Study on adsorption and catalytic oxidation characteristics of toluene on Co3O4 modified USY molecular sieve

doi:10.11949/0438-1157.20201735

Abstract

Abstract:

Co₃O₄/USY composite material was synthesized by a hydrothermal method. Experimental study was conducted to investigate its absorption and catalytic oxidation characteristics of organic pollutant toluene. Since the Co₃O₄ can be efficiently heated by microwaves, the heating characteristics and catalytic oxidation of toluene on Co₃O₄ modified USY under microwave action were also investigated, with an aim to discuss the feasibility of microwave-assisted rapid regeneration of adsorbent whilst in-situ degradation of organic matter. By hydrothermal reaction, Co₃O₄ forms a porous cellular structure on the surface of USY. The USY loaded with Co₃O₄ maintains high adsorption capacity, and the adsorption capacity of Co₃O₄/USY-1.5m at room temperature is 85 mg/g. The prepared Co₃O₄/USY composite material exhibits excellent catalytic oxidation properties, CO₂ selectivity and stability at 325℃ in both dry and wet conditions. The prepared Co₃O₄/USY composite material can couple with microwave in an efficient way, leading to quick start up its catalytic function. Comparative study shows that the CO₂ selectivity and catalysis stability under the microwave heating scenario are better than conventional heating when the reaction temperature is controlled at 250℃. The above results indicate that the prepared Co₃O₄/USY composite material can be used as an adsorbent to adsorb toluene and regenerated by microwave heating whilst the desorbed organic matter can be efficiently degraded by in situ catalytic oxidation.

Key words: Co₃O₄/USY, composite material, molecular sieve, adsorption, catalytic oxidation, microwave, VOCs

摘要：

利用水热法合成Co₃O₄/USY复合材料，研究其对有机污染物甲苯的吸附和催化氧化特性，同时结合微波对Co₃O₄的精准加热特性，考察不同负载量Co₃O₄/USY在微波作用下的升温特性及催化甲苯氧化降解特性。结果表明，通过水热反应，Co₃O₄在USY表面形成多孔蜂窝状结构；负载Co₃O₄后的USY保持较高的吸附容量，Co₃O₄/USY-1.5m室温下的吸附容量为85 mg/g；Co₃O₄/USY在干、湿两种状态下均在325℃表现出优良的催化氧化特性、CO₂选择性和稳定性；Co₃O₄/USY能够与微波高效耦合，快速升温启动其催化作用，控制反应温度为250℃，发现微波诱导甲苯催化氧化过程的CO₂选择性优于常规催化，表明所制备Co₃O₄/USY复合材料具备吸附甲苯并进行微波快速再生协同有机污染物高效催化氧化降解的可行性。

关键词: Co₃O₄/USY, 复合材料, 分子筛, 吸附, 催化氧化, 微波, VOCs

CLC Number:

TQ 028.8

SUN Jing, DONG Yilin, LI Faqi, LI Wenxiang, MA Xiaoling, WANG Wenlong. Study on adsorption and catalytic oxidation characteristics of toluene on Co₃O₄ modified USY molecular sieve[J]. CIESC Journal, 2021, 72(6): 3306-3315.

孙静, 董一霖, 李法齐, 李文翔, 马晓玲, 王文龙. Co₃O₄改性USY分子筛吸附和催化氧化甲苯特性研究[J]. 化工学报, 2021, 72(6): 3306-3315.

Figures/Tables 10

Fig.1 Schematic diagram of adsorption / catalysis experimental system

Fig.2 XRD patterns of Co3O4/USY adsorbent

Fig.3 SEM images of USY (a), Co3O4/USY-1.5m (b), Co3O4/USY-2m (c) and Co3O4/USY-3m(d)

Table 1 BET analysis of USY and Co3O4/USY composite materials

材料	总比表面积/(m²/g)	微孔表面积/(m²/g)	外表面积/(m²/g)	总孔容/(cm³/g)	微孔孔容/(cm³/g)	介孔孔容/(cm³/g)	平均孔径/nm
USY	828	732	96	0.44	0.28	0.16	1.36
Co₃O₄/USY-1.5m	584	359	226	0.56	0.17	0.39	2.27
Co₃O₄/USY-2m	524	260	264	0.62	0.11	0.51	2.64
Co₃O₄/USY-3m	449	265	184	0.54	0.11	0.43	2.76

Fig.4 Curves of toluene adsorption by USY and Co3O4/USY composite materials

Fig.5 Catalytic performance of Co3O4/USY for toluene oxidation

Fig.6 Catalytic performance of Co3O4/USY for toluene oxidation under dry and wet conditions

Fig.7 Co3O4/USY-1.5m catalytic stability for toluene oxidation under dry state (a) and different humidity conditions(b)

