Co-Al2O3高效催化CO2氧化乙苯脱氢制苯乙烯

司智伟; 丹少鹏; 陈树伟; 潘大海; 王英雄; 闫晓亮; 李瑞丰

doi:10.19906/j.cnki.JFCT.2023039

Co-Al₂O₃高效催化CO₂氧化乙苯脱氢制苯乙烯

doi: 10.19906/j.cnki.JFCT.2023039

司智伟^{1, #,},
丹少鹏^{1, #,},
陈树伟^1, ,,
潘大海^1,,
王英雄^1,,
闫晓亮^2,,
李瑞丰^2,

1.
太原理工大学化学学院, 山西太原 030024
2.
太原理工大学化学工程与技术学院, 山西太原 030024

基金项目: 国家自然科学基金（22378286, 21975174）和中央引导地方科技发展资金（YDZJSX2021A014）资助

详细信息

通讯作者:
Tel: 0351-6018564, E-mail: csw603@163.com

#These authors contributed equally to this work and should be considered co-first authors.
中图分类号: O643.3
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出版历程
- 收稿日期: 2023-03-08
- 修回日期: 2023-05-04
- 录用日期: 2023-05-04
- 网络出版日期: 2023-05-06
- 刊出日期: 2023-11-13

Highly efficient Co-Al₂O₃ catalysts for oxidative dehydrogenation of ethylbenzene to styrene with CO₂

SI Zhi-wei^{1, #
,},
DAN Shao-peng^{1, #
,},
CHEN Shu-wei^{1
, ,},
PAN Da-hai^1
,,
WANG Ying-xiong^1
,,
YAN Xiao-liang^2
,,
LI Rui-feng^2
,

1.
College of Chemistry, Taiyuan University of Technology, Taiyuan 030024, China
2.
College of Chemical Engineering and Technology, Taiyuan University of Technology, Taiyuan 030024, China

Funds: The project was supported by the National Natural Science Foundation of China (22378286, 21975174) and Funds for Central Government to Guide Local Science and Technology Development (YDZJSX2021A014).

摘要

摘要: 采用溶胶-凝胶法制备了不同Co含量的nCo-Al₂O₃催化剂(n = 2%、5%、10%、15%、20%)，研究了Co含量对催化剂结构和CO₂氧化乙苯脱氢性能的影响。结果发现，nCo-Al₂O₃催化剂上孤立的Co^{2 +}离子与催化活性具有良好的对应关系，表明孤立的四面体Co^{2 +}物种是其活性位点。Co-Al₂O₃催化剂上的Co物种结构和催化性能与Co含量相关。Co含量较低（≤10%）时，催化剂上优先形成孤立的四面体Co^{2 +}物种；随着Co含量的增加，孤立的Co^{2 +}位点增加，催化剂活性随之提高。Co含量较高（>10%）时，催化剂上形成Co₃O₄晶体颗粒，导致孤立的Co^{2 +}位点减少，催化剂活性降低。10Co-Al₂O₃表现出最佳催化性能，550 ℃下乙苯转化率达64.4%，苯乙烯选择性为99.3%，反应30 h后，催化剂仍无明显失活，表明孤立的Co^{2 +}活性位点具有良好的结构稳定性和优异的抗积炭性能。
- Co基催化剂 /
- 乙苯 /
- 氧化脱氢 /
- 二氧化碳 /
- 苯乙烯
Abstract: nCo-Al₂O₃ catalysts with different Co contents (n=2%, 5%, 10%, 15%, 20%) were prepared by a sol-gel approach. The effect of Co content on the nCo-Al₂O₃ catalyst structure and performance in the oxidative dehydrogenation of ethylbenzene to styrene by CO₂ was investigated. The results showed that the isolated Co^{2 +} ions on the nCo-Al₂O₃ catalysts had a positive influence on the catalytic activity, where the isolated tetrahedral Co^{2 +} species were considered as the active sites. Co contents on the Co-Al₂O₃ catalyst greatly affected the structure of Co species and the catalytic performance. The isolated tetrahedral Co^{2 +} species are preferentially generated on the resultant nCo-Al₂O₃ catalyst when the content of Co (n) is less than 10%; as a result, an increase of Co content here leads to the formation of more isolated Co^{2 +} sites and then improves the catalytic activity of nCo-Al₂O₃ in the dehydrogenation of ethylbenzene. When Co content exceeded 10%, crystalline Co₃O₄ particles were obtained on the formed catalyst, which resulted in the decline of the isolated Co^{2 +} sites and catalytic activity. Among various nCo-Al₂O₃ catalysts, 10Co-Al₂O₃ exhibited the best catalytic performance, with 64.4% conversion rate for ethylbenzene and 99.3% selectivity for styrene at 550 ℃. This catalyst remained stable without obvious deactivation for 30 h of reaction, which suggests that the isolated Co^{2 +} species as active sites presented excellent structural stability and excellent anti-coke deposition.
- Co-based catalyst /
- ethylbenzene /
- oxidative dehydrogenation /
- CO₂ /
- styrene
注释:

1) #These authors contributed equally to this work and should be considered co-first authors.

