<i>M</i>/ZSM-5 (<i>M</i>=Cu、Mn、Fe、Ce、Ti) 催化氧化甲苯性能研究

彭新宇; 刘丽君; 沈伯雄; 边瑶; 苏立超

doi:10.1016/S1872-5813(22)60069-0

M/ZSM-5 (M=Cu、Mn、Fe、Ce、Ti) 催化氧化甲苯性能研究

doi: 10.1016/S1872-5813(22)60069-0

彭新宇^{1, 2,},
刘丽君^{1, 2},
沈伯雄^{1, 2, ,},
边瑶^{1, 2},
苏立超³

1.
河北工业大学能源与环境工程学院, 天津 300401
2.
天津市清洁能源利用与污染物控制重点实验室, 天津 300401
3.
邻筑(河北)工程产业技术研究有限公司, 河北邢台 054001

基金项目: 国家自然科学基金区域联合重点(U20A20302)，河北省创新群体(E2021202006)，河北省科技专项(20373701D)，河北省重大成果转化(21283701Z)和河北省石家庄科技项目(216240117A)资助

详细信息

通讯作者:
E-mail：shenbx@hebut.edu.cn

中图分类号: X511
计量
- 文章访问数: 503
- HTML全文浏览量: 220
- PDF下载量: 92
- 被引次数: 0
出版历程
- 收稿日期: 2022-08-29
- 修回日期: 2022-10-16
- 录用日期: 2022-10-18
- 网络出版日期: 2022-10-31
- 刊出日期: 2023-06-15

Insight into the catalytic oxidation of toluene over M/ZSM-5 (M=Cu, Mn, Fe, Ce, Ti) catalysts

PENG Xin-yu^{1, 2
,},
LIU Li-jun^{1, 2},
SHEN Bo-xiong^{1, 2
, ,},
BIAN Yao^{1, 2},
SU Li-chao³

1.
School of Energy and Environment Engineering, Hebei University of Technology, Tianjin 300401, China
2.
Tianjin Key Laboratory of Clean Energy and Pollution Control, Tianjin 300401, China
3.
Lin Zhu (Hebei) Engineering Industry Technology Research Co. Ltd, Xingtai 054001, China

Funds: The project was supported by the Joint Funds of the National Natural Science Foundation of China (U20A20302), Innovative Group Projects in Hebei Province (E2021202006), Special Project of Science and Technology of Hebei province (20373701D), the Project of Science and Technology in the Shijiazhuang City of Hebei Province (216240117A), and Project of Great Transformation of Scientific and Technical Research in Hebei Province (21283701Z).

摘要

摘要: 以ZSM-5分子筛为载体，采用浸渍法负载Cu、Mn、Fe、Ce、Ti制备一系列金属氧化物催化剂，利用SEM、XRD、N₂吸附-脱附、XPS、H₂-TPR对催化剂的理化性质进行了表征，并考察了催化剂的催化氧化甲苯性能。结果表明，Cu/ZSM-5表面粗糙，金属元素分布均匀，具有较好的孔径结构、良好的低温还原性和丰富的吸附氧物种，且负载量为5%的Cu/ZSM-5表现出优异的甲苯催化活性和最佳的抗硫性，在SO₂环境下t₉₀为224 ℃ (GHSV=24000 h⁻¹)。原位红外测试结果表明，甲苯的降解遵循以下途径，甲苯首先被吸附在催化剂表面形成吸附态甲苯，随后在催化剂作用下依次被转化为苯甲醛和苯甲酸，再经过开环反应形成马来酸、羧酸等小分子有机物，最终被氧化为CO₂和H₂O。
- 甲苯 /
- 催化氧化 /
- Cu/ZSM-5
Abstract: A series of metal oxide catalysts were prepared by impregnating Cu, Mn, Fe, Ce and Ti on ZSM-5 molecular sieve. The physicochemical properties of the catalysts were characterized by SEM, XRD, N₂ adsorption/desorption, XPS, H₂-TPR, and the catalytic oxidation of toluene was investigated. The results showed that Cu/ZSM-5 had rough surface, uniform distribution of metal, good pore structure, superior low-temperature reducibility and abundant adsorbed oxygen species. Cu/ZSM-5 with 5% loading exhibited excellent catalytic activity for toluene oxidation and the best sulfur resistance performance, with t₉₀ (GHSV=24000 h⁻¹) being 224 ℃ in SO₂ environment. In-situ DRIFTS experiments revealed that the degradation path of toluene was as follows: toluene was first adsorbed on the surface of the catalyst to form adsorbed toluene, then it was converted into benzaldehyde and benzoic acid successively on the catalyst. And small molecule organics such as maleic acid and carboxylic acid were formed through ring opening reaction, and finally was oxidized to CO₂ and H₂O.
- toluene /
- catalytic oxidation /
- Cu/ZSM-5

