Citation: Yuan Pei, Chen Jian, Pan Deng, Bao Xiaojun. Adsorption and Reaction Kinetic Studies of the Heterogeneous Catalytic Hydrogenation for Polystyrene[J]. Acta Chimica Sinica, ;2016, 74(7): 603-611. doi: 10.6023/A16030117 shu

Adsorption and Reaction Kinetic Studies of the Heterogeneous Catalytic Hydrogenation for Polystyrene

Yuan Pei ^a,*,, ,
Chen Jian ^a ,
Pan Deng ^b ,
Bao Xiaojun ^b

a.
State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Beijing 102249
b.
The Key Laboratory of Catalysis, China University of Petroleum, Beijing 102249

Corresponding author: Yuan Pei, yuanpei@cup.edu.cn
Received Date: 4 March 2016

Fund Project: China National Petroleum Corp. 2012B-2805The National Natural Science Foundation of China 21106182The National Natural Science Foundation of China 21576290

Figures(10)

We applied silica hollow microspheres with through holes in the shell as supports to prepare Pd-based supported catalyst (Pd/SHMs) for heterogeneous catalytic hydrogenation of polystyrene (PS) and also systematically studied the adsorption and reaction behavior of PS molecules over Pd/SHMs. The dynamic adsorption and reaction models of PS molecules under different temperatures have been established and the partially hydrogenated products were also comprehensively analyzed. The result shows that both the adsorption capacity and saturation time are increased as the temperature increasing and this hydrogenation reaction is confirmed to be a first-order reaction and the activation energy is calculated to be 58.3 kJ·mol^-1. After separating and purifying three samples with different hydrogenation degrees, we further analyzed the partially hydrogenated products and the results show that they are all actually comprised of two kinds of substances with different properties, one with high hydrogenation conversion rate (ca. 85%) and the other with low hydrogenation ratio (ca. 25%). It is proved that PS heterogeneous hydrogenation process exists secondary adsorption and competitive adsorption phenomenon, and obeys the Blocky mechanism. This work lays the foundation for PS adsorption and hydrogenation reaction and is also favorable for the understanding of the adsorption and catalytic process for other unsaturated polymers over heterogeneous catalysts.
- hydrogenation,
- adsorption,
- kinetics,
- supported catalyst,
- unsaturated polymer
1. [1]
  Singha, N. K.; Bhattacharjee, S.; Sivaram, S. Rubber Chem. Technol. 1997, 70, 311.
2. [2]
  Xu, Z. D.; Hadjichristidis, N.; Carella, J. M.; Fetters, L. J. Macromolecules 1983, 16, 925. doi: 10.1021/ma00240a019
3. [3]
  Dondos, A.; Staikos, G. Colloid Polym. Sci. 1995, 273, 626. doi: 10.1007/BF00652254
4. [4]
  Garcia Escribiano, P.; Canovas, M. J.; Ojeda, M. C.; Del Rio, C.; Sanchez, F.; Acosta, J. L. Polym. Int. 2011, 60, 493. doi: 10.1002/pi.v60.3
5. [5]
  Wei, Z. L.; Wu, J. L.; Pan, Q. M.; Rempel, G. L. Macromol. Rapid Commun. 2005, 26, 1768. doi: 10.1002/(ISSN)1521-3927
6. [6]
  Monroy-Barreto, M.; Acosta, J. L.; Del Rio, C.; Ojeda, M. C.; Munoz, M.; Aguilar, J. C. J. Power Sources 2010, 195, 8052. doi: 10.1016/j.jpowsour.2010.06.105
7. [7]
  Jin, M.; Liao, M.; Zhai, J.; Jiang, L. Acta Chim. Sinica 2008, 66, 145.
8. [8]
