B-COPNA resin formation from ethylene tar light fractions: Process development and mechanical exploration by molecular simulation

doi:10.1016/j.cjche.2024.03.005

Abstract

Abstract: An efficient utilization strategy of ethylene tar (ET), the main by-product of the ethylene cracking unit, is urgently required to meet demands for modern petrochemical industry. On the other hand, condensed polynuclear aromatic resin of moderate condensation degree (B-COPNA) is a widely used carbon material due to its superb processability, the production of which is, however, seriously limited by the high cost of raw materials. Under such context, an interesting strategy was proposed in this study for producing B-COPNA resin using crosslinked light fractions of ethylene tar (ETLF, boiling point <260 ℃) facilitated by molecular simulation. 1,4-Benzenedimethanol (PXG) was first selected as the crosslinking agent according to the findings of molecular simulation. The effects of operating conditions, including reactions temperature, crosslinking agent, and catalyst content on the softening point and yield of B-COPNA resin products were then investigated to optimize the process. The reaction mechanism of resin production was studied by analyzing the molecular structure and transition state of ETLF and crosslinking agents. It was shown that PXG exhibited a superior capacity of withdrawing electrons and a higher electrophilic reactivity than other crosslinking agents. In addition to the highest yield and greatest heat properties, PXG-prepared resin contained the most condensed aromatics. The corresponding optimized conditions of resin preparation were 180 ℃, 1:1.9 (PXG:ETLF), and 3% (mass) of catalyst content with a resin yield of 78.57%. It was the electrophilic substitution reaction that occurred between the ETLF and crosslinking agent molecules that were responsible for the resin formation, according to the experimental characterization and molecular simulation. Hence, it was confirmed that the proposed strategy and demonstrated process can achieve a clean and high value-added utilization of ETLF via B-COPNA resin preparation, bringing huge economic value to the current petrochemical industry.

Key words: Ethylene tar, Crosslinking, COPNA resin, Molecular simulation, Transient state

摘要： An efficient utilization strategy of ethylene tar (ET), the main by-product of the ethylene cracking unit, is urgently required to meet demands for modern petrochemical industry. On the other hand, condensed polynuclear aromatic resin of moderate condensation degree (B-COPNA) is a widely used carbon material due to its superb processability, the production of which is, however, seriously limited by the high cost of raw materials. Under such context, an interesting strategy was proposed in this study for producing B-COPNA resin using crosslinked light fractions of ethylene tar (ETLF, boiling point <260 ℃) facilitated by molecular simulation. 1,4-Benzenedimethanol (PXG) was first selected as the crosslinking agent according to the findings of molecular simulation. The effects of operating conditions, including reactions temperature, crosslinking agent, and catalyst content on the softening point and yield of B-COPNA resin products were then investigated to optimize the process. The reaction mechanism of resin production was studied by analyzing the molecular structure and transition state of ETLF and crosslinking agents. It was shown that PXG exhibited a superior capacity of withdrawing electrons and a higher electrophilic reactivity than other crosslinking agents. In addition to the highest yield and greatest heat properties, PXG-prepared resin contained the most condensed aromatics. The corresponding optimized conditions of resin preparation were 180 ℃, 1:1.9 (PXG:ETLF), and 3% (mass) of catalyst content with a resin yield of 78.57%. It was the electrophilic substitution reaction that occurred between the ETLF and crosslinking agent molecules that were responsible for the resin formation, according to the experimental characterization and molecular simulation. Hence, it was confirmed that the proposed strategy and demonstrated process can achieve a clean and high value-added utilization of ETLF via B-COPNA resin preparation, bringing huge economic value to the current petrochemical industry.

关键词: Ethylene tar, Crosslinking, COPNA resin, Molecular simulation, Transient state

Hongyan Shen, Lingrui Cui, Xingguo Wei, Yuanqin Zhang, Lian Cen, Jun Xu, Fahai Cao. B-COPNA resin formation from ethylene tar light fractions: Process development and mechanical exploration by molecular simulation[J]. Chinese Journal of Chemical Engineering, 2024, 70(6): 118-129.

