Coal Geology & Exploration
Abstract
Significance Polycyclic aromatic hydrocarbons (PAHs), a predominant component in coal tar, can be used to produce jet fuels with high energy density and thermal stability through hydrogenation saturation. Based on the characteristics of the PAH hydrogenation process, this study proposed that primary challenges in PAH hydrogenation saturation include the resonance energy of PAHs themselves, the spatial site resistance of hydrogenation intermediates, and the competitive adsorption of feedstocks and intermediates on active sites in the catalysts. Progress Based on the review of research progress in catalysts for PAH hydrogenation saturation in recent years, this study analyzed the substantial factor influencing the catalyst performance, and key findings are as follows: (1) More hydrogenation active sites in catalysts can be obtained by increasing the dispersion of the active metal components in catalysts and reducing the sizes of metal particles in catalysts, with appropriate electron-deficient states of active metals in catalysts promoting the adsorption and activation of PAH molecules on the active sites and inhibiting the adverse effects caused by the competitive adsorption. (2) Catalyst carriers with abundant pore throats and mesopore structures (6‒8 nm) are favorable for the diffusion of PAHs and hydrogenation intermediates, thus reducing the adverse effects of hydrogenation intermediates' spatial site resistance on hydrogenation reactions. Meanwhile, these catalyst carriers can provide more reaction surfaces, thereby enhancing deep hydrogenation reactions. (3) The interactions between acidic suitable carriers and active components can promote the formation of suitable electron-deficient states of the active components. A summary of the thermodynamic and kinetic characteristics of the PAH hydrogenation saturation process revealed that the PAH hydrogenation reactions are exothermic and reversible, with the equilibrium constant and equilibrium conversion increasing with decreasing reaction temperature and increasing reaction pressure, the PAH diffusion intensifying with an increase in the reaction temperature, and the adsorption constant decreasing with an increase in the number of saturated rings. Prospects This study proposed suggestions for research on the design and adjustment of the active components and carriers of catalysts, along with the thermodynamics and kinetics of the PAH hydrogenation saturation process. The analyses and discussions of the hydrogenation saturation process of PAHs in coal tar and catalysts in this study will provide useful guidance for the efficient exploitation and utilization of tar-rich coal resources.
Keywords
coal tar, polycyclic aromatic hydrocarbon (PAH), hydrogenation saturation, catalyst, thermodynamics, kinetics
DOI
10.12363/issn.1001-1986.24.02.0099
Recommended Citation
HE Xinfu, GAO Fan, WU Hongju,
et al.
(2024)
"Advances in research on hydrogenation saturation of polycyclic aromatic hydrocarbons in coal tar,"
Coal Geology & Exploration: Vol. 52:
Iss.
7, Article 16.
DOI: 10.12363/issn.1001-1986.24.02.0099
Available at:
https://cge.researchcommons.org/journal/vol52/iss7/16
Reference
[1] 周秋成,席引尚,马宝岐. 我国煤焦油加氢产业发展现状与展望[J]. 煤化工,2020,48(3):3−8.
ZHOU Qiucheng,XI Yinshang,MA Baoqi. Development situation and trend of coal tar hydrogenation industry in China[J]. Coal Chemical Industry,2020,48(3):3−8.
[2] YUAN Yang,LI Dong,ZHANG Linna,et al. Development,status,and prospects of coal tar hydrogenation technology[J]. Energy Technology,2016,4(11):1338−1348.
[3] BREYSSE M,AFANASIEV P,GEANTET C,et al. Overview of support effects in hydrotreating catalysts[J]. Catalysis Today,2003,86(1/2/3/4):5−16.
[4] STANISLAUS A,COOPER B H. Aromatic hydrogenation catalysis:A review[J]. Catalysis Reviews,1994,36(1):75−123.
[5] MORALES–VALENCIA E M,CASTILLO–ARAIZA C O,GIRALDO S A,et al. Kinetic assessment of the simultaneous hydrodesulfurization of dibenzothiophene and the hydrogenation of diverse polyaromatic structures[J]. ACS Catalysis,2018,8(5):3926−3942.
[6] KORRE S C,KLEIN M T,QUANN R J. Polynuclear aromatic hydrocarbons hydrogenation. 1. experimental reaction pathways and kinetics[J]. Industrial & Engineering Chemistry Research,1995,34(1):101−117.
[7] 王薇,舒歌平,章序文,等. 煤直接液化条件下菲催化加氢反应行为研究[J]. 化学反应工程与工艺,2019,35(2):106−112.