HTML全文

FIG. 2389. FIG. 2389.

下载: 全尺寸图片幻灯片

图 1 (a)ZSM-5、(b)Cu/ZSM-5、(c)Ce/ZSM-5的SEM照片和(d) Cu/ZSM-5 (e) Ce/ZSM-5的EDS mapping照片

Figure 1 SEM images of (a) ZSM-5, (b) Cu/ZSM-5, (c) Ce/ZSM-5 and EDS mapping images of (d) Cu/ZSM-5, (e) Ce/ZSM-5

下载: 全尺寸图片幻灯片

图 2 不同催化剂的XRD谱图

Figure 2 XRD patterns of different catalysts

下载: 全尺寸图片幻灯片

图 3 不同催化剂的N₂吸附-脱附等温线

Figure 3 N₂ adsorption/desorption isotherms of different catalysts

下载: 全尺寸图片幻灯片

图 4 不同催化剂的XPS O 1s谱图

Figure 4 O 1s XPS spectra of different catalysts

下载: 全尺寸图片幻灯片

图 5 不同催化剂的H₂-TPR谱图

Figure 5 H₂-TPR profiles of different catalysts

下载: 全尺寸图片幻灯片

图 6 不同催化剂的(a)甲苯氧化效率和(b)反应速率

Figure 6 (a) Toluene oxidation and (b) reaction rates of different catalysts

下载: 全尺寸图片幻灯片

图 7 不同催化剂在SO₂存在下的甲苯氧化效率

Figure 7 Toluene oxidation of different catalysts with SO₂

下载: 全尺寸图片幻灯片

图 8 不同金属负载量Cu/ZSM-5的甲苯氧化效率

Figure 8 Toluene oxidation of Cu/ZSM-5 with different metal loading

下载: 全尺寸图片幻灯片

图 9 Cu/ZSM-5在不同甲苯体积分数下的甲苯氧化效率

Figure 9 Toluene oxidation of Cu/ZSM-5 at different toluene concentrations

下载: 全尺寸图片幻灯片

图 10 (a) Cu/ZSM-5、(b) Fe/ZSM-5、(c) Ce/ZSM-5在250 ℃和(d) Cu/ZSM-5不同温度下催化甲苯的原位红外光谱谱图

Figure 10 In-situ DRIFTS spectra of toluene oxidation over (a) Cu/ZSM-5, (b) Fe/ZSM-5, (c) Ce/ZSM-5 at 250 ℃ and (d) Cu/ZSM-5 at different temperatures

下载: 全尺寸图片幻灯片

图 11 甲苯催化氧化机理示意图

Figure 11 Reaction mechanism of toluene catalytic oxidation

下载: 全尺寸图片幻灯片

表 1 不同催化剂的孔结构参数

Table 1 Structure properties of different catalysts.