Fig.8 Heating characteristics of Co3O4/USY under microwave action

Fig.9 Comparison of catalytic toluene under conventional heating (a) and microwave heating conditions (b) at 250℃

References 30

1	李红, 彭良, 毕方, 等. 我国PM_2.5与臭氧污染协同控制策略研究[J]. 环境科学研究, 2019, 32(10): 1763-1778.
	Li H, Peng L, Bi F, et al. Strategy of coordinated control of PM_2.5 and ozone in China[J]. Research of Environmental Sciences, 2019, 32(10): 1763-1778.
2	中华人民共和国生态环境部. 关于印发«2020年挥发性有机物治理攻坚方案»的通知[EB/OL]. [2020-06-24]. .
	Ministry of Ecology and Environment, PRC. Notice on issuing the Tackling Plan for the Treatment of Volatile Organic Compounds in 2020[EB/OL]. [2020-06-24]. .
3	刘伟, 李立清, 姚小龙, 等. 活性炭孔隙结构在其甲苯吸附中的作用[J]. 环境工程学报, 2012, 6(9): 3210-3218.
	Liu W, Li L Q, Yao X L, et al. Pore structure effects on activated carbon adsorption behavior for toluene[J]. Chinese Journal of Environmental Engineering, 2012, 6(9): 3210-3218.
4	Lv Y, Sun J, Yu G Q, et al. Hydrophobic design of adsorbent for VOC removal in humid environment and quick regeneration by microwave[J]. Microporous and Mesoporous Materials, 2020, 294: 109869.
5	Qie Z P, Zhang Z K, Sun F, et al. Effect of pore hierarchy and pore size on the combined adsorption of SO₂ and toluene in activated coke[J]. Fuel, 2019, 257: 116090.
6	Li R N, Xue T S, Li Z, et al. Hierarchical structure ZSM-5/SBA-15 composite with improved hydrophobicity for adsorption-desorption behavior of toluene[J]. Chemical Engineering Journal, 2020, 392: 124861.
7	王敏, 翁艺斌, 陈进富, 等. 吸附法治理工业源挥发性有机物的研究进展[J]. 现代化工, 2020, 40(10): 15-19, 25.
	Wang M, Weng Y B, Chen J F, et al. Research progress on treatment of industrial sectors-based VOCs by adsorption[J]. Modern Chemical Industry, 2020, 40(10): 15-19, 25.
8	吴桐, 周玉香, 王芳, 等. 燃烧法用于VOCs末端治理的研究进展[J]. 山东化工, 2020, 49(4): 80-81, 84.
	Wu T, Zhou Y X, Wang F, et al. Research progress of combustion method in terminal treatment for volatile organic compounds[J]. Shandong Chemical Industry, 2020, 49(4): 80-81, 84.
9	Liu G Z, Tian Y J, Zhang B F, et al. Catalytic combustion of VOC on sandwich-structured Pt@ZSM-5 nanosheets prepared by controllable intercalation[J]. Journal of Hazardous Materials, 2019, 367: 568-576.
10	He C, Yu Y K, Shen Q, et al. Catalytic behavior and synergistic effect of nanostructured mesoporous CuO-MnO_x-CeO₂ catalysts for chlorobenzene destruction[J]. Applied Surface Science, 2014, 297: 59-69.
11	Zang M, Zhao C C, Wang Y Q, et al. A review of recent advances in catalytic combustion of VOCs on perovskite-type catalysts[J]. Journal of Saudi Chemical Society, 2019, 23(6): 645-654.
12	Pan K L, Pan G T, Chong S, et al. Removal of VOCs from gas streams with double perovskite-type catalysts[J]. Journal of Environmental Sciences, 2018, 69: 205-216.
13	Levasseur B, Kaliaguine S. Effects of iron and cerium in La_1-_yCe_yCo_1-_xFe_xO₃ perovskites as catalysts for VOC oxidation[J]. Applied Catalysis B: Environmental, 2009, 88(3/4): 305-314.
14	崔维怡, 惠继星, 谭乃迪. 非贵金属催化剂催化氧化甲醛的研究进展[J]. 化工进展, 2018, 37(11): 4286-4293.
	Cui W Y, Hui J X, Tan N D. Research progress on catalytic oxidation of formaldehyde over non-noble metal catalysts[J]. Chemical Industry and Engineering Progress, 2018, 37(11): 4286-4293.
15	冯爱虎, 于洋, 于云, 等. 沸石分子筛及其负载型催化剂去除VOCs研究进展[J]. 化学学报, 2018, 76(10): 757-773.
	Feng A H, Yu Y, Yu Y, et al. Recent progress in the removal of volatile organic compounds by zeolite and its supported catalysts[J]. Acta Chimica Sinica, 2018, 76(10): 757-773.
16	张兴, 裴文波, 侯志全, 等. 多孔复合金属氧化物的制备及其在消除挥发性有机物中的应用[J]. 工业催化, 2020, 28(4): 39-51.
