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. 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.
The reaction usually involves homogeneous and/or heterogeneous catalysts to improve the
quality of products and yields. 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, such as diesel, gasoline or jet-fuels.

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) and Snre et al. (2007))

Process
Most applications of hydrothermal liquefaction operate at temperatures between 250-550oC
and high pressures of 5-25 MPa as well as catalysts for 2060 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, sewage sludges, food process wasters, to emerging non-food

biomass such as algae. 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. 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. 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.).
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 depolymerizaiton without allowing further reactions to
occur.
Catalysts

While water acts as a catalyst in the reaction, other catalysts can be added to the reaction
vessel to optimize the conversion. 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 [citation needed].

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/kWh or 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). 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.
Hydrothermal liquefaction is a clean process that doesn't produce harmful compounds, such
as ammonia, NOx, or SOx. 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. 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.
The HTL oil can contain up to 80% of the feedstock carbon content (single pass). HTL oil has
good potential to yield bio-oil with "drop-in" properties that can be directly distributed in
existing petroleum infrastructure.

Direction Liquefaction of Biomass

Figure 8.2 shows a graphic of the three methods of thermochemical conversion of biomass,
with direct liquefaction highlighted (the fourth is combustion, not really a thermochemical
conversion of biomass).

Figure 8.2: Next thermochemical method direct liquefaction.

Credit: Dr. Caroline B. Clifford

There are differences for each of the thermal processes, as described in Lesson 5. Here we
focus on direct liquefaction. Direct liquefaction (particularly hydrothermal processing) occurs
in a non-oxidative atmosphere, where the biomass is fed into a unit as aqueous slurry at lower
temperatures, with bio-crude in liquid form being the product. The primary focus of these
particular processes is to produce a liquid product that is a hydrocarbon with atomic H:C ratio
of ~2, and a boiling range of 170-280 C.
Many of the processes developed are based on coal-to-liquids processing. The main purposes
in taking coal and biomass into a liquid is to produce liquids, to remove some of the less
desirable components (i.e., sulfur, oxygen, nitrogen, minerals), and to make a higher energy
density material that will flow.
One of the primary processes to convert coal into liquids directly is through a combination of
thermal decomposition and hydrogenation under pressure. There are several single and twostage processes that have been developed, but have not been made commercial in the US.
However, China opened a commercial direct liquefaction plant partially based on US designs
in 2008. Figure 8.3a shows the general schematic of the plant as well as the products they
make in Figure 8.3b. Design considerations include: 1) temperatures of ~400-450C, 2)
hydrogenation catalysts, 3) hydrocarbon solvents that are similar to fuels, 4) naturally
occurring aromatics in coal, 5) sulfur, nitrogen, minerals that must be removed in refining of
the liquid. Biomass can be processed in a similar manner, but biomass has significantly more
oxygen and less aromatic compounds, and decomposes differently than coal. Other processes
have been developed for biomass, that appear to do a better job of processing cellulose. One
process is hydrothermal processing in pressurized water using an acid catalyst such as LaCl3
at 250C - we won't go into more detail here, but it is different from the direct liquefaction
discussion in the next paragraph.

Figure 8.3a: Direct coal liquefaction schematic from Shenhua plant in China.
Credit: Cornerstone (link is external)

Figure 8.3b: Intermediates and final products from Shenhua plant the two on the right (Hydro-upgraded Diesel and Hydroupgraded Naphtha) are the final products.
Credit: Cornerstone (link is external)

So, what are the differences with direct liquefaction of biomass? On the surface it looks
pretty much the same as the process for coal liquefaction. It is a thermochemical conversion
process of organic material into liquid bio-crude and co-products. Depending on the process,
it is usually conducted under moderate temperatures (300-400C, lower than coal
liquefaction) and pressures (10-20 MPa, similar or maybe a little higher with primarily
hydrogen in coal to liquids) with added hydrogen or CO as a reducing agent. Unlike coal, the
biomass is wet, or at least wetter than coal, and can be processed as an aqueous slurry.
When processed as an aqueous slurry, the process is referred to in the literature as
hydrothermal processing and can be subcritical to supercritical for water. Figure 8.4 shows
the conditions for supercritical water; water behaves more like an acid/base system under
these conditions. Thus, it can also be a catalyst. There is also high solubility of organic
material in water under these conditions. This mainly occurs along the liquid/vapor line. The
basic reaction mechanisms can be described as:
1. depolymerization of biomass;
2. decomposition of biomass monomers by cleavage, dehydration,
decarboxylation, and deamination;
3. recombination of reactive fragments.

Diffrent types of biomasses react differently depending on the biomass source.

Carbohydrates, such as cellulose, hemicellulose, and starch can decompose in hydrothermal
water. The typical product formed under these conditions is glucose, and glucose can then be
fermented to make alcohols or further degrade in water to make glycoaldehyde,
glyceraldehyde, and dihydroxyacetone. The products made depend on the conditions: at
temperatures ~180C, products are sugar monomers, but at higher temperatures, 360-420C,
the aldehyde and acetone compounds are formed.