References

[1] Y. Li, J.H. Yu, Emerging applications of zeolites in catalysis, separation and host-guest assembly, Nat. Rev. Mater. 6 (2021) 1156-1174.
[2] P.C. Sabapathy, S. Devaraj, K. Meixner, P. Anburajan, P. Kathirvel, Y. Ravikumar, H.M. Zabed, X. Qi, Recent developments in Polyhydroxyalkanoates (PHAs) production-A review, Bioresour. Technol. 306 (2020) 123132.
[3] H. Mina, D. Kannan, S.M. Gholami-Zanjani, M. Biuki, Transition towards circular supplier selection in petrochemical industry: A hybrid approach to achieve sustainable development goals, J. Clean. Prod. 286 (2021) 125273.
[4] Y.F. Gao, L. Neal, D. Ding, W. Wu, C. Baroi, A.M. Gaffney, F.X. Li, Recent advances in intensified ethylene production-a review, ACS Catal. 9 (9) (2019) 8592-8621.
[5] J. Kim, W. Choi, J.W. Park, C. Kim, M. Kim, H. Song, Branched copper oxide nanoparticles induce highly selective ethylene production by electrochemical carbon dioxide reduction, J. Am. Chem. Soc. 141 (17) (2019) 6986-6994.
[6] K.J.P. Schouten, Z.S. Qin, E. Perez Gallent, M.T.M. Koper, Two pathways for the formation of ethylene in CO reduction on single-crystal copper electrodes, J. Am. Chem. Soc. 134 (24) (2012) 9864-9867.
[7] A. Ozden, Y.H. Wang, F.W. Li, M.C. Luo, J. Sisler, A. Thevenon, A. Rosas-Hernandez, T. Burdyny, Y. Lum, H. Yadegari, T. Agapie, J.C. Peters, E.H. Sargent, D. Sinton, Cascade CO₂ electroreduction enables efficient carbonate-free production of ethylene, Joule 5 (3) (2021) 706-719.
[8] Y.Y. Borisova, N.A. Mironov, S.G. Yakubova, D.N. Borisov, I.P. Kosachev, M.R. Yakubov, Application of ethylene tar as an additive in visbreaking of petroleum vacuum residue, Energy Fuels 35 (19) (2021) 15684-15694.
[9] K. Shi, J.X. Yang, C. Ye, H.B. Liu, X.K. Li, A comparison of ethylene-tar-derived isotropic pitches prepared by air blowing and nitrogen distillation methods and their carbon fibers, Materials 12 (2) (2019) 305.
[10] X.L. Cheng, Q.F. Zha, J.T. Zhong, X.J. Yang, Needle coke formation derived from co-carbonization of ethylene tar pitch and polystyrene, Fuel 88 (11) (2009) 2188-2192.
[11] L. Ling, K. Li, L. Liu, S. Miyamoto, Y. Korai, S. Kawano, I. Mochida, Removal of SO₂ over ethylene tar pitch and cellulose based activated carbon fibers, Carbon 37 (3) (1999) 499-504.
[12] M.B. Wu, Y.Y. Shi, S.B. Li, N. Guo, Y.W. Wang, J.T. Zheng, J.S. Qiu, Synthesis and characterization of condensed poly-nuclear aromatic resin using heavy distillate from ethylene tar, Carbon 55 (2012) 377.
[13] C.Z. Ge, Z.L. Sun, H.X. Yang, D.H. Long, W.M. Qiao, L.C. Ling, Preparation and characterization of high softening point and homogeneous isotropic pitches produced from distilled ethylene tar by a novel bromination method, Carbon 134 (2018) 537.
[14] K. Shi, X.X. Zhang, W. Wu, J.X. Yang, H.B. Liu, X.K. Li, Effect of the oxygen content and the functionality of spinnable pitches derived from ethylene tar by distillation on the mechanical properties of carbon fibers, Carbon 150 (2019) 555.
