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Hydrodeoxygenation (HDO) of Bio-oil Model Compounds with Synthesis Gas Using a Water–Gas Shift Catalyst with a Mo/Co/K Catalyst

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Handbook of Climate Change Mitigation and Adaptation

Abstract

Bio-oil is a renewable and carbon-neutral energy source. It is made by the fast pyrolysis of biomass at elevated temperatures followed by condensation of vapors and aerosols that are removed rapidly from the pyrolysis chamber. Raw bio-oil contains significant amounts of oxygenated compounds which reduce its fuel quality. Upgrading raw bio-oil using hydrodeoxygenation (HDO) is one solution to increase fuel quality. Guaiacol and furfural are important model oxygen-containing compounds present in raw bio-oil. HDO of guaiacol and furfural with a dual Cu-based water–gas shift and Mo/Co/K HDO catalyst system in a static catalyst basket was studied in the gas phase in a batch autoclave using H2/CO at 4.0 MPa (total partial pressure of CO + H2) and temperatures of 200 °C, 250 °C, and 300 °C. Syngas HDO using two syngas mixtures (H2/CO/N2 ratios of 47:47:6 (50/50 syngas) and 18:23:46 (bio-syngas)) was compared to hydrogen alone, which is traditionally used in bio-oil upgrading. Liquid and gas products were analyzed using GC/MS. Temperature and catalyst both exert significant effects on conversion and product selectivity. Guaiacol conversions of 79–86 % were observed in both 50/50 syngas and bio-syngas systems at 300 °C, with 24–29 % cyclohexane formed in 4 h. Furfural exhibited ~100 % conversion in 4 h at 300 °C with both syngas systems. Reaction products from upgrading with syngases had a higher total heat of combustion but lower energy density than the products from reactions with pure H2. For example, 0.04 mol (4.96 g) of guaiacol has a total heat of combustion of 143.4 kJ with an energy density of 28.9 kJ/g (3.59 MJ/mol). Reaction products from upgrading the same amount of guaiacol with H2 had a total energy content and energy density of 146.6 ± 0.4 kJ and 38.8 ± 0.2 kJ/g (3.66 MJ/mol), respectively, compared to 153.6 ± 0.4 kJ and 35.8 ± 0.1 kJ/g (3.84 MJ/mol) for the product upgraded with bio-syngas. This, and product selectivity, suggests incorporation of some C from CO in these syngas reactions.

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References

  • Adjaye JD, Bakhshi NN (1995a) Catalytic conversion of a biomass-derived oil to fuels and chemicals I: model compound studies and reaction pathways. Biomass Bioenergy 8(3):131–149

    Article  Google Scholar 

  • Adjaye JD, Bakhshi NN (1995b) Production of hydrocarbons by catalytic upgrading of a fast pyrolysis bio-oil. Part I: conversion over various catalysts. Fuel Process Technol 45(3):161–183

    Article  Google Scholar 

  • Alonso DM, Bond JQ, Dumesic JA (2010) Catalytic conversion of biomass to biofuels. Green Chem 12(9):1493–1513

    Article  Google Scholar 

  • Ashworth AJ, Sadaka SS, Allen FL, Sharara MA, Keyser PD (2014) Influence of pyrolysis temperature and production conditions on switchgrass biochar for use as a soil amendment. BioResources 9(4):7622–7635, 14 pp

    Article  Google Scholar 

  • Boateng AA, Mullen CA, Goldberg N, Hicks KB, Jung H-JG, Lamb JFS (2008) Production of bio-oil from alfalfa stems by fluidized-bed fast pyrolysis. Ind Eng Chem Res 47(12):4115–4122

    Article  Google Scholar 

  • Bredenberg JBS, Huuska M, Räty J, Korpio M (1982) Hydrogenolysis and hydrocracking of the carbon-oxygen bond: I. Hydrocracking of some simple aromatic O-compounds. J Catal 77(1):242–247

    Article  Google Scholar 

  • Bridgwater AV (1994) Catalysis in thermal biomass conversion. Appl Catal Gen 116(1–2):5–47

    Article  Google Scholar 

  • Bridgwater AV (1996) Production of high grade fuels and chemicals from catalytic pyrolysis of biomass. Catal Today 29(1–4):285–295

    Article  Google Scholar 

  • Bridgwater AV (2003) Renewable fuels and chemicals by thermal processing of biomass. Chem Eng J 91(2–3):87–102