WANG Wei,SHU Geping,ZHANG Xuwen,et al. Catalytic hydrogenation reaction of phenanthrene under direct coal liquefaction conditions[J]. Chemical Reaction Engineering and Technology,2019,35(2):106−112.
[8] OH S K,KU Huiji,HAN G B,et al. Hydrogenation of polycyclic aromatic hydrocarbons over Pt/γ–Al2O3 catalysts in a trickle bed reactor[J]. Catalysis Today,2023,411:113831.
[9] 赵济伯. 苯环计数法计算多环苯型烃的共振能[J]. 北京工业大学学报,1986,12(2):51−66.
ZHAO Jibo. Calcuiation of resonance energies for benzenoid polycyclic aromatic hydrocarbons by benzene ring count method[J]. Journal of Beijing University of Technology,1986,12(2):51−66.
[10] KALENCHUK A,BOGDAN V,DUNAEV S,et al. Influence of steric factors on reversible reactions of hydrogenation–dehydrogenation of polycyclic aromatic hydrocarbons on a Pt/C catalyst in hydrogen storage systems[J]. Fuel,2020,280:118625.
[11] BELTRAMONE A R,RESASCO D E,ALVAREZ W E,et al. Simultaneous hydrogenation of multiring aromatic compounds over NiMo catalyst[J]. Industrial & Engineering Chemistry Research,2008,47(19):7161−7166.
[12] 刘道诚. Ni基尖晶石结构催化剂制备及菲加氢饱和性能研究[D]. 太原:太原理工大学,2021.
LIU Daocheng. Synthesis of Ni–based catalysts with spinel and its hydrogenation saturation performance of phenanthrene[D]. Taiyuan:Taiyuan University of Technology,2021.
[13] WANG Meiling,QIAN Xiaoqi,XIE Liqiang,et al. Synthesis of a Ni phyllosilicate with controlled morphology for deep hydrogenation of polycyclic aromatic hydrocarbons[J]. ACS Sustainable Chemistry & Engineering,2019,7(2):1989−1997.
[14] LIU Daocheng,CHEN Yu,JING Jieying,et al. Synthesis of Ni/NiAlOx catalysts for hydrogenation saturation of phenanthrene[J]. Frontiers in Chemistry,2021,9:757908.
[15] 李会峰,刘锋,刘泽龙,等. 菲在不同加氢催化剂上的转化[J]. 石油学报(石油加工),2011,27(1):20−25.
LI Huifeng,LIU Feng,LIU Zelong,et al. Hydrogenation of phenanthrene over different catalysts[J]. Acta Petrolei Sinica (Petroleum Processing Section),2011,27(1):20−25.
[16] CHEN Xiao,WANG Xingbao,HAN Shuhua,et al. Overcoming limitations in the strong interaction between Pt and irreducible SiO2 enables efficient and selective hydrogenation of anthracene[J]. ACS Applied Materials & Interfaces,2022,14(1):590−602.
[17] RAAD Z,TOUFAILY J,HAMIEH T,et al. TiO2–supported Pd as an efficient and stable catalyst for the mild hydrotreatment of tar–type compounds[J]. Nanomaterials,2021,11(9):2380.
[18] MANRÍQUEZ M E,NACIONAL I P,HERNANDEZ–PICHARDO M L,et al. Enhanced catalytic activity on the naphtalene hydrogenation reaction over Pt–Pd/Al2O3–CeO2 catalysts[J]. Revista Mexicana De Ingeniería Química,2018,17(3):913−925.
[19] 钱胜. Pd基金属催化多环芳烃加氢过程研究[D]. 太原:太原理工大学,2022.
QIAN Sheng. Study on hydrogenation of polycyclic aromatic hydrocarbons catalyzed by Pd based metals[D]. Taiyuan:Taiyuan University of Technology,2022.
[20] WANG Donge,LI Jiahe,ZHENG Anda,et al. Quasi–single–layer MoS2 on MoS2/TiO2 nanoparticles for anthracene hydrogenation[J]. ACS Applied Nano Materials,2019,2(8):5096−5107.
[21] WANG Donge,LI Jiahe,MA Huaijun,et al. Layer–structure adjustable MoS2 catalysts for the slurry–phase hydrogenation of polycyclic aromatic hydrocarbons[J]. Journal of Energy Chemistry,2021,63:294−304.
