RESEARCH ARTICLE

Highly selective catalytic hydrodeoxygenation of guaiacol to cyclohexane over Pt/TiO2 and NiMo/Al2O3 catalysts

  • Zhong HE ,
  • Xianqin WANG
Expand
  • Department of Chemical, Biological and Pharmaceutical Engineering, New Jersey Institute of Technology, Newark, NJ 07102, USA

Received date: 05 Apr 2014

Accepted date: 10 Apr 2014

Published date: 11 Oct 2014

Copyright

2014 Higher Education Press and Springer-Verlag Berlin Heidelberg

Abstract

Catalysts Pt/TiO2 and NiMo/Al2O3 are highly active and selective for the hydrodeoxygenation of guaiacol in a fixed bed reactor at 300 °C and 7.1 MPa, leading to the hydrogenation of aromatic ring, followed by demethylation and dehydroxylation to produce cyclohexane. For a complete hydrodeoxygenation of guaiacol, metal sites and acid sites are required. NiMo/Al2O3 and Pt/Al2O3 are more active and selective for cyclohexane formation as compared with Pt/TiO2 at 285 °C and 4 MPa. However, Pt/TiO2 is stable while the other two catalysts deactivate due to the nature and amount of coke formation during the reaction.

Cite this article

Zhong HE , Xianqin WANG . Highly selective catalytic hydrodeoxygenation of guaiacol to cyclohexane over Pt/TiO2 and NiMo/Al2O3 catalysts[J]. Frontiers of Chemical Science and Engineering, 2014 , 8(3) : 369 -377 . DOI: 10.1007/s11705-014-1435-9

Acknowledgment

This work was financially supported by Dr. Wang’s NJIT startup package. The authors thank Yong Pu for GC-MS analysis to clarify the product species, and Jinwen Liu, Zafar Iqbal, George Barnes and Yogesh Gandhi at NJIT for their help during experiments.
1
Kunkes E L, Simonetti D A, West R M, Serrano-Ruiz J C, Gärtner C A, Dumesic J A. Catalytic conversion of biomass to monofunctional hydrocarbons and targeted liquid-fuel classes. Science, 2008, 322(5900): 417–421

2
Furimsky E. Catalytic hydrodeoxygenation. Applied Catalysis A, General, 2000, 199(2): 147–190

3
Zhao C, He J, Lemonidou A A, Li X, Lercher J A. Aqueous-phase hydrodeoxygenation of bio-derived phenols to cycloalkanes. Journal of Catalysis, 2011, 280(1): 8–16

4
Laurent E, Delmon B. Study of the hydrodeoxygenation of carbonyl, carboxylic and guaiacyl groups over sulfided CoMo/γ-Al2O3 and NiMo/γ-Al2O3 catalyst. II. Influence of water, ammonia and hydrogen sulfide. Applied Catalysis A, General, 1994, 109(1): 97–115

5
Laurent E, Delmon B. Study of the hydrodeoxygenation of carbonyl, carboxylic and guaiacyl groups over sulfided CoMo/γ-Al2O3 and NiMo/γ-Al2O3 catalysts. I. Catalytic reaction schemes. Applied Catalysis A, General, 1994, 109(1): 77–96

6
Bui V N, Laurenti D, Delichère P, Geantet C. Hydrodeoxygenation of guaiacol. Applied Catalysis B: Environmental, 2011, 101(3–4): 246–255

7
Lin Y C, Li C L, Wan H P, Lee H T, Liu C F. Catalytic hydrodeoxygenation of guaiacol on Rh-based and sulfided CoMo and NiMo catalysts. Energy & Fuels, 2011, 25(3): 890–896

8
Centeno A, Laurent E, Delmon B. Influence of the support of CoMo sulfide catalysts and of the addition of potassium and platinum on the catalytic performances for the hydrodeoxygenation of carbonyl, carboxyl, and guaiacol-type molecules. Journal of Catalysis, 1995, 154(2): 288–298

9
Gutierrez A, Kaila R K, Honkela M L, Slioor R, Krause A O I. Hydrodeoxygenation of guaiacol on noble metal catalysts. Catalysis Today, 2009, 147(3–4): 239–246