Catalyst	BET surface area / (m²·g⁻¹)	Micropore volume / (cm³·g⁻¹)	Mesopore volume / (cm³·g⁻¹)	Pore volume / (cm³·g⁻¹)	Average pore diameter / nm
ZSM-5	400.7	0.085	0.175	0.261	2.60
Cu/ZSM-5	276.8	0.083	0.097	0.180	2.61
Mn/ZSM-5	291.1	0.082	0.106	0.188	2.58
Fe/ZSM-5	264.9	0.089	0.077	0.166	2.50
Ce/ZSM-5	294.6	0.098	0.078	0.175	2.38
Ti/ZSM-5	310.4	0.075	0.134	0.209	2.69

下载: 导出CSV

表 2 不同催化剂中氧物种物质的量比和耗氢量

Table 2 Molar ratio of oxygen species of different catalysts and H₂ consumption

Catalyst	Cu/ZSM-5	Mn/ZSM-5	Fe/ZSM-5	Ti/ZSM-5	Ce/ZSM-5
O_latt /%	3.98	16.75	12.81	27.98	15.81
O_ads /%	94.27	81.31	87.19	67.17	80.87
O_ads/O_latt	23.69	4.85	6.81	2.40	5.12
H₂ consumption /(mmol·g⁻¹)	2.10	1.44	2.19	0.54	0.15

下载: 导出CSV

参考文献(44)

