Hydrothermal liquefaction

Hydrothermal liquefaction (HTL) is a thermal depolymerization process used to convert wet biomass into crude-like oil -sometimes referred to as bio-oil or biocrude- under moderate temperature and high pressure.[1] The crude-like oil (or bio-oil) has high energy density with a lower heating value of 33.8-36.9 MJ/kg and 5-20 wt% oxygen and renewable chemicals.[2][3]

The reaction usually involves homogeneous and/or heterogeneous catalysts to improve the quality of products and yields.[1] Carbon and hydrogen of an organic material, such as biomass, peat or low-ranked coals (lignite) are thermo-chemically converted into hydrophobic compounds with low viscosity and high solubility. Depending on the processing conditions, the fuel can be used as produced for heavy engines, including marine and rail or upgraded to transportation fuels,[4] such as diesel, gasoline or jet-fuels.

History

As early as the 1920s, the concept of using hot water and alkali catalysts to produce oil out of biomass was proposed.[5] This was the foundation of later HTL technologies that attracted research interest especially during the 1970s oil embargo. It was around that time that a high-pressure (hydrothermal) liquefaction process was developed at the Pittsburgh Energy Research Center (PERC) and later demonstrated (at the 100 kg/h scale) at the Albany Biomass Liquefaction Experimental Facility at Albany, Oregon, US.[2][6] In 1982, Shell Oil developed the HTU™ process in the Netherlands.[6] Other organizations that have previously demonstrated HTL of biomass include Hochschule für Angewandte Wissenschaften Hamburg, Germany, SCF Technologies in Copenhagen, Denmark, EPA’s Water Engineering Research Laboratory, Cincinnati, Ohio, USA, and Changing World Technology Inc. (CWT), Philadelphia, Pennsylvania, USA.[6] Today, technology companies such as Licella/Ignite Energy Resources (Australia), Altaca Energy (Turkey), Bio2Oil ApS (Denmark), Steeper Energy (Denmark, Canada), and Nabros Energy (India) continue to explore the commercialization of HTL.[7]

Chemical reactions

In hydrothermal liquefaction processes, long carbon chain molecules in biomass are thermally cracked and oxygen is removed in the form of H2O (dehydration) and CO2 (decarboxylation). These reactions result in the production of high H/C ratio bio-oil. Simplified descriptions of dehydration and decarboxylation reactions can be found in the literature (e.g. Asghari and Yoshida (2006)[8] and Snåre et al. (2007)[9])

Process

Most applications of hydrothermal liquefaction operate at temperatures between 250-550 °C and high pressures of 5-25 MPa as well as catalysts for 20–60 minutes,[2][3] although higher or lower temperatures can be used to optimize gas or liquid yields, respectively.[6] At these temperatures and pressures, the water present in the biomass becomes either subcritical or supercritical, depending on the conditions, and acts as a solvent, reactant, and catalyst to facilitate the reaction of biomass to bio-oil.

The exact conversion of biomass to bio-oil is dependent on several variables:[1]

  • Feedstock composition
  • Temperature and heating rate
  • Pressure
  • Solvent
  • Residence time
  • Catalysts

Feedstock

Theoretically, any biomass can be converted into bio-oil using hydrothermal liquefaction regardless of water content, and various different biomasses have been tested, from forestry and agriculture residues,[10] sewage sludges, food process wastes, to emerging non-food biomass such as algae.[1][5][6] The composition of cellulose, hemicellulose, protein, and lignin in the feedstock influence the yield and quality of the oil from the process.

Temperature and Heating Rate

Temperature plays a major role in the conversion of biomass to bio-oil. The temperature of the reaction determines the depolymerization of the biomass to bio-oil, as well as the repolymerization into char.[1] While the ideal reaction temperature is dependent on the feedstock used, temperatures above ideal lead to an increase in char formation and eventually increased gas formation, while lower than ideal temperatures reduce depolymerization and overall product yields.