10
Jongerius A L, Jastrzebski R, Bruijnincx P C A, Weckhuysen B M. CoMo sulfide-catalyzed hydrodeoxygenation of lignin model compounds: An extended reaction network for the conversion of monomeric and dimeric substrates. Journal of Catalysis, 2012, 285(1): 315–323

11
Şenol O İ, Ryymin E M, Viljava T R, Krause A O I. Effect of hydrogen sulphide on the hydrodeoxygenation of aromatic and aliphatic oxygenates on sulphided catalysts. Journal of Molecular Catalysis A Chemical, 2007, 277(1–2): 107–112

12
Şenol O İ, Viljava T R, Krause A O I. Effect of sulphiding agents on the hydrodeoxygenation of aliphatic esters on sulphided catalysts. Applied Catalysis A, General, 2007, 326(2): 236–244

13
Bridgwater A V. Catalysis in thermal biomass conversion. Applied Catalysis A, General, 1994, 116(1–2): 5–47

14
Zhao H Y, Li D, Bui P, Oyama S T. Hydrodeoxygenation of guaiacol as model compound for pyrolysis oil on transition metal phosphide hydroprocessing catalysts. Applied Catalysis A, General, 2011, 391(1–2): 305–310

15
González-Borja M A, Resasco D E. Anisole and guaiacol hydrodeoxygenation over monolithic Pt-Sn catalysts. Energy & Fuels, 2011, 25(9): 4155–4162

16
Filley J, Roth C. Vanadium catalyzed guaiacol deoxygenation. Journal of Molecular Catalysis A Chemical, 1999, 139(2–3): 245–252

17
Bykova M V, Bulavchenko O A, Ermakov D Y, Lebedev M Y, Yakovlev V A, Parmon V N. Guaiacol hydrodeoxygenation in the presence of Ni-containing catalysts. Catalysis in Industry, 2011, 3(1): 15–22

18
Ghampson I T, Sepúlveda C, Garcia R, Frederick B G, Wheeler M C, Escalona N, DeSisto W J. Guaiacol transformation over unsupported molybdenum-based nitride catalysts. Applied Catalysis A, General, 2012, 413–414(31): 78–84

19
Bykova M V, Ermakov D Y, Kaichev V V, Bulavchenko O A, Saraev A A, Lebedev M Y, Yakovlev V A. Ni-based sol-gel catalysts as promising systems for crude bio-oil upgrading: Guaiacol hydrodeoxygenation study. Applied Catalysis B: Environmental, 2012, 113–114: 296–307

20
He Z, Wang X. Hydrodeoxygenation of model compounds and catalytic systems for pyrolysis bio-oils upgrading. Catalysis for Sustainable Energy, 2012, 1: 28–52

21
He Z, Wang X. Required catalytic properties for alkane production from carboxylic acids: Hydrodeoxygenation of acetic acid. Journal of Energy Chemistry, 2013, 22(6): 883–894

22
Miller J T, Meyers B L, Modica F S, Lane G S, Vaarkamp M, Koningsberger D C. Hydrogen temperature-programmed desorption (H2 TPD) of supported platinum catalysts. Journal of Catalysis, 1993, 143(2): 395–408

23
Lee C R, Yoon J S, Suh Y W, Choi J W, Ha J M, Suh D J, Park Y K. Catalytic roles of metals and supports on hydrodeoxygenation of lignin monomer guaiacol. Catalysis Communications, 2012, 17: 54–58

24
Viljava T R, Saari E R M, Krause A O I. Simultaneous hydrodesulfurization and hydrodeoxygenation: Interactions between mercapto and methoxy groups present in the same or in separate molecules. Applied Catalysis A, General, 2001, 209(1–2): 33–43

25
Viljava T R, Komulainen R S, Krause A O I. Effect of H2S on the stability of CoMo/Al2O3 catalysts during hydrodeoxygenation. Catalysis Today, 2000, 60(1–2): 83–92

26
Hong Y K, Lee D W, Eom H J, Lee K Y. The catalytic activity of Pd/WOx/γ-Al2O3 for hydrodeoxygenation of guaiacol. Applied Catalysis B: Environmental, 2014, 150–151: 438–445

27
Hong D Y, Miller S J, Agrawal P K, Jones C W. Hydrodeoxygenation and coupling of aqueous phenolics over bifunctional zeolite-supported metal catalysts. Chemical Communications, 2010, 46(7): 1038–1040