  Xu, L.; Li, W.; Yang, M. Acta Chim. Sinica 2007, 65, 1917.
9. [9]
  Zhang, S.; Bai, Y.; Peng, J.; Hu, Y.; Lai, G. Prog. Chem. 2013, 25, 707.
10. [10]
  Przybyszewska, M.; Zaborski, M. Composite Interfaces 2009, 16, 131. doi: 10.1163/156855409X402920
11. [11]
  Yoon, K.; Kim, K. O.; Schaefer, M.; Yoon, D. Y. Polymer 2012, 53, 2290. doi: 10.1016/j.polymer.2012.02.047
12. [12]
  Choi, M.; Kim, Y.; Ha, C. Prog. Polym. Sci. 2008, 33, 581. doi: 10.1016/j.progpolymsci.2007.11.004
13. [13]
  Gehlsen, M. D.; Bates, F. S. Macromolecules 1993, 26, 4122. doi: 10.1021/ma00068a009
14. [14]
  Huang, H.; Fan, Y.; Tao, S.; Gao, H. New Chem. Mater. 2013, 41, 178.
15. [15]
  Ness, J. S.; Brodil, J. C.; Bates, F. S.; Hahn, S. F.; Hucul, D. A.; Hillmyer, M. A. Macromolecules 2001, 35, 602.
16. [16]
  Dong, L. B.; Turgman-Cohen, S.; Roberts, G. W.; Kiserow, D. J. Ind. Eng. Chem. Res. 2010, 49, 11280. doi: 10.1021/ie1011905
17. [17]
  Xu, D.; Carbonell, R. G.; Kiserow, D. J.; Roberts, G. W. Ind. Eng. Chem. Res. 2003, 42, 3509. doi: 10.1021/ie0301841
18. [18]
  Hucul, D. A.; Hahn, S. F. Adv. Mater. 2000, 12, 1855. doi: 10.1002/(ISSN)1521-4095
19. [19]
  Aylward, F.; Sawistowka, M.; Arthur, F.; Robert, C. B.; Shirley, H. Chem. Rev. 1965, 65, 51. doi: 10.1021/cr60233a002
20. [20]
  Parent, J. S.; Mcmanus, N. T.; Rempel, G. L. Ind. Eng. Chem. Res. 1996, 35, 4417. doi: 10.1021/ie9506680
21. [21]
  Martin, P.; Mcmanus, N. T.; Rempel, G. L. J. Mol. Catal. A: Chem. 1997, 126, 115. doi: 10.1016/S1381-1169(97)00102-7
22. [22]
  Bhattacharjee, S.; Bhowmick, A. K.; Avasthi, B. N. J. Polym. Sci. Part A: Polym. Chem. 1992, 30, 471. doi: 10.1002/pola.1992.080300314
23. [23]
  Bond, G. C. Heterogeneous Catalysis: Principles and Applications, 2nd Ed., Clarendon Press, Oxford, 1987, p. 120.
24. [24]
  Bussard, A.; Dooley, K. M. AIChE J. 2008, 54, 1064. doi: 10.1002/(ISSN)1547-5905
25. [25]
  Zhou, H.; Qiang, M.; Li, J.; Li, Y.; Wang, J. Polym. Mater. Sci. Eng. 2011, 27, 73.
26. [26]
  Almusaiteer, K. A. Top. Catal. 2012, 55, 498. doi: 10.1007/s11244-012-9821-3
27. [27]
  Hutchings, G. J. J. Mater. Chem. 2009, 19, 1222. doi: 10.1039/B812300B
28. [28]
  Fang, F.; Satulovsky, J.; Szleifer, I. Biophys. J. 2005, 89, 1516. doi: 10.1529/biophysj.104.055079
29. [29]
  Rosedale, J. H.; Bates, F. S. J. Am. Chem. Soc. 1988, 110, 3542. doi: 10.1021/ja00219a032
30. [30]
  Huang, H.; Zhou, J.; Ying, Q.; Tao, S. Mod. Chem. Ind. 2014, 34, 70.
31. [31]
  Cassano, G. A.; Vallés, E. M.; Quinzani, L. M. Polymer 1998, 39, 5573. doi: 10.1016/S0032-3861(97)10080-5
32. [32]
  Tsukagoshi, T.; Kondo, Y.; Yoshino, N. Colloids Surf. B-Biointerfaces 2007, 54, 101. doi: 10.1016/j.colsurfb.2006.10.004
33. [33]
  Linse, P.; Kallrot, N. Macromolecules 2010, 43, 2054. doi: 10.1021/ma902338m
34. [34]
  Kawaguchi, M.; Anada, S.; Nishikawa, K.; Kurata, N. Macromolecules 1992, 25, 1588. doi: 10.1021/ma00031a035
35. [35]
  Kawaguchi, M.; Sakata, Y.; Anada, S.; Kato, T.; Takahashi, A. Langmuir 1994, 10, 538. doi: 10.1021/la00014a033
36. [36]
  Rybicka, J.; Sikorski, A. Macromol. Theory Simul. 2010, 19, 135.
37. [37]
  Scheutjens, J. M. H. M.; Fleer, G. J. J. Phys. Chem. 1979, 83, 1619. doi: 10.1021/j100475a012
38. [38]
