Reaction Kinetics, Mechanisms and Catalysis

, Volume 127, Issue 2, pp 961–978 | Cite as

Production of liquid fuels from low-temperature coal tar via hydrogenation over CoMo/USY catalysts

  • Jipeng Meng
  • Jiake Yang
  • Jie Fang
  • Na Li
  • Yang He
  • Huizi Huang
  • Jiangyin LuEmail author


In the present work, CoMo/USY catalysts with various Mo loading were prepared by ultrasonic-assisted incipient-wetness impregnation method and characterized by XRD, BET, SEM, TEM, EDX-Mapping, H2-TPR, NH3-TPD and Py-FTIR techniques. The catalytic performance was investigated for hydrogenation of low-temperature coal tar. The product distribution including gaseous and liquid hydrocarbon was determined. The total light oil (≤ 300 °C) yield was 90 wt% with gasoline fraction (≤ 180 °C) of 47 wt% and diesel fraction (180–300 °C) of 43 wt%. Sulfur and nitrogen contents of below 10 and 50 μg g−1 in gasoline fraction, < 20 and 100 μg g−1 in diesel fraction were achieved. The research octane number (RON) value of gasoline fraction can reach 87, and the cetane number of diesel fraction was 44. Moreover, the hydrocarbon group composition of gasoline and diesel fractions were analyzed. These results demonstrated that the raw coal tar could be upgraded through a fixed bed over the prepared CoMo/USY catalysts, and clean fuels from the hydrogenated product could be a wonderful blending oil for high quality fuels.


CoMo/USY catalyst Hydrogenation Low-temperature coal tar Gasoline Diesel 



Financial support from the National Natural Science Foundation of China (Grant No. 21163019) is gratefully acknowledged.

Supplementary material

11144_2019_1576_MOESM1_ESM.docx (3.5 mb)
Supplementary material 1 (DOCX 3591 kb)


