钒磷氧合成条件对丁烷选择性氧化催化性能的影响

doi:10.19894/j.issn.1000-0518.200283

摘要/Abstract

摘要： 正丁烷氧化制备顺酐是低碳烷烃高值化利用的典型代表,钒磷氧(VPO)催化剂是该反应唯一的工业催化剂。通过调控有机相法合成过程中还原时间、回流时间和磷钒物质的量比3种实验参数,合成系列VPO催化剂,结合多种分析手段,探索合成条件对催化剂结构的影响规律,获得精细调控催化剂合成的方法和最优条件,催化正丁烷选择性氧化反应,转化率可达93.8％,顺酐收率达62.4％。进而精准构筑VPO催化剂,揭示VPO催化正丁烷选择性氧化制顺酐反应中的构效关系。

关键词: 钒磷氧, 合成条件, 正丁烷, 选择性氧化, 顺酐

Abstract: Oxidation of n-butane to maleic anhydride (MA) is a typical representative of selective oxidation of light alkanes, and vanadium phosphorus oxide (VPO) catalyst is the most effective and only industrial catalyst for this reaction. In this thesis, by adjusting three groups of experimental parameters including reduction time, reflux time and P/V ratio, a series of VPO catalysts was synthesized. Combined with a variety of analysis methods, the influence of synthesis conditions on the catalyst structure was explored to accurately construct VPO catalysts, and the optimal synthesis conditions were obtained, the conversion and yield of MA were 93.8% and 62.4% respectively. Furthermore, the structure-activity relationship of VPO catalysts for catalyzing selective oxidation of n-butane to MA was revealed.

Key words: Vanadium phosphorus oxide, Synthesis conditions, n-Butane, Selective oxidation, Maleic anhydride

中图分类号:

O643.3

谢志琦, 张婷, 李英崴, 王周君, 代飞, 张瑞锐, 刘瑞霞. 钒磷氧合成条件对丁烷选择性氧化催化性能的影响[J]. 应用化学, 2021, 38(4): 414-421.

XIE Zhi-Qi, ZHANG Ting, LI Ying-Wei, WANG Zhou-Jun, DAI Fei, ZHANG Rui-Rui, LIU Rui-Xia. Effect of Synthesis Conditions of Vanadium Phosphorus Oxygen (VPO) Catalyst on Catalytic Performance for Selective Oxidation of Butane[J]. Chinese Journal of Applied Chemistry, 2021, 38(4): 414-421.

参考文献

[1] MICHALAKOS P M, BELLIS H E, BRUSKY P, et al. Synthesis of vanadium phosphorus oxide catalysts by aerosol processing[J]. Ind Eng Chem Res, 1995, 34(6): 1994-2000.
[2] NAKATO T, FURUMI Y, TERAO N, et al. Reaction of layered vanadium phosphorus oxides, VOPO₄·2H₂O and VOHPO₄·0.5H₂O, with amines and formation of exfoliative intercalation compounds[J]. J Mater Chem, 2000, 10(3): 737-743.
[3] HIYOSHI N, YAMAMOTO N, OKUHARA T. Novel preparation of vanadyl pyrophosphate for selective oxidation of n-butane utilizing intercalation and exfoliation[J]. Chem Lett, 2001, (6): 484-485.
[4] TAKITA Y, HASHIGUCHI T, MATSUNOSAKO H. The vapor-phase preparation of V-P-O catalysts effective for butane oxidation to maleic-anhydride[J]. Bull Chem Soc Jpn, 1988, 61(10): 3737-3739.
[5] MIQUEL P F, BORDES E, KATZ J L. Flame generation of two new precursors of vanadyl pyrophosphate[J]. J Solid State Chem, 1996, 124(1): 95-103.
[6] LOPEZ-SANCHEZ J A, BARTLEY J K, BURROWS A, et al. Effects of cobalt additive on amorphous vanadium phosphate catalysts prepared using precipitation with supercritical CO₂ as an antisolvent[J]. New J Chem, 2002, 26(12): 1811-1816.
[7] HUTCHINGS G J, BARTLEY J K, WEBSTER J M, et al. Amorphous vanadium phosphate catalysts from supercritical antisolvent precipitation[J]. J Catal, 2001, 197(2): 232-235.
[8] HUTCHINGS G J, LOPEZ-SANCHEZ J A, BARTLEY J K, et al. Amorphous vanadium phosphate catalysts prepared using precipitation with supercritical CO₂ as an antisolvent[J]. J Catal, 2002, 208(1): 197-210.
[9] HUTCHINGS G J. Catalyst synthesis using supercritical carbon dioxide: a green route to high activity materials[J]. Top Catal, 2009, 52(8): 982-987.
[10] LEONG L K, CHIN K S, TAUFIQ-YAP Y H. Effect of varying reflux durations on the physico-chemical and catalytic performance of vanadium phosphate catalysts synthesized via vanadyl hydrogen phosphate sesquihydrate[J]. Appl Catal A-Gen, 2012, 415:53-58.
[11] GARBASSI F, BART J C J, MONTINO F, et al. Preparation and characterization of vanadium-phosphorus oxidation catalysts[J]. Appl Catal, 1985, 16(3): 271-287.
[12] RUIZ P, BASTIANS P, CAUSSIN L, et al. New aspects of the cooperation between phases in vanadium phosphate catalysts[J]. Catal Today, 1993, 16(1): 99-111.
[13] ZHANG T, ZHANG R, ZHANG Y, et al. Phosphoric acid: a key role in control of structure and properties of vanadium phosphorus oxide catalysts during synthesis[J]. Chemistryselect, 2021,6(4): 513-521.
[14] HOROWITZ H S, BLACKSTONE C M, SLEIGHT A W, et al. V-P-O catalysts for oxidation of butane to maleic anhydride-influence of (VO)₂H₄P₂O₉ precursor morphology on catalytic properties[J]. Appl Catal, 1988, 38(2): 193-210.
[15] CAVANI F, LUCIANI S, ESPOSTI E D, et al. Surface dynamics of a vanadyl pyrophosphate catalyst for n-butane oxidation to maleic anhydride: an in situ raman and reactivity study of the effect of the P/V atomic ratio[J]. Chemistry, 2010, 16(5): 1646-1655.
[16] 黄仲涛, 耿建铭. 工业催化[M]. 第二版. 北京:化学工业出版社, 2007.
HUANG Z T, GENG J M. Industrial catalysis[M]. 2nd ed. Beijing: Chemical Industry Press, 2007.
[17] BÖCKLEIN S, MESTL G, AURAS S V, et al. On the Correlation of structure and catalytic performance of VPO catalysts[J]. Top Catal, 2017, 60(19-20): 1682-1697.
[18] ZIOLOTKOWSKI J, BORDES E, COURTINE P. Dynamic description of the oxidation of n-butane on various facts of (VO)₂P₂O₇ in terms of the crystallochemical model of active-sites[J]. J Mol Catal, 1993, 84: 307-326.