  Scheutjens, J. M. H. M.; Fleer, G. J. J. Phys. Chem. 1980, 84, 178. doi: 10.1021/j100439a011
39. [39]
  Doi, Y.; Yano, A.; Soga, K.; Burfield, D. R. Macromolecules 1986, 19, 2409. doi: 10.1021/ma00163a013
40. [40]
  Tangthongkul, R.; Prasassarakich, P.; Mcmanus, N. T.; Rempel, G. L. J. Appl. Polym. Sci. 2004, 91, 3259. doi: 10.1002/(ISSN)1097-4628
41. [41]
  Hinchiranan, N.; Charmondusit, K.; Prasassarakich, P.; Rempel, G. L. J. Appl. Polym. Sci. 2006, 100, 4219. doi: 10.1002/(ISSN)1097-4628
42. [42]
  Pan, D.; Shi, G.; Zhang, T.; Yuan, P.; Fan, Y.; Bao, X. J. Mater. Chem. A 2013, 1, 9597. doi: 10.1039/c3ta11824j
43. [43]
  Dijt, J. C.; Cohen Stuart, M. A.; Fleer, G. J. Macromolecules 1994, 27, 3207. doi: 10.1021/ma00090a014
44. [44]
  Kislenko, V. N.; Berlin, A. A.; Kawaguchi, M.; Kato, T. Langmuir 1996, 12, 768. doi: 10.1021/la950478u
45. [45]
  Tóth, J. Adsorption: Theory, Modeling, and Analysis, Marcel Dekker, New York, 2002, p. 26.
46. [46]
  Whittier, R. E. MS Thesis, North Carolina State University, Raleigh, 2004.
1. [1]
  Hailian Tang , Siyuan Chen , Qiaoyun Liu , Guoyi Bai , Botao Qiao , Liu Fei . Stabilized Rh/hydroxyapatite Catalyst for Furfuryl Alcohol Hydrogenation: Application of Oxidative Strong Metal-Support Interactions in Reducing Conditions. Acta Physico-Chimica Sinica, 2025, 41(4): 2408004-0. doi: 10.3866/PKU.WHXB202408004
2. [2]
  Hui Wang , Abdelkader Labidi , Menghan Ren , Feroz Shaik , Chuanyi Wang . Recent Progress of Microstructure-Regulated g-C₃N₄ in Photocatalytic NO Conversion: The Pivotal Roles of Adsorption/Activation Sites. Acta Physico-Chimica Sinica, 2025, 41(5): 100039-0. doi: 10.1016/j.actphy.2024.100039
3. [3]
  Heng Zhang . Determination of All Rate Constants in the Enzyme Catalyzed Reactions Based on Michaelis-Menten Mechanism. University Chemistry, 2024, 39(4): 395-400. doi: 10.3866/PKU.DXHX202310047
4. [4]
  Zhiwen HU , Ping LI , Yulong YANG , Weixia DONG , Qifu BAO . Morphology effects on the piezocatalytic performance of BaTiO₃. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 339-348. doi: 10.11862/CJIC.20240172
5. [5]
  Mahmoud Sayed , Han Li , Chuanbiao Bie . Challenges and prospects of photocatalytic H₂O₂ production. Acta Physico-Chimica Sinica, 2025, 41(9): 100117-0. doi: 10.1016/j.actphy.2025.100117
6. [6]
  Jingke LIU , Jia CHEN , Yingchao HAN . Nano hydroxyapatite stable suspension system: Preparation and cobalt adsorption performance. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1763-1774. doi: 10.11862/CJIC.20240060
7. [7]
  Ying Yang , Yonghan Wu , Zixuan Li , Lu Zhang , Rongqin Lin , Yefan Zhang , Jiquan Liu , Xiaohui Ning , Yan Li , Bin Cui . Visualization Simulation Experiment of Cyclic Voltammetry (CV) Based on Python. University Chemistry, 2025, 40(10): 233-242. doi: 10.12461/PKU.DXHX202412024
8. [8]
  Peng XU , Shasha WANG , Nannan CHEN , Ao WANG , Dongmei YU . Preparation of three-layer magnetic composite Fe₃O₄@polyacrylic acid@ZiF-8 for efficient removal of malachite green in water. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 544-554. doi: 10.11862/CJIC.20230239
9. [9]