  1. 1.
    Xie K, Li W, Zhao W (2010) Coal chemical industry and its sustainable development in China. Energy 35:4349–4355CrossRefGoogle Scholar
  2. 2.
    Li D, Niu M, Yang Z, Wang S, Fan Z, Feng X, Li W (2018) Effect of phosphorus modification on the coal tar hydrogenation activity of the Ni–Mo/γ-Al2O3 catalyst. Reac Kinet Mech Cat 125:271–286CrossRefGoogle Scholar
  3. 3.
    Li D, Cui W, Zhang X, Meng Q, Zhou Q, Ma B, Niu M, Li W (2017) Production of clean fuels by catalytic hydrotreating a low temperature coal tar distillate in a pilot-scale reactor. Energy Fuels 31:11495–11508CrossRefGoogle Scholar
  4. 4.
    Cui W, Li W, Gao R, Ma H, Li D, Niu M, Lei X (2017) Hydroprocessing of low-temperature coal tar for the production of clean fuel over fluorinated NiW/Al2O3-SiO2 catalyst. Energy Fuels 31:3768–3783CrossRefGoogle Scholar
  5. 5.
    Niu M, Sun X, Gao R, Li D, Cui W, Li W (2016) Effect of dephenolization on low-temperature coal tar hydrogenation to produce fuel oil. Energy Fuels 30:10215–10221CrossRefGoogle Scholar
  6. 6.
    Kusy J, Andel L, Safarova M, Vales J, Ciahotny K (2012) Hydrogenation process of the tar obtained from the pyrolisis of brown coal. Fuel 101:38–44CrossRefGoogle Scholar
  7. 7.
    Dai F, Gao M, Li C, Xiang S, Zhang S (2011) Detailed description of coal tar hydrogenation process using the kinetic lumping approach. Energy Fuels 25:4878–4885CrossRefGoogle Scholar
  8. 8.
    Kan T, Wang H, He H, Li C, Zhang S (2011) Experimental study on two-stage catalytic hydroprocessing of middle-temperature coal tar to clean liquid fuels. Fuel 90:3404–3409CrossRefGoogle Scholar
  9. 9.
    Kan T, Sun X, Wang H, Li C, Muhammad U (2012) Production of gasoline and diesel from coal tar via its catalytic hydrogenation in serial fixed beds. Energy Fuels 26:3604–3611CrossRefGoogle Scholar
  10. 10.
    Yuan Y, Li D, Zhang L, Zhu Y, Wang L, Li W (2016) Development, status, and prospects of coal tar hydrogenation technology. Energy Technol 4:1338–1348CrossRefGoogle Scholar
  11. 11.
    Wang R, Ci D, Cui X, Bai Y, Liu C, Kong D, Zhao S, Long Y, Guo X (2016) Pilot-plant study of upgrading of medium and low-temperature coal tar to clean liquid fuels. Fuel Process Technol 155:153–159CrossRefGoogle Scholar
  12. 12.
    Niu M, Sun X, Li D, Cui W, Zhang X, Bai X, Li W (2017) The hydrodeoxygenation, hydrogenation, hydrodealkylation and ring-opening reaction in the hydrotreating of low temperature coal tar over Ni–Mo/γ-Al2O3 catalyst. Reac Kinet Mech Cat 121:487–503CrossRefGoogle Scholar
  13. 13.
    Zheng J, Guo M, Song C (2008) Characterization of Pd catalysts supported on USY zeolites with different SiO2/Al2O3 ratios for the hydrogenation of naphthalene in the presence of benzothiophene. Fuel Process Technol 89:467–474CrossRefGoogle Scholar
  14. 14.
    Yasuda H, Sato T, Yoshimura Y (1999) Influence of the acidity of USY zeolite on the sulfur tolerance of Pd–Pt catalysts for aromatic hydrogenation. Catal Today 50:63–71CrossRefGoogle Scholar
  15. 15.
    Wang H, Jiao T, Li Z, Li C, Zhang S, Zhang J (2015) Study on palm oil hydrogenation for clean fuel over Ni-Mo-W/γ-Al2O3-ZSM-5 catalyst. Fuel Process Technol 139:91–99CrossRefGoogle Scholar
  16. 16.
    Gu Z, Chang N, Hou X, Wang J, Liu Z (2012) Experimental study on the coal tar hydrocracking process in supercritical solvents. Fuel 91:33–39CrossRefGoogle Scholar
  17. 17.
    Leckel D (2006) Catalytic hydroprocessing of coal-derived gasification residues to fuel blending stocks: effect of reaction variables and catalyst on hydrodeoxygenation (HDO), hydrodenitrogenation (HDN), and hydrodesulfurization (HDS). Energy Fuels 20:1761–1766CrossRefGoogle Scholar
  18. 18.
    Wang Y, Shen B, Li J, Feng B, Li X, Ren S, Guo Q (2014) Interaction of coupled titanium and phosphorous on USY to tune hydrodesulfurization of 4,6-DMDBT and FCC LCO over NiW catalyst. Fuel Process Technol 128:166–175CrossRefGoogle Scholar