    Article  Google Scholar 

  • Bridgwater T (2006) Biomass for energy. J Sci Food Agric 86(12):1755–1768

    Article  Google Scholar 

  • Bridgwater AV, Peacocke GVC (1999) Fast pyrolysis processes for biomass. Renew Sustain Energy Rev 4(1):1–73

    Article  Google Scholar 

  • Bridgwater AV, Meier D, Radlein D (1999) An overview of fast pyrolysis of biomass. Org Geochem 30(12):1479–1493

    Article  Google Scholar 

  • Bridgwater AV, Czernik S, Piskorz J (2001) An overview of fast pyrolysis. Blackwell, Oxford, pp 977–997

    Google Scholar 

  • Bykova MV, Ermakov DY, Kaichev VV, Bulavchenko OA, Saraev AA, Lebedev MY, Yakovlev VА (2012) Ni-based sol–gel catalysts as promising systems for crude bio-oil upgrading: guaiacol hydrodeoxygenation study. Appl Catal Environ 113–114:296–307

    Article  Google Scholar 

  • Centeno A, Laurent E, Delmon B (1995) 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. J Catal 154(2):288–298

    Article  Google Scholar 

  • Czernik S, Bridgwater AV (2004) Overview of applications of biomass fast pyrolysis oil. Energy Fuel 18(2):590–598

    Article  Google Scholar 

  • de Miguel Mercader F, Groeneveld MJ, Kersten SRA, Way NWJ, Schaverien CJ, Hogendoorn JA (2010) Production of advanced biofuels: co-processing of upgraded pyrolysis oil in standard refinery units. Appl Catal Environ 96(1–2):57–66

    Article  Google Scholar 

  • Delgado J, Aznar MP, Corella J (1997) Biomass gasification with steam in fluidized bed: effectiveness of CaO, MgO, and CaO–MgO for hot raw gas cleaning. Ind Eng Chem Res 36(5):1535–1543

    Article  Google Scholar 

  • Elliott DC (2007) Historical developments in hydroprocessing bio-oils. Energy Fuel 21(3):1792–1815

    Article  Google Scholar 

  • Elliott DC, Hart TR, Neuenschwander GG, Rotness LJ, Zacher AH (2009) Catalytic hydroprocessing of biomass fast pyrolysis bio-oil to produce hydrocarbon products. Environ Prog Sustain Energy 28(3):441–449

    Article  Google Scholar 

  • Ferrari M, Maggi R, Delmon B, Grange P (2001) Influences of the hydrogen sulfide partial pressure and of a nitrogen compound on the hydrodeoxygenation activity of a CoMo/Carbon catalyst. J Catal 198(1):47–55

    Article  Google Scholar 

  • Ferrari M, Delmon B, Grange P (2002) Influence of the impregnation order of molybdenum and cobalt in carbon-supported catalysts for hydrodeoxygenation reactions. Carbon 40(4):497–511

    Article  Google Scholar 

  • Fisk CA, Morgan T, Ji Y, Crocker M, Crofcheck C, Lewis SA (2009) Bio-oil upgrading over platinum catalysts using in situ generated hydrogen. Appl Catal Gen 358(2):150–156

    Article  Google Scholar 

  • Furimsky E (2000) Catalytic hydrodeoxygenation. Appl Catal Gen 199(2):147–190

    Article  Google Scholar 

  • Grange P, Laurent E, Maggi R, Centeno A, Delmon B (1996) Hydrotreatment of pyrolysis oils from biomass: reactivity of the various categories of oxygenated compounds and preliminary techno-economical study. Catal Today 29(1–4):297–301

    Article  Google Scholar 

  • Huber GW, Corma A (2007) Synergies between bio- and oil refineries for the production of fuels from biomass. Angew Chem Int Ed 46(38):7184–7201

    Article  Google Scholar 

  • Huber GW, Chheda JN, Barrett CJ, Dumesic JA (2005) Production of liquid alkanes by aqueous-phase processing of biomass-derived carbohydrates. Science 308(5727):1446–1450

    Article  Google Scholar 

  • Huber GW, Iborra S, Corma A (2006) Synthesis of transportation fuels from biomass: chemistry, catalysts, and engineering. Chem Rev 106(9):4044–4098

    Article  Google Scholar 

  • Ingram L, Mohan D, Bricka M, Steele P, Strobel D, Crocker D, Mitchell B, Mohammad J, Cantrell K, Pittman CU Jr (2007) Pyrolysis of wood and bark in an auger reactor: physical properties and chemical analysis of the produced bio-oils. Energy Fuel 22(1):614–625

