V4+和V5+比例对钒磷氧催化NO2氧化环己烷性能的影响

doi:10.11949/0438-1157.20221481

摘要/Abstract

摘要：

采用浸渍法制备不同钒价态结构的钒磷氧（VPO）复合氧化物催化剂，测试其对NO₂氧化环己烷制备己二酸的催化性能，并采用XRD、XPS、H₂-TPR和UV-Vis DRS等手段进行表征，考察不同过渡金属掺杂对VPO中钒价态结构的影响，以及催化氧化环己烷性能的影响。研究结果表明，过渡金属的引入能够改变VPO中β-VOPO₄和（VO）₂P₂O₇两种晶相结构，从而调变V⁵⁺和V⁴⁺的比例，且钒的价态比例对NO₂氧化环己烷反应具有重要影响。同时含有V⁵⁺和V⁴⁺ 的M/AlVPO催化剂的催化性能明显高于纯V⁵⁺的β-VOPO₄和纯V⁴⁺的（VO）₂P₂O₇催化剂。其中，以V⁴⁺/V⁵⁺ 为0.52的Cu/AlVPO为催化剂时环己烷的转化率最高为65.4%，以V⁴⁺/V⁵⁺ 为0.66的Ni/AlVPO为催化剂时己二酸的选择性最高为84.8%。

关键词: 钒磷氧复合氧化物, 环己烷, 己二酸, 催化氧化, 催化机理

Abstract:

Vanadium phosphorus oxide (VPO) catalysts doped with different transition metals were prepared by impregnation method, and their catalytic performance for cyclohexane oxidation by NO₂ to adipic acid were tested. The XRD, XPS, H₂-TPR and UV-Vis DRS were used to investigate the effect of transition metal doping on the valence structure of vanadium in VPO catalysts and the catalytic performance for oxidation of cyclohexane. The results showed that the introduction of transition metals could change the phase structure ratio of β-VOPO₄ and (VO)₂P₂O₇ in VPO samples, thus changing the ratio of V⁵⁺ and V⁴⁺. In addition, the valence structure of vanadium in VPO catalysts played an important effect in the oxidation of cyclohexane to adipic acid by NO₂. The catalytic performance of M/AlVPO catalyst containing both V⁵⁺ and V⁴⁺ was significantly higher than that of the pure V⁵⁺ β-VOPO₄ and pure V⁴⁺ (VO)₂P₂O₇ catalysts. Among them, when Cu/AlVPO with V⁴⁺/V⁵⁺ of 0.52 was used as the catalyst, the conversion rate of cyclohexane was 65.4%, and the selectivity of adipic acid was 84.8% when Ni/AlVPO with V⁴⁺/V⁵⁺ of 0.66 was used as the catalyst.

Key words: VPO composite oxides, cyclohexane, adipic acid, catalytic oxidation, catalytic mechanism

中图分类号:

TQ 235

蹇建, 张嘉明, 佘祥, 周虎, 游奎一, 罗和安. V⁴⁺和V⁵⁺比例对钒磷氧催化NO₂氧化环己烷性能的影响[J]. 化工学报, 2023, 74(4): 1570-1577.

Jian JIAN, Jiaming ZHANG, Xiang SHE, Hu ZHOU, Kuiyi YOU, Hean LUO. Correlation with the redox V⁴⁺/V⁵⁺ ratio in VPO catalysts for oxidation of cyclohexane by NO₂[J]. CIESC Journal, 2023, 74(4): 1570-1577.

图/表 9

图1 浸渍型M/Al-VPO复合催化剂的XRD谱图

Fig.1 XRD patterns of M/Al-VPO composite catalysts

表1 M/Al-VPO系列催化剂中β-VOPO4、（VO）2P2O7和AlV18PO49晶相的相对比例

Table 1 The relative ratio of β-VOPO4，（VO）2P2O7 and AlV18PO49 crystalline phases in M/Al-VPO catalysts

Catalyst	Crystal phase ratio/%
Catalyst	β-VOPO₄	(VO)₂P₂O₇	AlV₁₈PO₄₉
Cr/Al-VPO	85.41	2.34	12.25
Co/Al-VPO	59.88	22.82	17.31
Cu/Al-VPO	33.10	38.72	28.18
Ni/Al-VPO	32.55	45.33	22.12
Mn/Al-VPO	33.41	46.95	19.64