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FIG. 2767. FIG. 2767.

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图 1 nCo-Al₂O₃催化剂的N₂吸附-脱附等温线(a)和孔径分布(b)

Figure 1 N₂ adsorption-desorption isotherms (a) and pore-size distribution (b) of nCo-Al₂O₃ catalysts

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图 2 nCo-Al₂O₃催化剂的XRD谱图

Figure 2 XRD patterns of nCo-Al₂O₃ catalysts

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图 3 nCo-Al₂O₃催化剂的紫外-可见漫反射光谱谱图

Figure 3 UV-vis DR spectra of nCo- Al₂O₃ catalysts

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图 4 nCo-Al₂O₃催化剂的H₂-TPR谱图

Figure 4 H₂-TPR profiles of nCo- Al₂O₃ catalysts

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图 5 nCo- Al₂O₃催化剂的Co 2p XPS谱图

Figure 5 Co 2p XPS spectra of nCo- Al₂O₃ catalysts

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图 6 nCo-Al₂O₃催化剂的TEM照片

Figure 6 TEM images of nCo-Al₂O₃ catalysts

(a): 5Co-Al₂O₃; (b): 10Co-Al₂O₃; (c): 15Co-Al₂O₃; (d): 20Co-Al₂O₃

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图 7 nCo- Al₂O₃催化剂上乙苯转化率和苯乙烯选择性随反应时间的变化

Figure 7 EB conversion and ST selectivity as a function of time over nCo-Al₂O₃ catalysts

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图 8 Co- Al₂O₃催化CO₂氧化乙苯脱氢的稳定性和再生性能

Figure 8 Stability and regeneration of Co- Al₂O₃ catalysts for CO₂-ODEB

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图 9 反应前后Co-Al₂O₃催化剂的XRD谱图

Figure 9 XRD patterns of the fresh and used Co-Al₂O₃ catalysts

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图 10 反应后Co-Al₂O₃催化剂的TG-DSC谱图

Figure 10 TG-DSC profiles of the used Co-Al₂O₃ catalysts

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表 1 nCo-Al₂O₃催化剂的织构性质

Table 1 Textural properties of nCo-Al₂O₃ catalysts

Sample	S_BET/(m²·g⁻¹)^a	v_p/(cm³·g⁻¹)^b	d_p/nm^c
Al₂O₃(HSA)	386	0.79	7.81
2Co-Al₂O₃	376	0.73	7.64
5Co-Al₂O₃	350	0.68	6.95
10Co-Al₂O₃	329	0.62	5.72
15Co-Al₂O₃	260	0.56	5.25
20Co-Al₂O₃	237	0.43	4.84
^a BET surface areas were obtained from N₂ adsorption isotherms; ^b pore volume based on the Multi-point BET method; ^c average pore diameter based on the BJH method

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表 2 nCo-Al₂O₃催化剂的XPS表征

Table 2 XPS results of nCo- Al₂O₃ catalysts

Sample	Binding energy /eV		ΔE /eV	Co^{2 +}/Co^{3 +}
Sample	Co 2p_3/2	Co 2p_1/2	ΔE /eV	Co^{2 +}/Co^{3 +}
2Co-Al₂O₃	781.8	797.6	15.8	100∶0
5Co-Al₂O₃	781.8	797.5	15.7	95∶5
10Co-Al₂O₃	781.6	797.1	15.5	89∶11
15Co-Al₂O₃	781.1	796.3	15.2	63∶37
20Co-Al₂O₃	780.7	795.8	15.1	45∶55

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表 3 550 ℃下nCo-Al₂O₃催化CO₂氧化乙苯脱氢活性

Table 3 Activity of nCo-Al₂O₃ catalysts for CO₂-ODEB at 550 ℃

Sample	EB conversion /%		ST selectivity /%		ST yield /%
Sample	1 h	12 h	1 h	12 h	1 h	12 h
2Co-Al₂O₃	17.1	17.5	98.4	98.7	16.8	17.3
5Co-Al₂O₃	27.5	37.6	98.5	98.6	27.1	37.1
10Co-Al₂O₃	39.5	55.6	98.4	98.8	38.9	54.9
10Co-Al₂O₃^a	45.2	33.1	87.6	88.3	39.6	29.2
15Co-Al₂O₃	32.5	40.8	98.3	98.7	31.9	40.3
20Co-Al₂O₃	20.8	19.2	98.3	98.6	20.4	18.9
^a: Under an inert He atmosphere