Figure 8.4: Conditions for water to be supercritical and subcritical on phase

diagram.
Credit: DOI: 10.1016/j.energy.2011.03.013

Lignin and fatty acids also decompose in hydrothermal water, but the products are very
different because the substrate is different. For lignin, the products are similar to the building
blocks for lignin, as shown in Figure 5.20a of Lesson 5 (p-coumaryl, coniferyl and sinapyl
alcohols), although the functional groups vary depending on the hydrothermal conditions.
Bembenic and Clifford used hydrothermal water at 365C and ~13 MPa to form methoxy
phenols, using different gases to change the product slate (hydrogen, carbon monoxide,
carbon dioxide, and nitrogen). For lipid or triglyceride (fats and oils) reaction in
hydrothermal water at 330-340C and 13.1 MPa, the main products are the free fatty acids
(HC COOH) and glycerol (C3H8O3). The free fatty acids can then be reacted to straightchain hydrocarbons that can be used for diesel or jet fuel, although the temperature usually
needs to be a little higher (400C) for this to take place. Figure 8.5 shows the schematic of a
hydrothermal water process to convert algae into liquid fuels, making use of heat from an
integrated heat and power system. Flue gas from a power generation facility is used to grow
algae. Algae is then harvested and concentrated in water. The algae is then reacted in a
hydrothermal unit followed by catalytic hydrogenation to make the straight chain
hydrocarbon liquid fuels.

Figure 8.5: Schematic for hydrothermal liquefaction of algae for production of liquid fuels (diesel, jet fuel).
Credit: USDE OSTI (link is external)

Many types of catalysts can be used, although it depends on the process stage which catalysts
are used and what feed material is used. In hydrothermal processing, the more common
catalysts used are acid and base catalysts. Particle size for biomass needs to be fine, with a
size of < 0.5 mm. Introduction of the feed into the reactor is also challenging, as it is fed into
a high-pressure reactor. Some advantages of using this process for biomass: 1) it is possible to
process feeds with high water content, as much as 90%, 2) it is possible to process many
different types of waste materials, including MSW, food processing waste, and animal
manure, and 3) the process serves the dual roles of waste treatment and renewable energy
production.
Process parameters include solids content, temperature, pressure, residence time, and use of
catalysts. Often simultaneous reactions are taking place, which makes the overall
understanding of the reactions complicated. The types of reactions taking place include:
solubilization, depolymerizaton, decarboxylation, hydrogenation, condensation, and
hydrogenolysis.
For one particular process, hydrothermal liquefaction requires the use of catalyst. One typical
catalyst used is sodium carbonate combined with water and CO to produce sodium formate:

Na2CO3+H2O + CO2HCO2Na + CO2

This dehydrates the hydroxyl groups to carbonyl compounds, then reduces the carbonyl
group to an alcohol:

HCO2Na + C6H10O5C6H10H4+NaHCO3H2+C6H10O5C6H10H4+H2O
The formate and hydrogen can be regenerated and recycled. Other catalysts used that behave
in a similar manner include K2CO3, KOH, NaOH, and other bases. For simultaneous
decomposition and hydrogenation, nickel (Ni) catalysts are used.
Similar to pyrolysis, the major product of this process is a liquid biocrude, which is a viscous
dark tar or asphalt material. Up to 70% of the carbon is converted into biocrude; lighter
products are obtained when different catalysts are used. Co-products include gases (CO2,
CH4, and light hydrocarbons) as well as water-soluble materials. The liquid biofuel has a
similar carbon to hydrogen ratio as in the original feedstock and is a complex mixture of
aromatics, aromatic oligomers, and other hydrocarbons. In this process, the oxygen is reduced
and is 10-20% less than typical pyrolysis oils, with a heating value higher than pyrolysis oils,
35-40 MJ/kg on a dry basis. However, the USDA has developed a pyrolysis process using
recycled gases that produces a fairly light hydrocarbon with very little oxygen content.
(Mullens et al.) I will discuss this more in the next section. Table 8.2 shows a comparison of
biocrudes from various processes and feed materials. The quality of the biocrude shown from
hydrothermal processing is for a heavy biocrude. Other processes will make a lighter
material, but also produce more co-products that must be utilized as well.

Table 8.2: Comparison of biocrude from hydrothermal processing, biooil from fast
pyrolysis, and heavy petroleum fuel.
Characteristic

Hydrothermal
Bio-oil

Fast
pyrolysis
Bio-oil

Water Content, wt
%

3-5

15-25

0.1

4.8

Insoluble solids, %

0.5-0.8

0.01

n/a

30

17

40

34.0

Density, g/ml

1.10

1.23

0.94

n/a

Viscosity, cp

3,000-17,000

10-150

180

n/a

HHV, MJ/kg

Heavy Petroleum USDA Oil

Fuel
Oak

Wet

Dry

Wet

Dry

73.0

77.0

39.5

55.8

85.2

80.2

8.0

7.8

7.5

6.1

11.1

5.9

Oxygen, %

16.0

13.0

52.6

37.9

1.0

11.8

Nitrogen, %

<0.1

<0.1

<0.1

<0.1

0.3

2.1

Sulfur, %

<0.05

<0.5

<0.05 <0.5

2.3

n/a

Ash, %

0.3-0.5 0.3-0.5 0.3-0.5

<0.1

n/a

Carbon, %
Hydrogen, %

0.20.3

BEEMS Module, He, Hu, and Li. Mullens et al., USDA.