    Article  Google Scholar 

  • Kwon KC, Mayfield H, Marolla T, Nichols B, Mashburn M (2011) Catalytic deoxygenation of liquid biomass for hydrocarbon fuels. Renew Energy 36(3):907–915

    Article  Google Scholar 

  • Lange J-P (2007) Lignocellulose conversion: an introduction to chemistry, process and economics. Biofuels Bioprod Biorefin 1(1):39–48

    Article  Google Scholar 

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

    Article  Google Scholar 

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

    Article  Google Scholar 

  • Linstrom PJ, Mallard WG. NIST Chemistry WebBook, NIST standard reference database number 69. National Institute of Standards and Technology, Gaithersburg

    Google Scholar 

  • Liu S, Gujar AC, Thomas P, Toghiani H, White MG (2009) Synthesis of gasoline-range hydrocarbons over Mo/HZSM-5 catalysts. Appl Catal Gen 357(1):18–25

    Article  Google Scholar 

  • Mallat T, Baiker A (2000) Selectivity enhancement in heterogeneous catalysis induced by reaction modifiers. Appl Catal Gen 200(1–2):3–22

    Article  Google Scholar 

  • Massoth FE, Politzer P, Concha MC, Murray JS, Jakowski J, Simons J (2006) Catalytic hydro deoxygenation of methyl-substituted phenols: correlations of kinetic parameters with molecular properties. J Phys Chem B 110(29):14283–14291

    Article  Google Scholar 

  • Matos MAR, Miranda MS, Morais VMF (2003) Thermochemical study of the methoxy- and dimethoxyphenol isomers. J Chem Eng Data 48(3):669–679

    Article  Google Scholar 

  • McCall MJ, Brandvold TA, Elliott DC (2012) Fuel and fuel blending components from biomass derived pyrolysis oil. Google Patents

    Google Scholar 

  • Modak A, Deb A, Patra T, Rana S, Maity S, Maiti D (2012) A general and efficient aldehyde decarbonylation reaction by using a palladium catalyst. Chem Commun 48(35):4253–4255

    Article  Google Scholar 

  • Mohan D, Pittman CU Jr, Steele PH (2006) Pyrolysis of wood/biomass for bio-oil: a critical review. Energy Fuel 20(3):848–889

    Article  Google Scholar 

  • Mullen CA, Boateng AA (2008) Chemical composition of bio-oils produced by fast pyrolysis of two energy crops. Energy Fuel 22(3):2104–2109

    Article  Google Scholar 

  • Nimmanwudipong T, Runnebaum R, Block D, Gates B (2011) Catalytic reactions of guaiacol: reaction network and evidence of oxygen removal in reactions with hydrogen. Catal Lett 141(6):779–783

    Article  Google Scholar 

  • Patt J, Moon D, Phillips C, Thompson L (2000) Molybdenum carbide catalysts for water–gas shift. Catal Lett 65(4):193–195

    Article  Google Scholar 

  • Romero Y, Richard F, Brunet S (2010) Hydrodeoxygenation of 2-ethylphenol as a model compound of bio-crude over sulfided Mo-based catalysts: promoting effect and reaction mechanism. Appl Catal Environ 98(3–4):213–223

    Article  Google Scholar 

  • Shafiee S, Topal E (2009) When will fossil fuel reserves be diminished? Energy Policy 37(1):181–189

    Article  Google Scholar 

  • Shen ZL, Jiang XZ, Mo WM, Hu BX, Sun N (2005) Catalytic O-methylation of phenols with dimethyl carbonate to aryl methyl ethers using [BMIm]Cl. Green Chem 7(2):97–99

    Article  Google Scholar 

  • Stöcker M (2008) Biofuels and biomass-to-liquid fuels in the biorefinery: catalytic conversion of lignocellulosic biomass using porous materials. Angew Chem Int Ed 47(48):9200–9211

    Article  Google Scholar 

  • Sun Y, Hla SS, Duffy GJ, Cousins AJ, French D, Morpeth LD, Edwards JH, Roberts DG (2010) High temperature water–gas shift Cu catalysts supported on Ce–Al containing materials for the production of hydrogen using simulated coal-derived syngas. Catal Commun 12(4):304–309

    Article  Google Scholar 

  • van Steen E, Claeys M (2008) Fischer-tropsch catalysts for the biomass-to-liquid (BTL)-process. Chem Eng Technol 31(5):655–666