图2 浸渍型M/Al-VPO复合催化剂的UV-Vis DRS谱图

Fig.2 UV-Vis DRS spectra of M/Al-VPO composite catalysts

图3 浸渍型M/Al-VPO复合催化剂的V 2p3/2谱图

Fig.3 XPS spectra of V 2p3/2 of M/Al-VPO composite catalysts

表2 浸渍型M/Al-VPO催化剂V5+ 与V4+ 含量

Table 2 The percentages of V5+ and V4+ in various M/Al-VPO composite catalysts

Catalyst	V 2p_2/3/eV		V⁵⁺/%	V⁴⁺/%	V⁴⁺/V⁵⁺
Catalyst	V⁵⁺	V⁴⁺	V⁵⁺/%	V⁴⁺/%	V⁴⁺/V⁵⁺
β-VOPO₄	518.1	—	100	0	0
Cr/Al-VPO	518.4	517.0	89.0	11.0	0.12
Co/Al-VPO	518.7	516.5	72.1	27.9	0.39
Cu/Al-VPO	518.7	516.6	65.6	34.4	0.52
Ni/Al-VPO	518.3	516.9	60.3	39.7	0.66
Mn/Al-VPO	518.8	516.6	55.1	44.9	0.81

图4 浸渍型M/Al-VPO复合催化剂的H2-TPR图

Fig.4 The H2-TPR profiles of M/Al-VPO composite catalysts

图5 V4+/V5+比例对环己烷催化氧化反应的影响

Fig.5 Effect of V4+/V5+ ratio on the catalytic oxidation of cyclohexane

表3 自由基捕捉实验结果

Table 3 Results of radical capture experiment

催化剂	CBrCl₃转化率/%	选择性/%
催化剂	CBrCl₃转化率/%	溴代环己烷	氯代环己烷
无	0.11	trace	trace
(VO)₂P₂O₇	22.9	94.3	4.2
β-VOPO₄	68.6	83.5	12.8
Cu/Al-VPO	87.4	83.9	11.8
Ni/Al-VPO	76.6	84.3	12.1
Mn/Al-VPO	73.4	86.5	11.2
Co/Al-VPO	72.5	84.9	12.3
Cr/Al-VPO	72.2	85.2	12.6
Ni/Al-VPO^①	0	—	—