Similarly to temperature, the rate of heating plays a critical role in the production of the different phase streams, due to the prevalence of secondary reactions at non-optimum heating rates.[1] Secondary reactions become dominant in heating rates that are too low, leading to the formation of char. While high heating rates are required to form liquid bio-oil, there is a threshold heating rate and temperature where liquid production is inhibited and gas production is favored in secondary reactions.

Pressure

Pressure (along with temperature) determines the super- or subcritical state of solvents as well as overall reaction kinetics and the energy inputs required to yield the desirable HTL products (oil, gas, chemicals, char etc.).[1]

Residence Time

Hydrothermal liquefaction is a fast process, resulting in low residence times for depolymerization to occur. Typical residence times are measured in minutes (15 to 60 minutes); however, the residence time is highly dependent on the reaction conditions, including feedstock, solvent ratio and temperature. As such, optimization of the residence time is necessary to ensure a complete depolymerization without allowing further reactions to occur.[1]

Catalysts

While water acts as a catalyst in the reaction, other catalysts can be added to the reaction vessel to optimize the conversion.[11] Previously used catalysts include water-soluble inorganic compounds and salts, including KOH and Na2CO3, as well as transition metal catalysts using Ni, Pd, Pt, and Ru supported on either carbon, silica or alumina. The addition of these catalysts can lead to an oil yield increase of 20% or greater, due to the catalysts converting the protein, cellulose, and hemicellulose into oil. This ability for catalysts to convert biomaterials other than fats and oils to bio-oil allows for a wider range of feedstock to be used.

Environmental Impact

Biofuels that are produced through hydrothermal liquefaction are carbon neutral, meaning that there are no net carbon emissions produced when burning the biofuel. The plant materials used to produce bio-oils use photosynthesis to grow, and as such consume carbon dioxide from the atmosphere. The burning of the biofuels produced releases carbon dioxide into the atmosphere, but is nearly completely offset by the carbon dioxide consumed from growing the plants, resulting in a release of only 15-18 g of CO2 per kWh of energy produced. This is substantially lower than the releases rate of fossil fuel technologies, which can range from releases of 955 g/kWh (coal), 813 g/kWh (oil), and 446 g/kWh (natural gas).[1] Recently, Steeper Energy announced that the Carbon Intensity (CI) of its Hydrofaction™ oil is 15 CO2eq/MJ according to GHGenius model (version 4.03a), while diesel fuel is 93.55 CO2eq/MJ.[12]

Hydrothermal liquefaction is a clean process that doesn't produce harmful compounds, such as ammonia, NOx, or SOx.[1] Instead the heteroatoms, including nitrogen, sulfur, and chlorine, are converted into harmless byproducts such as N2 and inorganic acids that can be neutralized with bases.

Compare with Pyrolysis and other BtL technologies

The HTL process differs from pyrolysis as it can process wet biomass and produce a bio-oil that contains approximately twice the energy density of pyrolysis oil. Pyrolysis is a related process to HTL, but biomass must be processed and dried in order to increase the yield.[13] The presence of water in pyrolysis drastically increases the heat of vaporization of the organic material, increasing the energy required to decompose the biomass. Typical pyrolysis processes require a water content of less than 40% to suitably convert the biomass to bio-oil. This requires considerable pretreatment of wet biomass such as tropical grasses, which contain a water content as high as 80-85%, and even further treatment for aquatic species, which can contain higher than 90% water content.[1]

The HTL oil can contain up to 80% of the feedstock carbon content (single pass).[14] HTL oil has good potential to yield bio-oil with "drop-in" properties that can be directly distributed in existing petroleum infrastructure.[14][15]