    Article  Google Scholar 

  • Vargas A, Bürgi T, Baiker A (2004) Adsorption of activated ketones on platinum and their reactivity to hydrogenation: a DFT study. J Catal 222(2):439–449

    Article  Google Scholar 

  • Venderbosch RH, Prins W (2010) Fast pyrolysis technology development. Biofuels Bioprod Biorefin 4(2):178–208

    Article  Google Scholar 

  • Venderbosch RH, Ardiyanti AR, Wildschut J, Oasmaa A, Heeres HJ (2010) Stabilization of biomass-derived pyrolysis oils. J Chem Technol Biotechnol 85(5):674–686

    Article  Google Scholar 

  • Wijayapala R, Yu F, Pittman CU Jr, Mlsna TE (2014) K-promoted Mo/Co- and Mo/Ni-catalyzed Fischer–Tropsch synthesis of aromatic hydrocarbons with and without a Cu water gas shift catalyst. Appl Catal Gen 480:93–99

    Article  Google Scholar 

  • Wildschut J, Mahfud FH, Venderbosch RH, Heeres HJ (2009) Hydrotreatment of fast pyrolysis oil using heterogeneous noble-metal catalysts. Ind Eng Chem Res 48(23):10324–10334

    Article  Google Scholar 

  • Williams PT, Besler S (1996) The influence of temperature and heating rate on the slow pyrolysis of biomass. Renew Energy 7(3):233–250

    Article  Google Scholar 

  • Yakovlev VA, Khromova SA, Sherstyuk OV, Dundich VO, Ermakov DY, Novopashina VM, Lebedev MY, Bulavchenko O, Parmon VN (2009) Development of new catalytic systems for upgraded bio-fuels production from bio-crude-oil and biodiesel. Catal Today 144(3–4):362–366

    Article  Google Scholar 

  • Zhang Q, Chang J, Wang TJ, Xu Y (2006) Upgrading bio-oil over different solid catalysts. Energy Fuel 20(6):2717–2720

    Article  Google Scholar 

  • Zhang J, Toghiani H, Mohan D, Pittman CU Jr, Toghiani RK (2007) Product analysis and thermodynamic simulations from the pyrolysis of several biomass feedstocks. Energy Fuel 21(4):2373–2385

    Article  Google Scholar 

  • Zhao C, Kou Y, Lemonidou AA, Li X, Lercher JA (2009) Highly selective catalytic conversion of phenolic bio-oil to alkanes. Angew Chem 121(22):4047–4050

    Article  Google Scholar 

Download references

Acknowledgments

This material is based upon work performed through the Sustainable Energy Research Center at Mississippi State University and is supported by the US Department of Energy under award DE-FG3606GO86025 and US Department of Agriculture under award AB567370MSU.

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Authors and Affiliations

  1. Department of Chemistry, Mississippi State University, Starkville, MS, 39762, USA

    Rangana Wijayapala, Akila G. Karunanayake, Damion Proctor, Charles U. Pittman & Todd E. Mlsna

  2. Agricultural and Biological Engineering, Mississippi State University, Starkville, MS, 39762, USA

    Fei Yu

Authors
  1. Rangana Wijayapala
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  2. Akila G. Karunanayake
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  3. Damion Proctor
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  4. Fei Yu
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  5. Charles U. Pittman
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  6. Todd E. Mlsna
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Correspondence to Todd E. Mlsna .

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Editors and Affiliations

  1. University of Mississippi Dept. Chemical Engineering, University, Mississippi, USA

    Wei-Yin Chen

  2. Advanced Manufacturing Research Inst. Functional Assembly Technology Group, National Institute of Advanced Industrial Science & Technology (AIST), Nagoya, Japan

    Toshio Suzuki

  3. und Technische Biowissenschaften, TU Wien Inst. Verfahrenstechnik, Umwelttechnik, Wien, Austria

    Maximilian Lackner

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Wijayapala, R., Karunanayake, A.G., Proctor, D., Yu, F., Pittman, C.U., Mlsna, T.E. (2015). Hydrodeoxygenation (HDO) of Bio-oil Model Compounds with Synthesis Gas Using a Water–Gas Shift Catalyst with a Mo/Co/K Catalyst. In: Chen, WY., Suzuki, T., Lackner, M. (eds) Handbook of Climate Change Mitigation and Adaptation. Springer, New York, NY. https://doi.org/10.1007/978-1-4614-6431-0_79-1

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  • DOI: https://doi.org/10.1007/978-1-4614-6431-0_79-1

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