图6 M/Al-VPO复合氧化物催化的NO2液相氧化环己烷可能的反应机理

Fig.6 The possible reaction path of cyclohexane and NO2 over M/Al-VPO composites

参考文献 37

1	Liang F T, Zhong W Z, Xiang L P, et al. Synergistic hydrogen atom transfer with the active role of solvent: preferred one-step aerobic oxidation of cyclohexane to adipic acid by N-hydroxyphthalimide[J]. Journal of Catalysis, 2019, 378: 256-269.
2	Vernekar D, Dayyan M, Ratha S, et al. Direct oxidation of cyclohexane to adipic acid by a WFeCoO(OH) catalyst: role of Brønsted acidity and oxygen vacancies[J]. ACS Catalysis, 2021, 11(17): 10754-10766.
3	Wei H L, Liu S E, Li G X, et al. Numerical modeling of a microreactor for the synthesis of adipic acid via KA oil oxidation[J]. Chemical Engineering Science, 2021, 230: 116208.
4	巩有奎, 赵强, 彭永臻. 不同C/N下SBBR脱氮过程N₂O释放及胞外多聚物变化[J].化工学报, 2019, 70(12): 4847-4855.
	Gong Y K, Zhao Q, Peng Y Z. Variation of N₂O emission and EPS production during simultaneous nitrification and denitrification in SBBR under different C/N ratio[J]. CIESC Journal, 70(12): 4847-4855.
5	Sato K, Aoki M, Noyori R. A “green” route to adipic acid: direct oxidation of cyclohexenes with 30 percent hydrogen peroxide[J]. Science, 1998, 281(5383): 1646-1647.
6	Tortajada A, Ninokata R, Martin R. Ni-catalyzed site-selective dicarboxylation of 1,‍3-dienes with CO₂ [J]. Journal of the American Chemical Society, 2018, 140(6): 2050-2053.
7	Deng W P, Yan L F, Wang B J, et al. Efficient catalysts for the green synthesis of adipic acid from biomass[J]. Angewandte Chemie-International Edition, 2021, 60(9): 4712-4719.
8	Wei L F, Zhang J X, Deng W P, et al. Catalytic transformation of 2,5-furandicarboxylic acid to adipic acid over niobic acid-supported Pt nanoparticles[J]. Chemical Communication, 2019, 55: 8013-8016.
9	Wang X, Bian W Y, Ma Y R, et al. Hydroxyl-terminated carbon dots for efficient conversion of cyclohexane to adipic acid[J]. Journal of Colloid and Interface Science, 2021, 591: 281-289.
10	Kuznetsov M L, Pombeiro A J L. Metal-free and iron (Ⅱ)-assisted oxidation of cyclohexane to adipic acid with ozone: a theoretical mechanistic study[J]. Journal of Catalysis, 2021, 399: 52-66.
11	Shahzeydi A, Ghiaci M, Farrokhpour H, et al. Facile and green synthesis of copper nanoparticles loaded on the amorphous carbon nitride for the oxidation of cyclohexane[J]. Chemical Engineering Journal, 2019, 370: 1310-1321.
12	Guo X K, Xu M X, She M Y, et al. Morphology reserved synthesis of discrete nanosheets of CuO@SAPO-34 and pore mouth catalysis for one-pot oxidation of cyclohexane[J]. Angewandte Chemie-International Edition, 2020, 59: 2606-2611.
13	Acharyya S S, Ghosh S, Bal R. Nanoclusters of Cu (Ⅱ) supported on nanocrystalline W (Ⅵ) oxide: a potential catalyst for single-step conversion of cyclohexane to adipic acid[J]. Green Chemistry, 2015,17(6): 3490-3499.
14	Hwang K C, Sagadevan A. One-pot room-temperature conversion of cyclohexane to adipic acid by ozone and UV light[J]. Science, 2014, 346(6216): 1495-1498.
15	Jian J, You K Y, Duan X Z, et al. Boosting one-step conversion of cyclohexane to adipic acid by NO₂ and VPO composite catalysts[J]. Chemical Communication, 2016, 52(16): 3320-3323.
16	Jian J, You K Y, Luo Q, et al. Supported Ni-Al-VPO/MCM-41 as efficient and stable catalysts for highly selective one-step synthesis of adipic acid from cyclohexane with NO₂ [J]. Industrial & Engineering Chemistry Research, 2016, 55(13): 3729-3735.
17	刘瑞霞, 贺滨, 罗琛, 等. 钒磷氧复合氧化物及其在催化领域的应用[J].化工学报, 2018, 69(4): 1261-1275.
	Liu R X, He B, Luo C, et al. Vanadium phosphorous oxide and its catalytic application[J]. CIESC Journal, 2018, 69(4): 1261-1275.
18	Taufiq-Yap Y H, Saw C S. Effect of different calcination environments on the vanadium phosphate catalysts for selective oxidation of propane and n-butane[J]. Catalysis Today, 2008, 131(1/2/3/4): 285-291.