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参考文献(25)

[1]	LEE E H. iron oxide catalysts for dehydrogenation of ethylbenzene in the presence of steam iron oxide catalysts for dehydrogenation of ethylbenzene in the presence of steam[J]. Catal Rev,2006,8(1):285−305.
[2]	RAHMAN S T, CHOI J R, LEE J H, PARK S J. The role of CO₂ as a mild oxidant in oxidation and dehydrogenation over catalysts: A Review[J]. Catalysts,2020,10(9):1075−1100. doi: 10.3390/catal10091075
[3]	王光耀. 重油性质对油煤浆表观黏度的影响[J]. 煤炭转化,2022,45(2):74−83. doi: 10.19726/j.cnki.ebcc.202202009 WANG Guang-yao. Effect of heavy oil properties on apparent viscosity of oil-coal slurry[J]. Coal Convers,2022,45(2):74−83. doi: 10.19726/j.cnki.ebcc.202202009
[4]	MIMURA N, TAKAHARA I, SAITO M, HATTORI T, ANDO M. Dehydrogenation of ethylbenzene over iron oxide-based catalyst in the presence of carbon dioxide[J]. Catal Today,1998,45(1):61−64.
[5]	MUKHERJEE D, PARK S E, REDDY B M. CO₂ as a soft oxidant for oxidative dehydrogenation reaction: An eco benign process for industry[J]. J CO₂ Util,2016,16:301−312. doi: 10.1016/j.jcou.2016.08.005
[6]	ANSARI M B, PARK S E. Carbon dioxide utilization as a soft oxidant and promoter in catalysis[J]. Energy Environ sci,2012,5:9419−9437. doi: 10.1039/c2ee22409g
[7]	WANG T, QI L, LU H, JI M. Flower-like Al₂O₃-supported iron oxides as an efficient catalyst for oxidative dehydrogenation of ethlybenzene with CO₂[J]. J CO₂ Util,2017,17:162−169. doi: 10.1016/j.jcou.2016.12.005
[8]	张淑娇, 李文英, 李晓红. 制备方法对Fe₂O₃/Al₂O₃-ZrO₂在乙苯脱氢反应中催化性能的影响[J]. 燃料化学学报,2015,43(4):437−441. doi: 10.1016/S1872-5813(15)30012-8 ZHANG Shu-jiao, LI Wen-ying, LI Xiao-hong. Effect of preparation methods on the catalytic properties of Fe₂O₃/Al₂O₃-ZrO₂ for ethylbenzene dehydrogenation[J]. J Fuel Chem Technol,2015,43(4):437−441. doi: 10.1016/S1872-5813(15)30012-8
[9]	CHEN S W, XU Z Q, TAN D C, PAN D H, LI R F. Oxidative dehydrogenation of ethylbenzene to styrene with CO₂ over Al-MCM-41-supported vanadia catalysts: Al-MCM-41-supported vanadia catalysts for CO₂-ODEB[J]. Appl Organomet Chem,2019,34(2):1−10.
[10]	YANG G Q, WANG H, GONG T, SONG Y H, FENG H, GE H Q, GE H B, LIU Z T, LIU Z W. Understanding the active-site nature of vanadia-based catalysts for oxidative dehydrogenation of ethylbenzene with CO₂ via atomic layer deposited VO_x on γ-Al₂O₃[J]. J Catal,2019,380(5):195−203.
[11]	BETIHA M A, RABIE A M, ELFADLY A M, YEHIA F Z. Microwave assisted synthesis of a VO_x-modified disordered mesoporous silica for ethylbenzene dehydrogenation in presence of CO₂[J]. Microporous Mesoporous Mater,2016,222(1):44−54.
[12]	张海新, 陈树伟, 崔杏雨, 潘大海, 秦张峰, 王建国. Ce助剂对V/SiO₂催化CO₂氧化乙苯脱氢性能的影响[J]. 物理化学学报,2014,30(2):351−358. doi: 10.3866/PKU.WHXB201312021 ZHANG Hai-xin, CHEN Shu-wei, CUI Xin-yu, PAN Da-hai, QING Zhang-feng, WANG Jan-guo. Effect of Ce promoter on catalytic performance of V/SiO₂ in oxidative dehydrogenation of ethylbenzene with carbon dioxide[J]. Acta Phys-Chim Sin,2014,30(2):351−358. doi: 10.3866/PKU.WHXB201312021
