工业钒磷氧催化剂的失活规律研究

石油炼制与化工 ›› 2026, Vol. 57 ›› Issue (6): 99-103.

工业钒磷氧催化剂的失活规律研究

郭金¹,张霞¹,李澜鹏¹,李剑²,杨效军²

1. 中石化（大连）石油化工研究院有限公司
2. 中国石化仪征化纤有限责任公司

收稿日期:2025-10-24 修回日期:2026-01-23 出版日期:2026-06-12 发布日期:2026-05-22
通讯作者: 张霞 E-mail:zhangxia.fshy@sinopec.com
基金资助:
中国石油化工股份有限公司资助项目

STUDY ON DEACTIVATION OF AN INDUSTRIAL VANADIUM PHOSPHORUS OXIDE CATALYST

Received:2025-10-24 Revised:2026-01-23 Online:2026-06-12 Published:2026-05-22

摘要/Abstract

摘要： 在补磷条件下，研究了正丁烷氧化制顺丁烯二酸酐（顺酐）工业钒磷氧催化剂应用性能的变化规律。对比了新鲜催化剂与工业运转4年后的催化剂，采用多种表征手段分析了催化剂的晶相结构、表面酸性、元素组成及价态等性质。结果表明，长周期运转后的催化剂比表面积、孔体积及孔径变化不大，但晶相结构发生显著变化，含V⁵⁺磷酸氧钒（VOPO₄）晶相逐渐消失，而含V⁴⁺的焦磷酸氧钒[(VO)₂P₂O₇]晶相存在。同时，催化剂表面磷元素流失严重，导致酸量下降，钒的平均价态降低，表面氧浓度减少。随着运转时间的延长，平均反应温度逐渐升高，顺酐的摩尔收率逐渐下降。

关键词: 钒磷氧催化剂, 晶相组成, 正丁烷, 选择性氧化

Abstract: The performance variation of industrial vanadium phosphorus oxide (VPO) catalyst for n-butane oxidation to maleic anhydride under phosphorus replenishment conditions was investigated. By comparing the fresh catalyst with the catalyst after four years of industrial operation, various physicochemical characterization techniques were employed to analyze the crystal phase structure, surface acidity, elemental composition, and valence state of the catalyst. The results indicated that the specific surface area, pore volume, and pore size of the catalyst after long-term operation changed insignificantly, but the crystal phase structure underwent significant changes. The vanadium(V) phosphate (VOPO₄) phase gradually disappeared, and the catalyst mainly existed in the form of the vanadium(Ⅳ) pyrophosphate ((VO)₂P₂O₇) phase. Meanwhile, severe phosphorus loss occurred on the catalyst surface, leading to a decrease in acidity, a reduction in the average vanadium valence, and a decrease in surface oxygen concentration. In the reactor, as the operation time extended, the average reaction temperature gradually increased, and the molar yield of maleic anhydride gradually decreased.

Key words: VPO catalyst, crystal composition, n-butane, selective oxidation

郭金张霞李澜鹏李剑杨效军. 工业钒磷氧催化剂的失活规律研究[J]. 石油炼制与化工, 2026, 57(6): 99-103.

参考文献

[1]M.ABON,KE. BERE,A. TUEL,P. DELICHERE.Evolution of a VPO Catalyst in n-butane oxidation reaction during the activation time[J].J. Catal., 1995, 156(1):28-36 [2]J XU, R.JI,YSUN,X.YAN,R. HUANG,C. LI..Boron doping highly improves the low-Temperature reactivity of VPO catalysts by partially reconstructing the catalyst structures[J].ACS Catal., 2025, 15(8):6581-6594 [3]G.ZICHITTELLA,VPAUNOVIC,A.P. AMRUTE,J. PEREZ-RAMIREZ..Catalytic oxychlorination versus oybromination for methane functionalization[J].ACS Catal., 2017, 7(1):1805-1817 [4]X ZHANG, H WANG,LGOU,L. LI,A. DUAN,Z. CAO..Synthesis of an efficient VPO catalyst for the selective oxidation of n-butane to the MA product: Mechanism of crystal transformation[J].Chem. Eng. Sci., 2023, 274(1):118708-118712 [5]J. XU, N. LI, X. LI, R. JI, X. YAN, R. HUANG, C. LI..Role of regulating synthetic solvents in enhancing the catalytic performance of VPO catalysts for n-butane oxidation to maleic anhydride[J].Chem. Eng. J., 2024, 496(1):153635-153639 [6]K A T-LACHGAR, A.TUEL,MBRUN,J.M. HERRMANN，J.M. KRAFFT,J.R. MARTIN,J. C. VOLTA,M. ABON..Selective oxidation of n-butane to maleic anhydride on vanadyl pyrophosphate. II. Characterization of the oxygen-treated catalyst by electrical conductivity,Raman,XPS and NMR spectroscopies[J].J. Catal., 1998, 177(1):383-390 [7]张霞, 陈志明, 王海波, 等.晶相组成对钒磷氧催化剂性能的影响[J].精细石油化工, 2023, 40(1):31-35 [8]曾翎, 季伟捷, 陈懿.活化气氛对钒磷氧催化剂物性的影响[J].石油与天然气化工, 2002, 31(3):111-113 [9]贾雪飞, 张东顺.正丁烷选择氧化制顺酐钒磷氧催化剂晶相结构的研究进展[J].石油化工, 2016, 45(6):749-755 [10]陈炳旭, 顾龙勤, 曾炜, 等.正丁烷氧化制顺酐催化剂失活研究[J].工业催化, 2022, 30(7):5-10 [11]Y ZHANG, R.P. ASNEEDEN,J. C. VOLTA..On the nature of the active sites of the VPO catalysts for n-butane oxidation to maleic anhydride[J].Catal. Today., 1993, 16(1):39-49 [12]M.ABON,JC. VOLTA..Vanadium phosphorus oxides for n-butane oxidation to maleic anhydride[J].Appl. Catal. A-Gen., 1997, 157(1):173-193 [13]X GUO, D.YANG,CZUO,Z. PENG,C. LI,S. ZHANG..Catalysts,process optimization,and kinetics for the production of methyl acrylate over vanadium phosphorus oxide catalysts.[J].Ind. Eng. Chem. Res., 2017, 56(20):5860-5871 [14]B Jiang, S.Yuan,MTong,H. Wang,Y. Yu,Z. Huang,Y. Yang..Influence of the Structural Characteristics of VPO Catalysts on the Temperature Sensitivity of the Oxidation Reaction of n-Butane to Maleic Anhydride.[J].Ind. Eng. Chem. Res., 2022, 61(37):13816-13826 [15]X ZHANG, H. WANG, L. GOU, L. LI, A. DUAN, Z. CAO..Effect of crystalline phases for VPO catalysts on the oxidation of butane: thermodynamics and kinetics.[J].Ind. Eng. Chem. Res., 2021, 60(42):15056-15063 [16]F CAVANI, D.D. SANTI, S. LUCIANI, A. L FBERG, E. BORDES-RICHARD, C. CORTELLI, R. LEANZA..Transient reactivity of vanadyl pyrophosphate, the catalyst for n-butane oxidation to maleic anhydride, in response to in-situ treatments[J].Appl. Catal. A, 2010, 376(1):66-75