[22] 冯超. NiMo/MCM–41催化剂制备及菲加氢过程的研究[D]. 太原:太原理工大学,2021.
FENG Chao. Preparation of NiMo/MCM–41 catalyst and study on hydrogenation of phenanthrene[D]. Taiyuan:Taiyuan University of Technology,2021.
[23] FU Wenqian,ZHANG Lei,WU Dongfang,et al. Mesoporous zeolite–supported metal sulfide catalysts with high activities in the deep hydrogenation of phenanthrene[J]. Journal of Catalysis,2015,330:423−433.
[24] 刘道诚,王九占,荆洁颖,等. 稠环芳烃加氢饱和催化剂研究进展[J]. 化工进展,2021,40(2):835−844.
LIU Daocheng,WANG Jiuzhan,JING Jieying,et al. Research progress on the catalysts for saturated hydrogenation of polycyclic aromatic hydrocarbons[J]. Chemical Industry and Engineering Progress,2021,40(2):835−844.
[25] OYAMA S T. Novel catalysts for advanced hydroprocessing:Transition metal phosphides[J]. Journal of Catalysis,2003,216(1/2):343−352.
[26] FU Wenqian,ZHAO Wenbo,ZHANG Lei,et al. ZSM–5 microspheres consisting of nanocrystals for preparing highly dispersed MoP clusters with good activity in phenanthrene hydrogenation[J]. Industrial & Engineering Chemistry Research,2019,58(37):17289−17299.
[27] 王九占. 菲加氢饱和Ni基催化剂结构及性能调控[D]. 太原:太原理工大学,2021.
WANG Jiuzhan. Structure and performance adjustment of Ni based catalyst for phenanthrene saturated hydrogenation[D]. Taiyuan:Taiyuan University of Technology,2021.
[28] WU Chenghong,CHEN Xiaopeng,FU Jiawei,et al. ZIF–derived Co/NCNTs as a superior catalyst for aromatic hydrocarbon resin hydrogenation:Scalable green synthesis and insight into reaction mechanism[J]. Chemical Engineering Journal,2022,443:136193.
[29] BOULLOSA–EIRAS S,LØDENG R,BERGEM H,et al. Catalytic hydrodeoxygenation (HDO) of phenol over supported molybdenum carbide,nitride,phosphide and oxide catalysts[J]. Catalysis Today,2014,223:44−53.
[30] ZHANG Haiyong,CHEN Genwei,BAI Lei,et al. Selective hydrogenation of aromatics in coal–derived liquids over novel NiW and NiMo carbide catalysts[J]. Fuel,2019,244:359−365.
[31] LIN S D,SONG Chunshan. Noble metal catalysts for low–temperature naphthalene hydrogenation in the presence of benzothiophene[J]. Catalysis Today,1996,31(1/2):93−104.
[32] 陈羽,王九占,李泽,等. Ni2P/Al2O3–TiO2催化剂制备及其菲加氢饱和性能[J]. 洁净煤技术,2022,28(4):94−102.
CHEN Yu,WANG Jiuzhan,LI Ze,et al. Synthesis of Ni2P/Al2O3–TiO2 catalyst and its phenanthrene hydrogenation saturation performance[J]. Clean Coal Technology,2022,28(4):94−102.
[33] NIU Xiaopo,SUN Jiuyi,ZHAO Wenli,et al. Strong electronic metal–support interactions on supported Pt catalysts for efficient perhydrogenation of polyaromatics to aviation fuels[J]. Fuel Processing Technology,2023,241:107622.
[34] MCNEARY W W,TACEY S A,LAHTI G D,et al. Atomic layer deposition with TiO2 for enhanced reactivity and stability of aromatic hydrogenation catalysts[J]. ACS Catalysis,2021,11(14):8538−8549.
[35] 张孔远,杨光,何金康,等. Pt–Pd/SiO2–Al2O3催化剂芳烃加氢饱和性能研究[J]. 石油炼制与化工,2022,53(12):31−38.
ZHANG Kongyuan,YANG Guang,HE Jinkang,et al. Study on aromatics hydrogenation saturation performance of Pt–Pd/SiO2–Al2O3 catalyst[J]. Petroleum Processing and Petrochemicals,2022,53(12):31−38.
[36] SÁNCHEZ J,MORENO A,MONDRAGÓN F,et al. Bifunctional MoS2–silica–alumina catalysts for slurry phase phenanthrene–decalin hydroconversion[J]. Energy & Fuels,2018,32(10):10910−10922.