[13]	李春光, 缪长喜, 聂颖颖, 乐英红, 顾松园, 杨为民, 华伟明, 高滋. CO₂气氛下MCF负载氧化钒催化剂上乙苯脱氢反应(英文)[J]. 催化学报,2010,31(8):993−998. LI Chun-guang, LIAO Chang-xi, NIE Yin-yin, LE Yin-hong, GU Song-yuan, YANG Wei-ming, HUA Wei-ming, GAO Zi. Ethylbenzene dehydrogenation in the presence of CO₂ over MCF-supported vanadium oxide catalysts[J]. J Catal,2010,31(8):993−998.
[14]	FAN H X, FENG J, LI W Y. Promotional effect of oxygen storage capacity on oxy-dehydrogenation of ethylbenzene with CO₂ over κ-Ce₂Zr₂O₈ (111)[J]. Appl Surf Sci,2019,486:411−419.
[15]	ZHANG L, WU Z, NELSON N C, SADOW A D, SLOWING I I, OVERBURY S H. Role of CO₂ as a soft oxidant for dehydrogenation of ethylbenzene to styrene over a high-surface-area ceria catalyst[J]. ACS Catal,2015,5(11):6426−6435. doi: 10.1021/acscatal.5b01519
[16]	DIAO J, HU M, LIAN Z, LI Z, LIU H. Ti₃C₂Tx MXene catalyzed ethylbenzene dehydrogenation: Active sites and mechanism exploration from both experimental and theoretical aspects[J]. ACS Catal,2018,8(11):10051−10057. doi: 10.1021/acscatal.8b02002
[17]	PAN D H, RU Y, LIU T L, WANG Y J, YU F, CHEN S W, YAN X L, FAN B B, LI R F. Highly efficient and stable ordered mesoporous Ti-Al composite oxide catalyst for oxidative dehydrogenation of ethylbenzene to styrene with CO₂[J]. Chem Eng Sci,2022,250:117388. doi: 10.1016/j.ces.2021.117388
[18]	LI Y F, SU J J, YU F, YAN X L, PAN D H, LI R F, YANG Y X. Dehydrogenation of ethylbenzene with CO₂ over porous Co/Al₂O₃-ZrO₂ catalyst[J]. Mater Chem Phys,2021,257:123773. doi: 10.1016/j.matchemphys.2020.123773
[19]	MADDULURI V R, RAO K S R. Correction to: Advantage of Co embedded γ-Al₂O₃ catalysts over MgO and SiO₂ solid oxides in the selective production of styrene monomer[J]. Catal Lett,2019,149(11):3253−3253. doi: 10.1007/s10562-019-02926-0
[20]	POCHAMONI R, NARANI A, VARKOLU M, GUDIMELLA M D, POTHARAJU S SAI P, BURRI D R, R. K S R. Studies on ethylbenzene dehydrogenation with CO₂ as soft oxidant over Co₃O₄/COK-12 catalysts[J]. J Chem Sci,2015,127(4):701−709. doi: 10.1007/s12039-015-0826-x
[21]	CHEN C, AHN W S. CO₂ capture using mesoporous alumina prepared by a sol-gel process[J]. Chem Eng J,2011,166(2):646−651. doi: 10.1016/j.cej.2010.11.038
[22]	SUN Y, WU Y, SHAN H, LI C. Studies on the nature of active cobalt species for the production of methane and propylene in catalytic dehydrogenation of propane[J]. Catal Lett,2015,145(7):1413−1419. doi: 10.1007/s10562-015-1533-4
[23]	DAI Y H, GU J J, TIAN S Y, WU Y, CHEN J C, LI F X, DU Y H, PENG L M, DING W P, YANG Y H. γ-Al₂O₃ sheet-stabilized isolate Co^{2 +} for catalytic propane dehydrogenation[J]. J Catal,2020,381(1):482−492.
[24]	高恋, 徐耀, 侯博, 吴东, 孙予罕. 介孔氧化硅球负载钴基催化剂在费托合成中的应用[J]. 化学学报,2008,66(16):1851−1856. doi: 10.3321/j.issn:0567-7351.2008.16.001 GAO Lian, XU Yao, HOU Bo, WU Dong, SUN Yu-han. Application of hollow mesoporous silica sphere supported cobalt catalysts in Fischer-Tropsch synthesis[J]. Acta Chim,2008,66(16):1851−1856. doi: 10.3321/j.issn:0567-7351.2008.16.001
[25]	LI X Y, WANG P Z, WANG H R, LI C Y. Effects of the state of Co species in Co/Al₂O₃ catalysts on the catalytic performance of propane dehydrogenation[J]. Appl Surf Sci,2018,441(1):688−693.