28
Sepúlveda C, Leiva K, García R, Radovic L R, Ghampson I T, DeSisto W J, Fierro J L G, Escalona N. Hydrodeoxygenation of 2-methoxyphenol over Mo2N catalysts supported on activated carbons. Catalysis Today, 2011, 172(1): 232–239

29
Zhao C, Kou Y, Lemonidou A A, Li X, Lercher J A. Highly selective catalytic conversion of phenolic bio-oil to alkanes. Angewandte Chemie, 2009, 121(22): 4047–4050

30
Shin E J, Keane M A. Gas-phase hydrogenation/hydrogenolysis of phenol over supported nickel catalysts. Industrial & Engineering Chemistry Research, 2000, 39(4): 883–892

31
Zhu X, Lobban L L, Mallinson R G, Resasco D E. Bifunctional transalkylation and hydrodeoxygenation of anisole over a Pt/HBeta catalyst. Journal of Catalysis, 2011, 281(1): 21–29

32
Zhao C, Lercher J A. Upgrading pyrolysis oil over Ni/HZSM-5 by cascade reactions. Angewandte Chemie International Edition, 2012, 51(24): 5935–5940

33
Popov A, Kondratieva E, Goupil J M, Mariey L, Bazin P, Gilson J P, Travert A, Maugé F. Bio-oils hydrodeoxygenation: Adsorption of phenolic molecules on oxidic catalyst supports. Journal of Physical Chemistry C, 2010, 114(37): 15661–15670

34
Pestman R, Koster R M, Pieterse J A Z, Ponec V. Reactions of carboxylic acids on oxides: 1. Selective hydrogenation of acetic acid to acetaldehyde. Journal of Catalysis, 1997, 168(2): 255–264

35
Thibodeau T J, Canney A S, DeSisto W J, Wheeler M C, Amar F G, Frederick B G. Composition of tungsten oxide bronzes active for hydrodeoxygenation. Applied Catalysis A, General, 2010, 388(1–2): 86–95

36
He Z, Yang M, Wang X, Zhao Z, Duan A. Effect of the transition metal oxide supports on hydrogen production from bio-ethanol reforming. Catalysis Today, 2012, 194(1): 2–8

37
Mattos L V, Rodino E, Resasco D E, Passos F B, Noronha F B. Partial oxidation and CO2 reforming of methane on Pt/Al2O3, Pt/ZrO2, and Pt/Ce-ZrO2 catalysts. Fuel Processing Technology, 2003, 83(1–3): 147–161

38
Mortensen P M, Grunwaldt J D, Jensen P A, Knudsen K G, Jensen A D. A review of catalytic upgrading of bio-oil to engine fuels. Applied Catalysis A, General, 2011, 407(1–2): 1–19

39
Yang J, Chen M, Ren J. Effect of Mo, W addition on performance of Ni/Al2O3 catalyst for hydrodeoxygenation. Chemical Industry and Engineering Progress, 2005, 24(12): 1386–1389

40
Bui V N, Laurenti D, Delichère P, Geantet C. Hydrodeoxygenation of guaiacol. Part II: Support effect for CoMoS catalysts on HDO activity and selectivity. Applied Catalysis B: Environmental, 2011, 101(3–4): 246–255

41
Olcese R, Bettahar M M, Malaman B, Ghanbaja J, Tibavizco L, Petitjean D, Dufour A. Gas-phase hydrodeoxygenation of guaiacol over iron-based catalysts. Effect of gases composition, iron load and supports (silica and activated carbon). Applied Catalysis B: Environmental, 2013, 129: 528–538

42
Valle B, Castaño P, Olazar M, Bilbao J, Gayubo A G. Deactivating species in the transformation of crude bio-oil with methanol into hydrocarbons on a HZSM-5 catalyst. Journal of Catalysis, 2012, 285(1): 304–314

43
Ibáñez M, Valle B, Bilbao J, Gayubo A G, Castaño P. Effect of operating conditions on the coke nature and HZSM-5 catalysts deactivation in the transformation of crude bio-oil into hydrocarbons. Catalysis Today, 2012, 195(1): 106–113

44
Guo J, Lou H, Zheng X. The deposition of coke from methane on a Ni/MgAl2O4 catalyst. Carbon, 2007, 45(6): 1314–1321

Outlines

/