[1]	LI W B, WANG J X, GONG H. Catalytic combustion of VOCs on non-noble metal catalysts [J]. Catal Today, 2009, 148(1–2): 81–87.
[2]	WANG H, NIE L, LI J, WANG Y, WANG G, WANG J, HAO Z. Characterization and assessment of volatile organic compounds (VOCs) emissions from typical industries[J]. Chin Sci Bull,2013,58(7):724−730. doi: 10.1007/s11434-012-5345-2
[3]	GUO Y L, WEN M C, LI G Y, AN T C. Recent advances in VOC elimination by catalytic oxidation technology onto various nanoparticles catalysts: a critical review[J]. Appl Catal B: Environ,2021,281:119447. doi: 10.1016/j.apcatb.2020.119447
[4]	ZHAI X, JING F, LI L, JIANG X, ZHANG J, MA J, CHU W. Toluene catalytic oxidation over the layered MOx-δ-MnO₂ (M = Pt, Ir, Ag) composites originated from the facile self-driving combustion method[J]. Fuel,2021,283:118888. doi: 10.1016/j.fuel.2020.118888
[5]	XIE Y, ZHANG L, JIANG Y, HAN S, WANG L, MENG X, XIAO F-S. Enhanced catalytic performance of methane combustion over zeolite-supported Pd catalysts with the lanthanum[J]. Catal Today,2021,364:16−20. doi: 10.1016/j.cattod.2019.11.030
[6]	LI J H, XIAO G F, GUO Z Y, LIN B L, HU Y, FU M L, YE D Q. ZSM-5-supported V-Cu bimetallic oxide catalyst for remarkable catalytic oxidation of toluene in coal-fired flue gas[J]. Chem Eng J,2021,419:129675. doi: 10.1016/j.cej.2021.129675
[7]	HU J, LI W B, LIU R F. Highly efficient copper-doped manganese oxide nanorod catalysts derived from CuMnO hierarchical nanowire for catalytic combustion of VOCs[J]. Catal Today,2018,314:147−153. doi: 10.1016/j.cattod.2018.02.009
[8]	LIN L-Y, BAI H. Salt-templated synthesis of Ce/Al catalysts supported on mesoporous silica for acetone oxidation[J]. Appl Catal B: Environ,2014,148-149:366−376. doi: 10.1016/j.apcatb.2013.11.026
[9]	ZHU L, ZHANG L, QU H X, ZHONG Q. A study on chemisorbed oxygen and reaction process of Fe-CuOx/ZSM-5 via ultrasonic impregnation method for low-temperature NH₃-SCR[J]. J Mol Catal A: Chem,2015,409:207−215. doi: 10.1016/j.molcata.2015.08.029
[10]	LI J R, ZHANG W P, LI C, XIAO H, HE C. Insight into the catalytic performance and reaction routes for toluene total oxidation over facilely prepared Mn-Cu bimetallic oxide catalysts[J]. Appl Surf Sci,2021,550:149179. doi: 10.1016/j.apsusc.2021.149179
[11]	LIU G, TIAN Y, ZHANG B, WANG L, ZHANG X. Catalytic combustion of VOC on sandwich-structured Pt@ZSM-5 nanosheets prepared by controllable intercalation[J]. J Hazard Mater,2019,367:568−576. doi: 10.1016/j.jhazmat.2019.01.014
[12]	AZIZ A, KIM S, KIM K S. Fe/ZSM-5 zeolites for organic-pollutant removal in the gas phase: Effect of the iron source and loading[J]. J Environ Chem Eng,2016,4(3):3033−3040. doi: 10.1016/j.jece.2016.06.021
[13]	SUN P, WANG W, DAI X, WENG X, WU Z. Mechanism study on catalytic oxidation of chlorobenzene over MnxCe₁-xO₂/H-ZSM5 catalysts under dry and humid conditions[J]. Appl Catal B: Environ,2016,198:389−397. doi: 10.1016/j.apcatb.2016.05.076
[14]	CHENG J, SONG L, WU R, LI S, SUN Y, ZHU H, QIU W, HE H. Promoting effect of microwave irradiation on CeO₂-TiO₂ catalyst for selective catalytic reduction of NO by NH₃[J]. J Rare Earth,2020,38(1):59−69. doi: 10.1016/j.jre.2019.04.014
[15]	LI S M, HAO Q L, ZHAO R Z, LIU D L, DUAN H Z, DOU B J. Highly efficient catalytic removal of ethyl acetate over Ce/Zr promoted copper/ZSM-5 catalysts[J]. Chem Eng J,2016,285:536−543. doi: 10.1016/j.cej.2015.09.097
[16]	ZHENG J, CHEN Z, FANG J F, WANG Z, ZUO S F. MCM-41 supported nano-sized CuO-CeO₂ for catalytic combustion of chlorobenzene[J]. J Rare Earth,2020,38(9):933−940. doi: 10.1016/j.jre.2019.06.005