[37] LI Pengfei,WANG Li,ZHANG Xiangwen,et al. Deep hydrogenation saturation of naphthalene facilitated by enhanced adsorption of the reactants on micro–mesoporous Pd/HY[J]. ChemistrySelect,2021,6(22):5524−5533.
[38] NIU Xiaopo,ZHAO Rong,HAN Yunxi,et al. Highly dispersed platinum clusters anchored on hollow ZSM–5 zeolite for deep hydrogenation of polycyclic aromatic hydrocarbons[J]. Fuel,2022,326:125021.
[39] FU Wenqian,ZHANG Lei,WU Dongfang,et al. Mesoporous zeolite ZSM–5 supported Ni2P catalysts with high activity in the hydrogenation of phenanthrene and 4,6–dimethyldibenzothiophene[J]. Industrial & Engineering Chemistry Research,2016,55(26):7085−7095.
[40] ZHANG Minghui,HE Zexing,ZHANG Mingwei,et al. Tuning the location of Pd on HY zeolite by a dual–solvent method for efficient deep hydrogenation saturation of naphthalene[J]. Fuel,2022,316:123166.
[41] 周可. 蒽在贵金属催化剂上的选择性加氢研究[D]. 西安:西北大学,2018.
ZHOU Ke. Selective hydrogenation of anthracene over noble metal catalysts[D]. Xi’an:Northwest University,2018.
[42] LIANG Zhenhui,GUO Shaoqing,DONG Hongyu,et al. Modification of activated carbon and its application in selective hydrogenation of naphthalene[J]. ACS Omega,2022,7(43):38550−38560.
[43] BAIKENOV M I,AITBEKOVA D E,BALPANOVA N Z,et al. Hydrogenation of polyaromatic compounds over NiCo/chrysotile catalyst[J]. Bulletin of the Karaganda University \"Chemistry\" Series,2021,103(3):74−82.
[44] LIU Zhongqiu,WEI Xianyong,LIU Fangjing,et al. Temperature–controlled hydrogenation of anthracene over nickel nanoparticles supported on attapulgite powder[J]. Fuel,2018,223:222−229.
[45] PENG Chong,ZHOU Zhiming,FANG Xiangchen,et al. Thermodynamics and kinetics insights into naphthalene hydrogenation over a Ni–Mo catalyst[J]. Chinese Journal of Chemical Engineering,2021,39:173−182.
[46] PENG Chong,LIU Peng,ZHOU Zhiming,et al. Detailed understanding on thermodynamic and kinetic features of phenanthrene hydroprocessing on Ni–Mo/HY catalyst[J]. AIChE Journal,2022,68(11):e17831.
[47] 侯朝鹏,李永丹,夏国富,等. 蒽和菲加氢反应热力学分析[J]. 石油化工,2013,42(7):761−766.
HOU Chaopeng,LI Yongdan,XIA Guofu,et al. Thermodynamic analysis for hydrogenation of anthracene and phenanthrene[J]. Petrochemical Technology,2013,42(7):761−766.
[48] 胡意文,达志坚,王子军. 几种芳烃加氢反应的热力学分析[J]. 石油学报(石油加工),2015,31(1):7−17.
HU Yiwen,DA Zhijian,WANG Zijun. Thermodynamic analysis on the hydrogenation reaction of several aromatic hydrocarbons[J]. Acta Petrolei Sinica (Petroleum Processing Section),2015,31(1):7−17.
[49] BIE Shiquan,JIANG Hongbo,WANG Wei,et al. Kinetics of naphthalene catalytic hydrogenation under high temperature and high pressure[J]. Petroleum Science and Technology,2020,38(3):266−270.
[50] YANG Huibin,WANG Yachun,JIANG Hongbo,et al. Kinetics of phenanthrene hydrogenation system over CoMo/Al2O3 catalyst[J]. Industrial & Engineering Chemistry Research,2014,53(31):12264−12269.
[51] DAI Fei,GONG Maoming,LI Chunshan,et al. New kinetic model of coal tar hydrogenation process via carbon number component approach[J]. Applied Energy,2015,137:265−272.
[52] DANG Yu,YAO Yuan,LIU Yibin,et al. Diffusion properties of aromatic hydrocarbons in mesoporous alumina:A molecular dynamics study[J]. Chemical Engineering Science,2019,204:110−117.
Included in
Earth Sciences Commons, Mining Engineering Commons, Oil, Gas, and Energy Commons, Sustainability Commons