[15] J.C. Liu, X.J. Chen, Q. Xie, D.C. Liang, Controllable synthesis of isotropic pitch precursor for general purpose carbon fiber using waste ethylene tar via bromination-dehydrobromination, J. Clean. Prod. 271 (2020) 122498.
[16] Y.Y. Yu, F. Wang, B. Wiafe Biney, K.Q. Li, S.H. Jiao, K. Chen, H. Liu, A.J. Guo, Co-carbonization of ethylene tar and fluid catalytic cracking decant oil: Development of high-quality needle coke feedstock, Fuel 322 (2022) 124170.
[17] D.Y. Han, Z.B. Cao, Y.F. Li, Investigation of naphthalene extraction from ethylene tar, Energy Sources Part A Recovery Util. Environ. Eff. 36 (9) (2014) 993-998.
[18] L. Chen, D.G. Cheng, F.Q. Chen, X.L. Zhan, A density functional theory study on the conversion of polycyclic aromatic hydrocarbons in hydrogen plasma, Int. J. Hydrog. Energy 45 (1) (2020) 309-321.
[19] C.Z. Ge, H.X. Yang, J.T. Wang, W.M. Qiao, D.H. Long, L.C. Ling, Highly effective utilization of ethylene tar for mesophase development via a molecular fractionation process, RSC Adv. 6 (1) (2016) 796-804.
[20] M. Ota, S. Otani, K. Kobayashi, The preparation and properties of the condensed polynuclear aromatic (COPNA) resins using an aromatic aldehyde as crosslinking agent, Chem. Lett. 18 (7) (1989) 1175-1178.
[21] M. Ota, S. Otani, S. Iizuka, T. Sawada, E. Ota, A. Kojima, Syntheses of polycondensed fused-polynuclear aromatics (COPNA). Resin from the mixture of pyrene and phenanthrene using dimethyl derivatives of benzenedimethanols as cross-linking agents, NIPPON KAGAKU KAISHI 3 (1988) 343-350.
[22] K. Nawa, Development of flexible polymer blend films from advanced copna resin and nylon 6, J. Appl. Polym. Sci. 61 (10) (1996) 1737-1746.
[23] K. Kusakabe, S. Gohgi, S. Morooka, Carbon molecular sieving membranes derived from condensed polynuclear aromatic (COPNA) resins for gas separations, Ind. Eng. Chem. Res. 37 (11) (1998) 4262-4266.
[24] K. Tanemura, T. Suzuki, Y. Nishida, T. Horaguchi, Synthesis of the strongly acidic sulfonated condensed polynuclear aromatic (S-COPNA) resins using aromatic aldehydes as cross-linking agents, Polym. Bull. 68 (3) (2012) 705-719.
[25] J.T. Xia, Z.L. Hu, Z.H. Chen, G.Y. Ding, Preparation of carbon brushes with thermosetting resin binder, Trans. Nonferrous Met. Soc. China 17 (6) (2007) 1379-1384.
[26] J.C. Zhang, J.L. Shi, Y. Zhao, Q.G. Guo, L. Liu, Z.H. Feng, Z. Fan, Structural changes in four different precursors with heat treatment at high temperature and resin carbon structural model, J. Mater. Sci. 47 (15) (2012) 5891-5899.
[27] W. Jiang, G.S. Ni, P.P. Zuo, S.J. Qu, Y.M. Li, H.X. Niu, W.Z. Shen, Controlling spinning pitch property by tetrahydrofuran-soluble fraction of coal tar pitch co-carbonization with petrolatum, Carbon Lett. 29 (5) (2019) 505-519.
[28] P. Alvarez, J. Sutil, R. Santamaria, C. Blanco, R. Menendez, M. Granda, Mesophase from anthracene oil-based pitches, Energy Fuels 22 (6) (2008) 4146-4150.