  19. 19.
    Nuntang S, Prasassarakich P, Ngamcharussrivichai C (2008) Comparative study on adsorptive removal of thiophenic sulfurs over Y and USY zeolites. Ind Eng Chem Res 47:7405–7413CrossRefGoogle Scholar
  20. 20.
    Ding L, Zheng Y, Zhang Z, Ring Z, Chen J (2007) Hydrotreating of light cycle oil using WNi catalysts containing hydrothermally and chemically treated zeolite Y. Catal Today 125:229–238CrossRefGoogle Scholar
  21. 21.
    Bataille F, Lemberton JL, Pérot G, Leyrit P, Cseri T, Marchal N, Kasztelan S (2001) Sulfided Mo and CoMo supported on zeolite as hydrodesulfurization catalysts: transformation of dibenzothiophene and 4,6-dimethyldibenzothiophene. Appl Catal A 220:191–205CrossRefGoogle Scholar
  22. 22.
    Kunisada N, Choi KH, Korai Y, Mochida I, Nakano K (2004) Optimum coating of USY as a support component of NiMoS on alumina for deep HDS of gas oil. Appl Catal A 276:51–59CrossRefGoogle Scholar
  23. 23.
    Fan Y, Xiao H, Shi G, Liu H, Qian Y, Wang T, Gong G, Bao X (2011) Citric acid-assisted hydrothermal method for preparing NiW/USY-Al2O3 ultradeep hydrodesulfurization catalysts. J Catal 279:27–35CrossRefGoogle Scholar
  24. 24.
    Jabbarnezhad P, Haghighi M, Taghavinezhad P (2014) Sonochemical synthesis of NiMo/Al2O3-ZrO2 nanocatalyst: effect of sonication and zirconia loading on catalytic properties and performance in hydrodesulfurization reaction. Fuel Process Technol 126:392–401CrossRefGoogle Scholar
  25. 25.
    Lee JJ, Kim H, Moon SH (2003) Preparation of highly loaded, dispersed MoS2/Al2O3 catalysts for the deep hydrodesulfurization of dibenzothiophenes. Appl Catal B 41:171–180CrossRefGoogle Scholar
  26. 26.
    Li C, Hirabayashi D, Suzuki K (2009) A crucial role of O2− and O2 2− on mayenite structure for biomass tar steam reforming over Ni/Ca12Al14O33. Appl Catal B 88:351–360CrossRefGoogle Scholar
  27. 27.
    Vishwakarma SK, Sundaramurthy V, Dalai AK, Adjaye J (2007) Performances of Co−W/γ-Al2O3 catalysts on hydrotreatment of light gas oil derived from athabasca bitumen. Ind Eng Chem Res 46:4778–4786CrossRefGoogle Scholar
  28. 28.
    Wang H, Cao Y, Li D, Muhammad U, Li C, Li Z, Zhang S (2013) Catalytic hydrorefining of tar to liquid fuel over multi-metals (W-Mo-Ni) catalysts. J Renew Sustain Energy 5:053114CrossRefGoogle Scholar
  29. 29.
    Wang H, Dai F, Li Z, Li C (2015) Upgrading shale oil distillation to clean fuel by coupled hydrogenation and ring opening reaction of aromatics on W-Ni/γ-Al2O3 catalysts. Energy Fuels 29:4902–4910CrossRefGoogle Scholar
  30. 30.
    Meng J, Wang Z, Ma Y, Lu J (2017) Hydrocracking of low-temperature coal tar over NiMo/Beta-KIT-6 catalyst to produce gasoline oil. Fuel Process Technol 165:62–71CrossRefGoogle Scholar
  31. 31.
    Parkhomchuk EV, Lysikov AI, Okunev AG, Parunin PD, Semeikina VS, Ayupov AB, Trunova VA, Parmon VN (2013) Meso/macroporous CoMo alumina pellets for hydrotreating of heavy oil. Ind Eng Chem Res 52:17117–17125CrossRefGoogle Scholar
  32. 32.
    Wang X, Fang H, Zhao Z, Duan A, Xu C, Chen Z, Zhang M, Du P, Song S, Zheng P, Chi K (2015) Effect of promoters on the HDS activity of alumina-supported Co-Mo sulfide catalysts. RSC Adv 5:99706–99711CrossRefGoogle Scholar
  33. 33.
    Du P, Zheng P, Song S, Wang X, Zhang M, Chi K, Xu C, Duan A, Zhao Z (2016) Synthesis of a novel micro/mesoporous composite material Beta-FDU-12 and its hydro-upgrading performance for FCC gasoline. RSC Adv 6:1018–1026CrossRefGoogle Scholar
  34. 34.
    Kumaran GM, Garg S, Soni K, Prasad VVDN, Sharma LD, Dhar GM (2006) Catalytic functionalities of H-β-zeolite-supported molybdenum hydrotreating catalysts. Energy Fuels 20:1784–1790CrossRefGoogle Scholar
  35. 35.