[17]	YANG K, SUN Q, XUE F, LIN D. Adsorption of volatile organic compounds by metal-organic frameworks MIL-101: Influence of molecular size and shape[J]. J Hazard Mater,2011,195:124−131. doi: 10.1016/j.jhazmat.2011.08.020
[18]	WANG J, LI J, JIANG C, ZHOU P, ZHANG P, YU J. The effect of manganese vacancy in birnessite-type MnO₂ on room-temperature oxidation of formaldehyde in air[J]. Appl Catal B: Environ,2017,204:147−155. doi: 10.1016/j.apcatb.2016.11.036
[19]	LEI J, WANG S, LI J, XU Y, LI S. Different effect of Y (Y = Cu, Mn, Fe, Ni) doping on Co₃O₄ derived from Co-MOF for toluene catalytic destruction[J]. Chem Eng Sci,2022,251:117436. doi: 10.1016/j.ces.2022.117436
[20]	SHI Y, GUO X, SHI Z, ZHOU R. Transition metal doping effect and high catalytic activity of CeO₂-TiO₂ for chlorinated VOCs degradation[J]. J Rare Earth,2022,40(5):745−752. doi: 10.1016/j.jre.2021.02.005
[21]	ZHANG S L, ZHONG Q, ZHAO W, LI Y T. Surface characterization studies on F-doped V₂O₅/TiO2 catalyst for NO reduction with NH₃ at low-temperature[J]. Chem Eng J,2014,253:207−216. doi: 10.1016/j.cej.2014.04.045
[22]	KIM J, JANG E, JEONG Y, BAIK H, CHO S J, KANG C Y, KIM C H, CHOI J. A Cu-impregnated ZSM-5 zeolite for active cold start hydrocarbon removal: Cation-type-dependent Cu species and their synergetic HC adsorption/oxidation functions[J]. Chem Eng J,2022,430:132552. doi: 10.1016/j.cej.2021.132552
[23]	XUE H, GUO X, MENG T, MAO D, MA Z. Poisoning effect of K with respect to Cu/ZSM-5 used for NO reduction[J]. Colloid Interfac Sci,2021,44:100465. doi: 10.1016/j.colcom.2021.100465
[24]	YASHNIK S A, TARAN O P, SUROVTSOVA T A, AYUSHEEV A B, PARMON V N. Cu- and Fe-substituted ZSM-5 zeolite as an effective catalyst for wet peroxide oxidation of Rhodamine 6 G dye[J]. J Environ Chem Eng,2022,10(3):107950. doi: 10.1016/j.jece.2022.107950
[25]	ZHA K, FENG C, HAN L, LI H, YAN T, KUBOON S, SHI L, ZHANG D. Promotional effects of Fe on manganese oxide octahedral molecular sieves for alkali-resistant catalytic reduction of NOx: XAFS and in situ DRIFTs study[J]. Chem Eng J,2020,381:122764. doi: 10.1016/j.cej.2019.122764
[26]	WU Y S, FENG R, SONG C J, XING S T, GAO Y Z, MA Z C. Effect of reducing agent on the structure and activity of manganese oxide octahedral molecular sieve (OMS-2) in catalytic combustion of o-xylene[J]. Catal Today,2017,281:500−506. doi: 10.1016/j.cattod.2016.05.024
[27]	MA Y, LI W, WANG H, CHEN J, WEN J, XU S, TIAN X, GAO L, HOU Z, ZHANG Q, YANG H. Enhanced performance of iron-cerium NO reduction catalysts by sulfuric acid treatment: The synergistic effect of surface acidity and redox capacity[J]. Appl Cacal A: Gen,2021,621:118200. doi: 10.1016/j.apcata.2021.118200
[28]	CAO X, LU J, ZHENG X, HE D, ZHU W, ZHAO Y, ZHANG W, TIAN R, LUO Y. Regulation of the reaction pathway to design the high sulfur/coke-tolerant Ce-based catalysts for decomposing sulfur-containing VOCs[J]. Chem Eng J,2022,429:132473. doi: 10.1016/j.cej.2021.132473
[29]	WANG J, GUO X, SHI Y, ZHOU R. Synergistic effect of Pt nanoparticles and micro-mesoporous ZSM-5 in VOCs low-temperature removal[J]. J Environ Sci,2021,107:87−97. doi: 10.1016/j.jes.2021.01.033
[30]	YAN Y, WANG L, ZHANG H P. Catalytic combustion of volatile organic compounds over Co/ZSM-5 coated on stainless steel fibers[J]. Chem Eng J,2014,255:195−204. doi: 10.1016/j.cej.2014.05.141