[29] H.G. Liu, T.H. Li, X.L. Wang, W.J. Zhang, T.K. Zhao, Preparation and characterization of carbon foams with high mechanical strength using modified coal tar pitches, J. Anal. Appl. Pyrolysis 110 (2014) 442-447.
[30] S. Otani, V. Raskovic, A. Oya, A. Kojima, Some properties of a condensed polynuclear aromatic resin (COPNA) as a binder for carbon fibre composites, J. Mater. Sci. 21 (6) (1986) 2027-2032.
[31] X. Ruan, Y. Dong, J. Zheng, C. Guo, Studies on synthesis of pyrene-benzaldehyde COPNA resin and its magnetic, J.Journal of Fuel Chemistry and Technology. 25(5)(1997):473.
[32] M Ota, H Omiya, K Itoh, S Otani, Effect of a-methylnaphthalene as a compatibilizing agent on the mechanical properties of the fiber spun from the coal tar pitch-based thermosetting resin, J.Polym Prepr. 222(2001):253.
[33] Q. L. Lin, T. H. Li, Synthesis and properties of condensed polynuclear aromatics resin using coal tar pitch as monomer and terephthalic aldehyde as cross-linking agent, Polymeric Materials Science and Engineering,23（2） (2007)62-64. （in Chinese）.
[34] Y.C. Guo, L.L. Chen, Q.F. Zha, G. Brebeanu, C. Dusescu, P. Rosca, Study on aromatic enrichment of FCC slurry for synthesizing COPNA. J.Revista de Chimie. 57(6)(2006): 645-649.
[35] W.L. Fang, L.R. Cui, Y.Q. Zhang, H.Y. Shen, J. Xu, M.N. Ren, F.H. Cao, Investigation on a novel preparation process of B-COPNA resin from catalytic cracking diesel, Fuel 320 (2022) 123916.
[36] W.F. Van Gunsteren, X. Daura, N. Hansen, A.E. Mark, C. Oostenbrink, S. Riniker, L.J. Smith, Validation of molecular simulation: An overview of issues, Angew. Chem. Int. Ed. 57 (4) (2018) 884-902.
[37] B. Aguilera-Mercado, C. Herdes, J. Murgich, E.A. Muller, Mesoscopic simulation of aggregation of asphaltene and resin molecules in crude oils, Energy Fuels 20 (1) (2006) 327-338.
[38] Y.J. Ding, B.M. Tang, Y.Z. Zhang, J.M. Wei, X.J. Cao, Molecular dynamics simulation to investigate the influence of SBS on molecular agglomeration behavior of asphalt, J. Mater. Civ. Eng. 27 (8) (2015) 4014001-4014007.
[39] X.Y. Ma, J.T. Wu, Q. Liu, W.C. Ren, M. Oeser, Molecular dynamics simulation of the bitumen-aggregate system and the effect of simulation details, Constr. Build. Mater. 285 (2021) 122886.
[40] D. Nazarian, J.S. Camp, D.S. Sholl, A comprehensive set of high-quality point charges for simulations of metal-organic frameworks, Chem. Mater. 28 (3) (2016) 785-793.
[41] T.M. Nymand, P. Linse, Ewald summation and reaction field methods for potentials with atomic charges, dipoles, and polarizabilities, J. Chem. Phys. 112 (14) (2000) 6152-6160.
[42] G. Venkatesh, C. Kamal, P. Vennila, M. Govindaraju, Y.S. Mary, S. Armakovic, S.J. Armakovic, S. Kaya, C.Y. Panicker, Molecular dynamic simulations, ALIE surface, Fukui functions geometrical, molecular docking and vibrational spectra studies of tetra chloro p and m-xylene, J. Mol. Struct. 1171 (2018) 253-267.
[43] F. Fallah, F. Khabaz, Y.R. Kim, S.R. Kommidi, H.F. Haghshenas, Molecular dynamics modeling and simulation of bituminous binder chemical aging due to variation of oxidation level and saturate-aromatic-resin-asphaltene fraction, Fuel 237 (2019) 71-80.