See also

References
  1. Akhtar, Javaid; Amin, Nor Aishah Saidina (2011-04-01). "A review on process conditions for optimum bio-oil yield in hydrothermal liquefaction of biomass". Renewable and Sustainable Energy Reviews. 15 (3): 1615–1624. doi:10.1016/j.rser.2010.11.054.
  2. Elliott, Douglas C. (2007-05-01). "Historical Developments in Hydroprocessing Bio-oils". Energy & Fuels. 21 (3): 1792–1815. doi:10.1021/ef070044u. ISSN 0887-0624.
  3. Goudriaan, F.; Peferoen, D.G.R. (1990-01-01). "Liquid fuels from biomass via a hydrothermal process". Chemical Engineering Science. 45 (8): 2729–2734. doi:10.1016/0009-2509(90)80164-a.
  4. Ramirez, Jerome; Brown, Richard; Rainey, Thomas (1 July 2015). "A Review of Hydrothermal Liquefaction Bio-Crude Properties and Prospects for Upgrading to Transportation Fuels". Energies. 8 (7): 6765. doi:10.3390/en8076765.
  5. Berl, E. (1944-04-21). "Production of Oil from Plant Material". Science. 99 (2573): 309–312. Bibcode:1944Sci....99..309B. doi:10.1126/science.99.2573.309. ISSN 0036-8075. PMID 17737216.
  6. Toor, Saqib Sohail; Rosendahl, Lasse; Rudolf, Andreas (May 2011). "Hydrothermal liquefaction of biomass: A review of subcritical water technologies". Energy. 36 (5): 2328–2342. doi:10.1016/j.energy.2011.03.013.
  7. Sergios Karatzos; James D. McMillan; Jack N. Saddler (July 2014). "The Potential and Challenges of Drop-in Biofuels" (PDF). A report by IEA Bioenergy Task 39. Retrieved 3 Sep 2015.
  8. Asghari, Feridoun Salak; Yoshida, Hiroyuki (2006-10-16). "Dehydration of fructose to 5-hydroxymethylfurfural in sub-critical water over heterogeneous zirconium phosphate catalysts". Carbohydrate Research. 341 (14): 2379–2387. doi:10.1016/j.carres.2006.06.025. PMID 16870164.
  9. Snåre, M.; Kubičková, I.; Mäki-Arvela, P.; Eränen, K.; Wärnå, J.; Murzin, D. Yu. (2007-11-01). "Production of diesel fuel from renewable feeds: Kinetics of ethyl stearate decarboxylation". Chemical Engineering Journal. Proceedings of the XVII International Conference on Chemical Reactors CHEMREACTOR-17 and Post-Symposium "Catalytic Processing of Renewable Sources: Fuel, Energy, Chemicals"CR-17 Special IssueProf. Alexander S. Noskov. 134 (1–3): 29–34. doi:10.1016/j.cej.2007.03.064.
  10. Kosinkova, Jana; Ramirez, Jerome; Jablonsky, Michal; Ristovski, Zoran; Brown, Richard; Rainey, Thomas (24 May 2017). "Energy and chemical conversion of five Australian lignocellulosic feedstocks into bio-crude through liquefaction". RSC Advances. 7 (44): 27707–27717. doi:10.1039/C7RA02335A.
  11. Duan, Peigao; Savage, Phillip E. (2011). "Hydrothermal Liquefaction of a Microalga with Heterogeneous Catalysts". Industrial & Engineering Chemistry Research. 50: 52–61. doi:10.1021/ie100758s.
  12. Steeper Energy (2015). "Milestones & Activities". Retrieved 3 Sep 2015.
  13. Bridgwater, A.V; Peacocke, G.V.C (March 2000). "Fast pyrolysis processes for biomass". Renewable and Sustainable Energy Reviews. 4: 1–73. doi:10.1016/s1364-0321(99)00007-6.
  14. Toor, Saqib Sohail; Rosendahl, Lasse; Rudolf, Andreas (2011-05-01). "Hydrothermal liquefaction of biomass: A review of subcritical water technologies". Energy. 36 (5): 2328–2342. doi:10.1016/j.energy.2011.03.013.
  15. AARHUS UNIVERSITY (6 Feb 2013). "Hydrothermal liquefaction -- the most promising path to a sustainable bio-oil production". Retrieved 3 Sep 2015 – via http://www.eurekalert.org/.
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