[31]	ZHANG C, HUANG H, LI G, WANG L, SONG L, LI X. Zeolitic acidity as a promoter for the catalytic oxidation of toluene over MnO_x/HZSM-5 catalysts[J]. Catal Today,2019,327:374−381. doi: 10.1016/j.cattod.2018.03.019
[32]	ZHANG Z X, GONG Y, XU J W, ZHANG Y, XIAO Q Y, XI R, XU X L, FANG X Z, WANG X. Dissecting La₂Ce₂O₇ catalyst to unravel the origin of the surface active sites devoting to its performance for oxidative coupling of methane (OCM)[J]. Catal Today,2022,400-401:73−81. doi: 10.1016/j.cattod.2021.11.012
[33]	WANG C P, WANG Z, MAO S J, CHEN Z R, WANG Y. Coordination environment of active sites and their effect on catalytic performance of heterogeneous catalysts[J]. Chin J Catal,2022,43(4):928−955. doi: 10.1016/S1872-2067(21)63924-4
[34]	VELLINGIRI K, KUMAR P, DEEP A, KIM K-H. Metal-organic frameworks for the adsorption of gaseous toluene under ambient temperature and pressure[J]. Chem Eng J,2017,307:1116−1126. doi: 10.1016/j.cej.2016.09.012
[35]	PAN H, CHEN Z, MA M, GUO T, LING X, ZHENG Y, HE C, CHEN J. Mutual inhibition mechanism of simultaneous catalytic removal of NO and toluene on Mn-based catalysts[J]. J Colloid Interface Sci,2022,607:1189−1200. doi: 10.1016/j.jcis.2021.09.110
[36]	WANG Z, XIE K, ZHENG J, ZUO S. Studies of sulfur poisoning process via ammonium sulfate on MnO₂/γ-Al₂O₃ catalyst for catalytic combustion of toluene[J]. Appl Catal B: Environ,2021,298:120595. doi: 10.1016/j.apcatb.2021.120595
[37]	HU P, WENG Q, LI D, LV T, WANG S, ZHUO Y. Effects of O₂, SO₂, H₂O and CO₂ on As₂O₃ adsorption by gamma-Al₂O₃ based on DFT analysis[J]. J Hazard Mater,2021,403:123866. doi: 10.1016/j.jhazmat.2020.123866
[38]	HOU Z, DAI L, LIU Y, DENG J, JING L, PEI W, GAO R, FENG Y, DAI H. Highly efficient and enhanced sulfur resistance supported bimetallic single-atom palladium-cobalt catalysts for benzene oxidation[J]. Appl Catal B: Environ,2021,285:119844. doi: 10.1016/j.apcatb.2020.119844
[39]	LIU H L, YE C, XU Y S, WANG Q S. Effect of activation conditions and iron loading content on the catalytic cracking of toluene by biochar[J]. Energy,2022,247:123409. doi: 10.1016/j.energy.2022.123409
[40]	AHMADI M, HAGHIGHI M, KAHFOROUSHAN D. Influence of active phase composition (Mn, Ni, Mn_xNi_10−x ) on catalytic properties and performance of clinoptilolite supported nanocatalysts synthesized using ultrasound energy toward abatement of toluene from polluted air[J]. Process Saf Environ Prot,2017,106:294−308. doi: 10.1016/j.psep.2016.06.029
[41]	WANG Z, YANG H, LIU R, XIE S, LIU Y, DAI H, HUANG H, DENG J. Probing toluene catalytic removal mechanism over supported Pt nano- and single-atom-catalyst[J]. J Hazard Mater,2020,392:122258. doi: 10.1016/j.jhazmat.2020.122258
[42]	XU W C, WANG N, CHEN Y D, CHEN J D, XU X X, YU L, CHEN L M, WU J L, FU M L, ZHU A M, YE D Q. In situ FT-IR study and evaluation of toluene abatement in different plasma catalytic systems over metal oxides loaded gamma-AL(2)O(3)[J]. Catal Commun,2016,84:61−66. doi: 10.1016/j.catcom.2016.06.004
[43]	WEI G C, ZHANG Q L, ZHANG D H, WANG J, TANG T, WANG H M, LIU X, SONG Z X, NING P. The influence of annealing temperature on copper-manganese catalyst towards the catalytic combustion of toluene: The mechanism study[J]. Appl Surf Sci,2019,497:143777. doi: 10.1016/j.apsusc.2019.143777
[44]	WANG Z W, MA P J, ZHENG K, WANG C, LIU Y X, DAI H X, WANG C C, HSI H C, DENG J G. Size effect, mutual inhibition and oxidation mechanism of the catalytic removal of a toluene and acetone mixture over TiO₂ nanosheet-supported Pt nanocatalysts[J]. Appl Catal B: Environ,2020,274:118963. doi: 10.1016/j.apcatb.2020.118963