[44] A. Samieadel, D. Oldham, E.H. Fini, Investigating molecular conformation and packing of oxidized asphaltene molecules in presence of paraffin wax, Fuel 220 (2018) 503-512.
[45] S.S. Ren, X.Y. Liu, Y. Zhang, P. Lin, P. Apostolidis, S. Erkens, M.L. Li, J. Xu, Multi-scale characterization of lignin modified bitumen using experimental and molecular dynamics simulation methods, Constr. Build. Mater. 287 (2021) 123058.
[46] G.N. Li, M.Z. Han, Y.Q. Tan, A.X. Meng, J.L. Li, S. Li, Research on bitumen molecule aggregation based on coarse-grained molecular dynamics, Constr. Build. Mater. 263 (2020) 120933.
[47] A.V. Marenich, C.J. Cramer, D.G. Truhlar, Universal solvation model based on solute electron density and on a continuum model of the solvent defined by the bulk dielectric constant and atomic surface tensions, J. Phys. Chem. B 113 (18) (2009) 6378-6396.
[48] S. Grimme, Semiempirical GGA-type density functional constructed with a long-range dispersion correction, J. Comput. Chem. 27 (15) (2006) 1787-1799.
[49] T. Lu, F.W. Chen, Multiwfn: A multifunctional wavefunction analyzer, J. Comput. Chem. 33 (5) (2012) 580-592.
[50] M.J.Frish, J.Hiscocks, M.Caricato, Gaussian 09: IOps Reference, Wallingford, CT, USA, 2009.
[51] P. Fuentealba, P. Perez, R. Contreras, On the condensed Fukui function, J. Chem. Phys. 113 (7) (2000) 2544-2551.
[52] S. Bahmanyar, K.N. Houk, Transition states of amine-catalyzed aldol reactions involving enamine intermediates: theoretical studies of mechanism, reactivity, and stereoselectivity, J. Am. Chem. Soc. 123 (45) (2001) 11273-11283.
[53] H.P. Li, W.S. Zhu, S.W. Zhu, J.X. Xia, Y.H. Chang, W. Jiang, M. Zhang, Y.W. Zhou, H.M. Li, The selectivity for sulfur removal from oils: an insight from conceptual density functional theory, AlChE. J. 62 (6) (2016) 2087-2100.
[54] E.A. Bayle, Modeling the transition state structure to probe a reaction mechanism on the oxidation of quinoline by quinoline 2-oxidoreductase, Chem. Cent. J. 10 (1) (2016) 70.
[55] Z.C. Zhao, P. Li, Q.W. Fan, H. Yan, Studies on predicting reactive sites of 3, 9-diazatetraasteranes by conceptual density functional theory and experiment, Struct. Chem. 30 (5) (2019) 1707-1714.
[56] W. Jiang, K. Zhu, H.P. Li, L.H. Zhu, M.Q. Hua, J. Xiao, C. Wang, Z.Z. Yang, G.Y. Chen, W.S. Zhu, H.M. Li, S. Dai, Synergistic effect of dual Broensted acidic deep eutectic solvents for oxidative desulfurization of diesel fuel, Chem. Eng. J. 394 (2020) 124831.
[57] L. Merzoud, F. Guégan, H. Chermette, C. Morell, Understanding the intermolecular Diels-Alder cycloaddition promotion: activation strain model/energy decomposition analysis model and conceptual density functional theory viewpoints, J. Comput. Chem. 42 (19) (2021) 1364-1372.
[58] C.A. Grambow, L. Pattanaik, W.H. Green, Reactants, products, and transition states of elementary chemical reactions based on quantum chemistry, Sci. Data 7 (1) (2020) 137.