	Zhang X, Pei W B, Hou Z Q, et al. Preparation of porous mixed metal oxides and their catalytic applications in the removal of volatile organic compounds[J]. Industrial Catalysis, 2020, 28(4): 39-51.
17	戴洪兴, 侯志全, 张兴, 等. 规整形貌和多孔催化剂对挥发性有机物氧化的催化性能[J]. 北京工业大学学报, 2019, 45(11): 1095-1114.
	Dai H X, Hou Z Q, Zhang X, et al. Catalytic performance of regularly morphological and porous catalysts for the oxidation of volatile organic compounds[J]. Journal of Beijing University of Technology, 2019, 45(11): 1095-1114.
18	Liu W, Liu R, Zhang H Y, et al. Fabrication of Co₃O₄ nanospheres and their catalytic performances for toluene oxidation: The distinct effects of morphology and oxygen species[J]. Applied Catalysis A: General, 2020, 597: 117539.
19	Xu W C, Xiao K B, Lai S F, et al. Designing a dumbbell-brush-type Co₃O₄ for efficient catalytic toluene oxidation[J]. Catalysis Communications, 2020, 140: 106005.
20	Wang B D, Gan F L, de Dai Z, et al. Air oxidation coupling NH₃ treatment of biomass derived hierarchical porous biochar for enhanced toluene removal[J]. Journal of Hazardous Materials, 2021, 403: 123995.
21	黄心远. 酸性分子筛催化的有机重排反应研究[D]. 上海: 华东师范大学, 2020.
	Huang X Y. Acidic molecular sieves catalyzed rearrangement reactions[D]. Shanghai: East China Normal University, 2020.
22	Shi Y J, Li Z M, Wang J L, et al. Synergistic effect of Pt/Ce and USY zeolite in Pt-based catalysts with high activity for VOCs degradation[J]. Applied Catalysis B: Environmental, 2021, 286: 119936.
23	高瑞忠, 赵红娟, 高雄厚, 等. USY分子筛的改性及应用进展[J]. 工业催化, 2017, 25(11): 8-12.
	Gao R Z, Zhao H J, Gao X H, et al. Progress in modification and application of USY zeolites[J]. Industrial Catalysis, 2017, 25(11): 8-12.
24	Huang Q Q, Xue X M, Zhou R X. Catalytic behavior and durability of CeO₂ or/and CuO modified USY zeolite catalysts for decomposition of chlorinated volatile organic compounds[J]. Journal of Molecular Catalysis A: Chemical, 2011, 344(1/2): 74-82.
25	Huang Q Q, Meng Z H, Zhou R X. The effect of synergy between Cr₂O₃-CeO₂ and USY zeolite on the catalytic performance and durability of chromium and cerium modified USY catalysts for decomposition of chlorinated volatile organic compounds[J]. Applied Catalysis B: Environmental, 2012, 115/116: 179-189.
26	刘秉国, 彭金辉, 张利波, 等. 碱式碳酸钴在微波场中的吸波特性及升温行为研究[J]. 无机盐工业, 2010, 42(3): 11-13, 16.
	Liu B G, Peng J H, Zhang L B, et al. Study on microwave-absorbing characteristics and temperature rise behavior of basic cobalt carbonate in microwave fields[J]. Inorganic Chemicals Industry, 2010, 42(3): 11-13, 16.
27	刘秉国, 彭金辉, 张利波, 等. 草酸钴在微波场中的吸波特性及升温行为研究[J]. 化工科技, 2010, 18(2): 1-4.
	Liu B G, Peng J H, Zhang L B, et al. Study on microwave-absorbing characteristics and temperature rise behavior of cobalt oxalate in microwave fields[J]. Science & Technology in Chemical Industry, 2010, 18(2): 1-4.
28	吕昱亭. 基于分子筛改性的VOCs吸附和催化氧化试验研究[D]. 济南: 山东大学, 2020.
	Lyu Y T. Experimental research on VOCs adsorption and catalytic oxidation based on modified molecular sieve[D]. Jinan: Shandong University, 2020.
29	宁轲, 卜龙利, 刘双, 等. 整体式催化剂活性组分负载策略及微波催化燃烧甲苯特性[J]. 燃料化学学报, 2020, 48(9): 1140-1152.
	Ning K, Bo L L Liu S, et al. Loading strategy for the active components of monolithic catalyst and its influences on the microwave enhanced catalytic combustion of toluene[J]. Journal of Fuel Chemistry and Technology, 2020, 48(9): 1140-1152.
30	Zhang F S, Song Z L, Zhu J Z, et al. Factors influencing CH₄-CO₂ reforming reaction over Fe catalyst supported on foam ceramics under microwave irradiation[J]. International Journal of Hydrogen Energy, 2018, 43(20): 9495-9502.