19	Liu Y, Guo W L, Guo H S, et al. Cu(Ⅱ)-doped V₂O₅ mediated persulfate activation for heterogeneous catalytic degradation of benzotriazole in aqueous solution[J]. Separation and Purification Technology, 2020, 230: 115848.
20	Zeng H M, Liu D Y, Zhang Y C, et al. Nanostructure Mn-doped V₂O₅ cathode material fabricated from layered vanadium jarosite[J]. Chemistry of Material, 2015, 27(21): 7331-7336.
21	Borah P, Datta A. Exfoliated VOPO₄·2H₂O dispersed on alumina as a novel catalyst for the selective oxidation of cyclohexane[J]. Applied Catalysis A: General, 2010, 376(1/2): 19-24.
22	Xiao C Y, Chen X, Wang Z Y, et al. The novel and highly selective fumed silica-supported VPO for partial oxidation of n-butane to maleic anhydride[J]. Catalysis Today, 2004, 93/94/95: 223-228.
23	Li W J, Xiao Y, Guo S P, et al. Increasing maleic anhydride selectivity for n-butane oxidation by Y-modified VPO catalysts[J]. Fuel, 2023, 333: 126214.
24	Zhu Y J, Li J, Xie X F, et al. Effect of different VOPO₄ phase catalysts on oxidative dehydrogenation of cyclohexane to cyclohexene in acetic acid[J]. Journal of Molecular Catalysis A: Chemical, 2006, 246: 185-189.
25	Feng R M, Yang X J, Ji W J, et al. VPO catalysts supported on H₃PO₄-treated ZrO₂ highly active for n-butane oxidation[J]. Journal of Catalysis, 2007, 246: 166-176.
26	He B, Li Z H, Zhang H L, et al. Synthesis of vanadium phosphorus oxide catalysts assisted by deep-eutectic solvents for n-butane selective oxidation[J]. Industrial & Engineering Chemistry Research, 2019, 58(8): 2857-2867.
27	黄继武,李周. 多晶材料X射线衍射:实验原理、方法与应用[M]. 北京:冶金工业出版社,2012: 97-108.
	Huang J W, Li Z. X-Ray Diffraction of Polycrystalline Materials: Experimental Principles, Methods and Applications[M]. Beijing: Metallurgical Industry Press, 2012: 97-108.
28	Rajan N P, Rao G S, Pavankumar V, et al. Vapour phase dehydration of glycerol over VPO catalyst supported on zirconium phosphate[J]. Catalysis Science & Technology, 2014, 4(1): 81-92.
29	Cavani F, Ligi S, Monti T, et al. Relationship between structural/surface characteristics and reactivity in n-butane oxidation to maleic anhydride: the role of V³⁺ species[J]. Catalysis Today, 2000, 61(1/2/3/4): 203-210.
30	Abon M, Bere K E, Tuel A, et al. Evolution of a VPO catalyst in n-butane oxidation reaction during the activation time[J]. Journal of Catalysis, 1995, 156(1): 28-36.
31	Kleimenov E, Bluhm H, Hävecker M, et al. XPS investigations of VPO catalysts under reaction conditions[J]. Surface Science, 2005, 575(1/2): 181-188.
32	Yang D, Sararuk C, Suzuki K, et al. Effect of calcination temperature on the catalytic activity of VPO for aldol condensation of acetic acid and formalin[J]. Chemical Engineering Journal, 2016, 300: 160-168.
33	徐淑媛, 李宁. 硝酸氧化醇酮生产己二酸反应机理和影响因素[J]. 工业催化, 2007, 15(10): 24-26.
	Xu S Y, Li N. Mechanism and influential factors for synthesis of adipic acid by oxidation of cyclohexanone/ol with nitric acid[J]. Industrial Catalysis, 2007, 15(10): 24-26.
34	Pierini B T, Lombardo E A. Structure and properties of Cr promoted VPO catalysts[J]. Materials Chemistry and Physics, 2005, 92(1): 197-204.
35	Li X K, Ji W J, Zhao J, et al. Ammonia decomposition over Ru and Ni catalysts supported on fumed SiO₂, MCM-41, and SBA-15[J]. Journal of Catalysis, 2005, 236(2): 181-189.
36	Sakaguchi S, Nishiwaki Y, Kitamura T, et al. Efficient catalytic alkane nitration with NO₂ under air assisted by N-hydroxyphthalimide[J]. Angewandte Chemie-International Edition, 2001, 40(1): 222-224.
37	Cook G K, Mayer J M. C—H bond activation by metal oxo species: oxidation of cyclohexane by chromyl chloride[J]. Journal of the American Chemical Society, 1994, 116(5): 1855-1868.

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V⁴⁺和V⁵⁺比例对钒磷氧催化NO₂氧化环己烷性能的影响

Correlation with the redox V⁴⁺/V⁵⁺ ratio in VPO catalysts for oxidation of cyclohexane by NO₂

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