    Zheng Q, Huo L, Li H, Mi S, Li X, Zhu X, Deng X, Shen B (2017) Exploring structural features of USY zeolite in the catalytic cracking of Jatropha curcas L. seed oil towards higher gasoline/diesel yield and lower CO2 emission. Fuel 202:563–571CrossRefGoogle Scholar
  36. 36.
    Sandoval Díaz LE, Aragon Quiroz JA, Ruíz Cardona YS, Domínguez Monterroza AR, Trujillo CA (2017) Fractal analysis at mesopore scale of modified USY zeolites by nitrogen adsorption: a classical thermodynamic approach. Microporous Mesoporous Mater 237:260–267CrossRefGoogle Scholar
  37. 37.
    Jia L, Sun X, Ye X, Zou C, Gu H, Huang Y, Niu G, Zhao D (2013) Core-shell composites of USY@Mesosilica: synthesis and application in cracking heavy molecules with high liquid yield. Microporous Mesoporous Mater 176:16–24CrossRefGoogle Scholar
  38. 38.
    Tu C, Li M, Li H, Chu Y, Liu F, Nie H, Li D (2016) Effects of sulfur compounds on the hydrogenation and isomerization of 1-hexene over a sulfided CoMo catalyst for hydrodesulfurization. RSC Adv 6:33177–33183CrossRefGoogle Scholar
  39. 39.
    Cid R, Neira J, Godoy J, Palacios JM, López Agudo A (1995) Thiophene hydrodesulfurization on sulfided nickel-exchanged USY zeolites. Effect of the pH of the catalyst preparation. Appl Catal A 125:169–183CrossRefGoogle Scholar
  40. 40.
    Niu L, Wei R, Jiang F, Zhou M, Liu C, Xiao G (2014) Selective hydrogenolysis of glycerol to 1,2-propanediol on the modified ultrastable Y-type zeolite dispersed copper catalyst. Reac Kinet Mech Cat 113:543–556CrossRefGoogle Scholar
  41. 41.
    Liu X, Jiang S, Lai W, Yi X, Yang L, Fang W (2017) Quantitative relationship model between support properties and dibenzothiophene hydrodesulfurization conversion over NiMo/Al2O3. Reac Kinet Mech Cat 121:673–687CrossRefGoogle Scholar
  42. 42.
    Ishutenko D, Mozhaev A, Salnikov V, Nikulshin P (2016) Selective hydrodesulfurization of model fluid catalytic cracking gasoline over sulfided Al2O3-supported Anderson heteropolyoxomolybdate-based catalysts. Reac Kinet Mech Cat 119:615–627CrossRefGoogle Scholar
  43. 43.
    Kokliukhin A, Nikulshina M, Sheldaisov-Meshcheryakov A, Mozhaev A, Nikulshin P (2018) CoMo hydrotreating catalysts supported on Al2O3, SiO2 and SBA-15 prepared from single Co2Mo10-heteropolyacid. In search of self-promotion effect. Catal Lett 148:2869–2879CrossRefGoogle Scholar
  44. 44.
    Liu X, Li X, Yan Z (2012) Facile route to prepare bimodal mesoporous γ-Al2O3 as support for highly active CoMo-based hydrodesulfurization catalyst. Appl Catal B 121:50–56CrossRefGoogle Scholar
  45. 45.
    Herrera JE, Balzano L, Borgna A, Alvarez WE, Resasco DE (2001) Relationship between the structure/composition of Co–Mo catalysts and their ability to produce single-walled carbon nanotubes by CO disproportionation. J Catal 204:129–145CrossRefGoogle Scholar
  46. 46.
    Rodríguez Castellón E, Jiménez López A, Eliche Quesada D (2008) Nickel and cobalt promoted tungsten and molybdenum sulfide mesoporous catalysts for hydrodesulfurization. Fuel 87:1195–1206CrossRefGoogle Scholar
  47. 47.
    Alibouri M, Ghoreishi SM, Aghabozorg HR (2009) Hydrodesulfurization of dibenzothiophene using CoMo/Al-HMS nanocatalyst synthesized by supercritical deposition. J Supercrit Fluids 49:239–248CrossRefGoogle Scholar
  48. 48.
    Wang A (2002) Hydrodesulfurization of dibenzothiophene over siliceous MCM-41-supported catalysts II. Sulfided Ni–Mo catalysts. J Catal 210:319–327CrossRefGoogle Scholar
  49. 49.
    Vakros J, Papadopoulou C, Lycourghiotis A, Kordulis C (2011) Hydrodesulfurization catalyst bodies with various Co and Mo profiles. Appl Catal A 399:211–220CrossRefGoogle Scholar
  50. 50.
    Chary KVR, Reddy KR, Kishan G, Niemantsverdriet JW, Mestl G (2004) Structure and catalytic properties of molybdenum oxide catalysts supported on zirconia. J Catal 226:283–291CrossRefGoogle Scholar
  51. 51.
