得到了近临界水中丙酸液相酮基化较佳的复合金属催化剂Ce₂ZrO_x。在340℃、Ce₂ZrO_x催化下丙酸水溶液酮基化反应30 h，丙酸转化率为85%、3-戊酮收率达81.6%，而且该复合金属氧化物具有良好的重复使用性能。对部分Ce-Zr复合金属氧化物开展了X射线衍射仪（XRD）、红外光谱仪（FT-IR）、透射电子显微镜（TEM）、比表面积及微介孔分析仪（BET）、X射线光电子能谱（XPS）、化学吸附仪（CO₂-TPD）等表征，阐明了Ce₂ZrO_x具有较高酮基化催化活性和水热稳定性的原因是形成了Ce-O-Zr固溶体结构、较高的氧空位浓度、较大的比表面积和较多数量的碱性位。此外，还开展了酮基化动力学研究，得到丙酸转化反应活化能为98.9 kJ·mol^-1、3-戊酮生成活化能为90.0 kJ·mol^-1、其他副产物生成活化能为105.7 kJ·mol^-1。研究工作可为高效、耐水性酮基化催化剂的研发提供借鉴。

关键词(KeyWords)： 液相酮基化;丙酸;Ce-Zr复合金属氧化物;近临界水

Abstract:

Keywords:

基金项目(Foundation): 国家自然科学基金（22078290）。

作者(Author): 李彦辰,吕喜蕾,陈旭杰,魏茜文,蒋雨希,田鹏辉,吕秀阳

DOI: 10.3969/j.issn.1003-9015.2021.06.007

参考文献(References)：

• [1] KUMAR R, ENJAMURI N, SHAH S, et al. Ketonization of oxygenated hydrocarbons on metal oxide based catalysts[J]. Catalysis Today, 2018, 302:16-49.
  [2] FRIEDEL C, UEBER S G.Gemischte acetone[J]. Justus Liebigs Annalen der Chemie, 1858, 108(1):122-125.
  [3] 丁爽, 葛庆峰, 祝新利. 金属氧化物催化生物质衍生羧酸酮基化研究进展[J]. 化学学报, 2017, 75(5):439-447. DING S, GE Q F, ZHU X L. Research progress in ketonization of biomass-derived carboxylic acids over metal oxides[J]. Acta Chimica Sinica, 2017, 75(5):439-447.
  [4] OROZCO L M, RENZ M, CORMA A. Cerium oxide as a catalyst for the ketonization of aldehydes:mechanistic insights and a convenient way to alkanes without the consumption of external hydrogen[J]. Green Chemistry, 2017, 19(6):1555-1569.
  [5] SERRANO-RUIZ J C, DUMESIC J A. Catalytic routes for the conversion of biomass into liquid hydrocarbon transportation fuels[J]. Energy & Environmental Science, 2011, 4(1):83-99.
  [6] PHAM T N, SHI D, RESASCO D E. Reaction kinetics and mechanism of ketonization of aliphatic carboxylic acids with different carbon chain lengths over Ru/TiO₂ catalyst[J]. Journal of Catalysis, 2014, 314:149-158.
  [7] LOPEZ-RUIZ J A, COOPER A R, LI G S, et al. Enhanced hydrothermal stability and catalytic activity of La_xZr_yO_z mixed oxides for the ketonization of acetic acid in the aqueous condensed phase[J]. ACS Catalysis, 2017, 7(10):6400-6412.
  [8] WU K J, YANG M D, HU H S, et al. ZrMn oxides for aqueous-phase ketonization of acetic acid:Effect of crystal and porosity[J]. Chemistry-An Asian Journal, 2018, 13(9):1180-1186.
  [9] DING S, WANG H, HAN J Y, et al. Ketonization of propionic acid to 3-pentanone over Ce_xZr_1-xO₂ catalysts:The importance of acid-base balance[J]. Industrial & Engineering Chemistry Research, 2018, 57(50):17086-17096.
  [10] LU F P, JIANG B B, WANG J D, et al. Insights into the improvement effect of Fe doping into the CeO₂ catalyst for vapor phase ketonization of carboxylic acids[J]. Molecular Catalysis, 2018, 444:22-33.
  [11] 吕秀阳, 何龙, 郑赞胜, 等. 近临界水中的绿色化工过程[J]. 化工进展, 2003, 22(4):477-481. LYU X Y, HE L, ZHENG Z S, et al. Green chemical processes in near critical water[J]. Chemical Industry and Engineering Progress, 2003, 22(4):477-481.
  [12] GLIŃSKI M, KIJENSKI J, JAKUBOWSKI A. Ketones from monocarboxylic acids:Catalytic ketonization over oxide systems[J]. Applied Catalysis A:General, 1995, 128(2):209-217.
  [13] GLIŃSKI M, ZALEWSKI G, BURNOE, et al. Catalytic ketonization over metal oxide catalysts. XIII. Comparative measurements of activity of oxides of 32 chemical elements in ketonization of propanoic acid[J]. Applied Catalysis A:General, 2014, 470:278-284.
  [14] CHEN L, HE B, HE S, et al. Fe-Ti oxide nano-adsorbent synthesized by co-precipitation for fluoride removal from drinking water and its adsorption mechanism[J]. Powder Technology, 2012, 227:3-8.
  [15] KAZUO N. Infrared and Raman spectra of inorganic and coordination compounds[M]. New York:John Wiley & Sons, 2006.
  [16] HASAN M A, ZAKI M I. Oxide-catalyzed conversion of acetic acid into acetone:An FTIR spectroscopic investigation[J]. Applied Catalysis, 2003, 243(1):81-87.
  [17] NELSON A E, SCHULZ K H. Surface chemistry and microstructural analysis of Ce_xZr_1-xO_2-y model catalyst surfaces[J]. Applied Surface Science, 2003, 210(3/4):206-221.
  [18] REDDY B M, KHAN A. Structural characterization of CeO₂-MO₂(M=Si⁴⁺,Ti⁴⁺and Zr⁴⁺) mixed oxides by Raman spectroscopy, X-ray photoelectron spectroscopy and other techniques[J]. Journal of Physical Chemistry, 2003, 107(41):11475-11484.
  [19] SNELL R W, HAKIM S H, DUMESIC J A, et al. Catalysis with ceria nanocrystals:Bio-oil model compound ketonization[J]. Applied Catalysis A:General, 2013, 464:288-295.