  Zeyu XU , Anlei DANG , Bihua DENG , Xiaoxin ZUO , Yu LU , Ping YANG , Wenzhu YIN . Evaluation of the efficacy of graphene oxide quantum dots as an ovalbumin delivery platform and adjuvant for immune enhancement. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1065-1078. doi: 10.11862/CJIC.20240099
10. [10]
  Jing Wang , Pingping Li , Yuehui Wang , Yifan Xiu , Bingqian Zhang , Shuwen Wang , Hongtao Gao . Treatment and Discharge Evaluation of Phosphorus-Containing Wastewater. University Chemistry, 2024, 39(5): 52-62. doi: 10.3866/PKU.DXHX202309097
11. [11]
  Guang Huang , Lei Li , Dingyi Zhang , Xingze Wang , Yugai Huang , Wenhui Liang , Zhifen Guo , Wenmei Jiao . Cobalt’s Valor, Nickel’s Foe: A Comprehensive Chemical Experiment Utilizing a Cobalt-based Imidazolate Framework for Nickel Ion Removal. University Chemistry, 2024, 39(8): 174-183. doi: 10.3866/PKU.DXHX202311051
12. [12]
  Fugui XI , Du LI , Zhourui YAN , Hui WANG , Junyu XIANG , Zhiyun DONG . Functionalized zirconium metal-organic frameworks for the removal of tetracycline from water. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 683-694. doi: 10.11862/CJIC.20240291
13. [13]
  Wei Li , Jinfan Xu , Yongjun Zhang , Ying Guan . 共价有机框架整体材料的制备及食品安全非靶向筛查应用——推荐一个仪器分析综合化学实验. University Chemistry, 2025, 40(6): 276-285. doi: 10.12461/PKU.DXHX202406013
14. [14]
  You Wu , Chang Cheng , Kezhen Qi , Bei Cheng , Jianjun Zhang , Jiaguo Yu , Liuyang Zhang . Efficient Photocatalytic Production of H₂O₂ over ZnO/D-A Conjugated Polymer S-scheme Heterojunction and Charge Transfer Dynamics Investigation. Acta Physico-Chimica Sinica, 2024, 40(11): 2406027-0. doi: 10.3866/PKU.WHXB202406027
15. [15]
  Jiayu Gu , Siqi Wang , Jun Ling . Kinetics of Living Copolymerization: A Brief Discussion. University Chemistry, 2025, 40(4): 100-107. doi: 10.12461/PKU.DXHX202406012
16. [16]
  Jiajie Cai , Chang Cheng , Bowen Liu , Jianjun Zhang , Chuanjia Jiang , Bei Cheng . CdS/DBTSO-BDTO S-scheme photocatalyst for H₂ production and its charge transfer dynamics. Acta Physico-Chimica Sinica, 2025, 41(8): 100084-0. doi: 10.1016/j.actphy.2025.100084
17. [17]
  Wenlong LI , Xinyu JIA , Jie LING , Mengdan MA , Anning ZHOU . Photothermal catalytic CO₂ hydrogenation over a Mg-doped In₂O_3-x catalyst. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 919-929. doi: 10.11862/CJIC.20230421
18. [18]
  Linlin Wu , Yonghua Zhou , Zhongbei Li , Liu Deng , Younian Liu , Limiao Chen , Jianhan Huang . Digital Education Promoting Applied Chemistry Comprehensive Experiments: A Case Study of Catalytic Oxidation of Hydrogen Chloride and Reaction Kinetics. University Chemistry, 2025, 40(9): 273-278. doi: 10.12461/PKU.DXHX202411018
19. [19]
  Xinyu Xu , Jiale Lu , Bo Su , Jiayi Chen , Xiong Chen , Sibo Wang . Steering charge dynamics and surface reactivity for photocatalytic selective methane oxidation to ethane over Au/Ti-CeO₂. Acta Physico-Chimica Sinica, 2025, 41(11): 100153-0. doi: 10.1016/j.actphy.2025.100153
20. [20]
  Qinhui Guan , Yuhao Guo , Na Li , Jing Li , Tingjiang Yan . Molecular sieve-mediated indium oxide catalysts for enhancing photocatalytic CO₂ hydrogenation. Acta Physico-Chimica Sinica, 2025, 41(11): 100133-0. doi: 10.1016/j.actphy.2025.100133

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(2207)
HTML views(512)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142