    Maity SK, Rana MS, Srinivas BN, Bej SK, Murali Dhar G, Prasada Rao TSR (2000) Characterization and evaluation of ZrO2 supported hydrotreating catalysts. J Mol Catal A: Chem 153:121–127CrossRefGoogle Scholar
  52. 52.
    Wang T, Fan Y, Wang X, Chou L, Lin H (2015) Selectivity enhancement of CoMoS catalysts supported on tri-modal porous Al2O3 for the hydrodesulfurization of fluid catalytic cracking gasoline. Fuel 157:171–176CrossRefGoogle Scholar
  53. 53.
    Li X, Zhang H, Liu B, Zhu Q, Wang J, Li X (2016) Mo-promoted catalysts for supercritical n-decane cracking. Appl Therm Eng 102:1238–1240CrossRefGoogle Scholar
  54. 54.
    Sumbogo Murti SD, Choi K-H, Korai Y, Mochida I (2005) Performance of spent sulfide catalysts in hydrodesulfurization of straight run and nitrogen-removed gas oils. Appl Catal A 280:133–139CrossRefGoogle Scholar
  55. 55.
    Yin H, Zhou T, Liu Y, Chai Y, Liu C (2011) NiMo/Al2O3 catalyst containing nano-sized zeolite Y for deep hydrodesulfurization and hydrodenitrogenation of diesel. J Nat Gas Chem 20:441–448CrossRefGoogle Scholar
  56. 56.
    Egia B, Cambra JF, Arias PL, Güemez MB, Legarreta JA, Pawelec B, Fierro JLG (1998) Surface properties and hydrocracking activity of NiMo zeolite catalysts. Appl Catal A 169:37–53CrossRefGoogle Scholar
  57. 57.
    Zhang D, Duan A, Zhao Z, Xu C (2010) Synthesis, characterization, and catalytic performance of NiMo catalysts supported on hierarchically porous Beta-KIT-6 material in the hydrodesulfurization of dibenzothiophene. J Catal 274:273–286CrossRefGoogle Scholar
  58. 58.
    Wang T, Li J, Su Y, Wang C, Gao Y, Chou L, Yao W (2015) The tuning of pore structures and acidity for Zn/Al layered double hydroxides: the application on selective hydrodesulfurization for FCC gasoline. J Energy Chem 24:432–440CrossRefGoogle Scholar
  59. 59.
    Sullivan RF, Egan CJ, Langlois GE (1964) Hydrocracking of alkylbenzenes and polycyclic aromatic hydrocarbons on acidic catalysts. Evidence for cyclization of the side chains. J Catal 3:183–195CrossRefGoogle Scholar
  60. 60.
    Ho TC, Qiao L (2010) Competitive adsorption of nitrogen species in HDS: kinetic characterization of hydrogenation and hydrogenolysis sites. J Catal 269:291–301CrossRefGoogle Scholar
  61. 61.
    Du H, Fairbridge C, Yang H, Ring Z (2005) The chemistry of selective ring-opening catalysts. Appl Catal A 294:1–21CrossRefGoogle Scholar
  62. 62.
    Lee JW, Shim WG, Moon H (2004) Adsorption equilibrium and kinetics for capillary condensation of trichloroethylene on MCM-41 and MCM-48. Microporous Mesoporous Mater 73:109–119CrossRefGoogle Scholar
  63. 63.
    Corma A, González Alfaro V, Orchillés AV (2001) Decalin and tetralin as probe molecules for cracking and hydrotreating the light cycle oil. J Catal 200:34–44CrossRefGoogle Scholar
  64. 64.
    Tang W, Fang M, Wang H, Yu P, Wang Q, Luo Z (2014) Mild hydrotreatment of low temperature coal tar distillate: product composition. Chem Eng J 236:529–537CrossRefGoogle Scholar
  65. 65.
    Girgis MJ, Gates BC (1991) Reactivities, reaction networks, and kinetics in high-pressure catalytic hydroprocessing. Ind Eng Chem Res 30:2021–2058CrossRefGoogle Scholar
  66. 66.
    Korre SC, Klein MT, Quann RJ (1995) Polynuclear aromatic hydrocarbons hydrogenation. 1. Experimental reaction pathways and kinetics. Ind Eng Chem Res 34:101–117CrossRefGoogle Scholar
  67. 67.
    Li D, Li Z, Li W, Liu Q, Feng Z, Fan Z (2013) Hydrotreating of low temperature coal tar to produce clean liquid fuels. J Anal Appl Pyrol 100:245–252CrossRefGoogle Scholar

Copyright information

© Akadémiai Kiadó, Budapest, Hungary 2019

Authors and Affiliations

  1. 1.Key Laboratory of Oil and Gas Fine Chemicals, Ministry of Education, College of Chemistry and Chemical EngineeringXinjiang UniversityUrumqiChina

Personalised recommendations