[1]	Lei WU, Jiao LIU, Changcong LI, Jun ZHOU, Gan YE, Tiantian LIU, Ruiyu ZHU, Qiuli ZHANG, Yonghui SONG. Catalytic microwave pyrolysis of low-rank pulverized coal for preparation of high value-added modified bluecoke powders containing carbon nanotubes [J]. CIESC Journal, 2023, 74(9): 3956-3967.
[2]	Yan GAO, Peng WU, Chao SHANG, Zejun HU, Xiaodong CHEN. Preparation of magnetic agarose microspheres based on a two-fluid nozzle and their protein adsorption properties [J]. CIESC Journal, 2023, 74(8): 3457-3471.
[3]	Bingchun SHENG, Jianguo YU, Sen LIN. Study on lithium resource separation from underground brine with high concentration of sodium by aluminum-based lithium adsorbent [J]. CIESC Journal, 2023, 74(8): 3375-3385.
[4]	Ruihang ZHANG, Pan CAO, Feng YANG, Kun LI, Peng XIAO, Chun DENG, Bei LIU, Changyu SUN, Guangjin CHEN. Analysis of key parameters affecting product purity of natural gas ethane recovery process via ZIF-8 nanofluid [J]. CIESC Journal, 2023, 74(8): 3386-3393.
[5]	Xingzhi HU, Haoyan ZHANG, Jingkun ZHUANG, Yuqing FAN, Kaiyin ZHANG, Jun XIANG. Preparation and microwave absorption properties of carbon nanofibers embedded with ultra-small CeO₂ nanoparticles [J]. CIESC Journal, 2023, 74(8): 3584-3596.
[6]	Jie WANG, Xiaolin QIU, Ye ZHAO, Xinyang LIU, Zhongqiang HAN, Yong XU, Wenhan JIANG. Preparation and properties of polyelectrolyte electrostatic deposition modified PHBV antioxidant films [J]. CIESC Journal, 2023, 74(7): 3068-3078.
[7]	Pan LI, Junyang MA, Zhihao CHEN, Li WANG, Yun GUO. Effect of the morphology of Ru/α-MnO₂ on NH₃-SCO performance [J]. CIESC Journal, 2023, 74(7): 2908-2918.
[8]	Ji CHEN, Ze HONG, Zhao LEI, Qiang LING, Zhigang ZHAO, Chenhui PENG, Ping CUI. Study on coke dissolution loss reaction and its mechanism based on molecular dynamics simulations [J]. CIESC Journal, 2023, 74(7): 2935-2946.
[9]	Yuming TU, Gaoyan SHAO, Jianjie CHEN, Feng LIU, Shichao TIAN, Zhiyong ZHOU, Zhongqi REN. Advances in the design, synthesis and application of calcium-based catalysts [J]. CIESC Journal, 2023, 74(7): 2717-2734.
[10]	Chen WANG, Xiufeng SHI, Xianfeng WU, Fangjia WEI, Haohong ZHANG, Yin CHE, Xu WU. Preparation of Mn₃O₄ catalyst by redox method and study on its catalytic oxidation performance and mechanism of toluene [J]. CIESC Journal, 2023, 74(6): 2447-2457.
[11]	Guangyu WANG, Kai ZHANG, Kaihua ZHANG, Dongke ZHANG. Heat and mass transfer and energy consumption for microwave drying of coal slime [J]. CIESC Journal, 2023, 74(6): 2382-2390.
[12]	Zhen LI, Bo ZHANG, Liwei WANG. Development and properties of PEG-EG solid-solid phase change materials [J]. CIESC Journal, 2023, 74(6): 2680-2688.
[13]	Shaoyun CHEN, Dong XU, Long CHEN, Yu ZHANG, Yuanfang ZHANG, Qingliang YOU, Chenglong HU, Jian CHEN. Preparation and adsorption properties of monolayer polyaniline microsphere arrays [J]. CIESC Journal, 2023, 74(5): 2228-2238.
[14]	Caihong LIN, Li WANG, Yu WU, Peng LIU, Jiangfeng YANG, Jinping LI. Effect of alkali cations in zeolites on adsorption and separation of CO₂/N₂O [J]. CIESC Journal, 2023, 74(5): 2013-2021.
[15]	Chenxin LI, Yanqiu PAN, Liu HE, Yabin NIU, Lu YU. Carbon membrane model based on carbon microcrystal structure and its gas separation simulation [J]. CIESC Journal, 2023, 74(5): 2057-2066.

Study on adsorption and catalytic oxidation characteristics of toluene on Co₃O₄ modified USY molecular sieve

Co₃O₄改性USY分子筛吸附和催化氧化甲苯特性研究

RichHTML

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 10

References 30

Related Articles 15

Recommended Articles

Metrics

Comments