Biomass Conversion

Processes: Liquefaction
Prof. Shushil Kumar
 General process train
Pretreatment
•Drying Primary conversion
•Milling •Combustion
Biomass from •Purification •Gasification
the fields •Loosening of •Pyrolysis
structure •Liquefaction
• Torrefaction •Fractionation
•….

Secondary conversion
Cleaning / •Turbine Cleaning /
Conditioning / •Catalytic gas conversion Conditioning / Products
Separation •Refining Separation
•Upgrading of bio-oil

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What is Direct Liquefaction?

100 bar

320oC

3
Direct liquefaction of biomass
• The liquefaction process is a thermochemical conversion technique that
transforms solid biomass into liquid bio-oil by breaking down complex
organic structures in the presence of heat, pressure, and often a
solvent or catalyst.

• Types:-

1. Hydrothermal liquefaction (solvent:- water)

2. Solvothermal liquefaction (solvent:- organic solvent/solvent + water)

Direct liquefaction of biomass
• The process takes place under a liquid phase conditions.

• It uses milder temperatures of 250-370oC but higher pressure of 20-

240 bar.

• Biomass is converted directly into a liquid, unlike in pyrolysis , in

which vapours are formed and then condensed.
Process T (oC) P (MPa) τ Drying Carrier medium

Liquefaction 150-370 0.1-24 5-30 min Un-necessary Water/Solvent

Pyrolysis 370-700 0.1-0.5 <2s Necessary Unnecessary/

Sweeping gas

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Why direct liquefaction process?
• No need to dry the feed

• High liquid yield

• No significant heat transfer limitation

• Robust process

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History of Direct Thermal
Liquefaction
Process steps of liquefaction
• Preparation of feedstock

• Slurrying the feedstock within a liquid carrier

• Heating the slurry to reaction conditions

• Addition of reducing gas (e.g. H2 or H2/CO) at elevated pressure

• Main reaction

• Product separation, and

• Recovery of solvent

• Usually catalysts of various functions are added to the slurry.

Reaction mechanism
Involves three key steps:

1. Depolymerization of the biomass

2. Decomposition of biomass monomers by cleavage, dehydration,

decarboxylisation and deammination

3. Recombination of reactive fragments

Water as a reaction medium
Reaction mechanism
Gas

-H2O
monomer Lights

High Temperature
-H2O
Lignocellulose Oligomer Distillates

-H2O
Polymer VR

Secondary
Primary char
char

Kumar et.al.; Industrial engineering and Chemistry Research 2014, 53(29), 11668. 11
Reaction mechanism
• A simplified reaction mechanism for carbohydrate degradation at sub-
and supercritical conditions
Reaction mechanism
• Simplified scheme of lignin degradation
HTL Process
HTL Process
Product Distribution:

• Bio-oil (Liquid Yield): Main product used for fuel and chemicals.

• Solid Residue (Bio-char): Rich in carbon and minerals.

• Gas: CO₂, H₂, CH₄, etc.

• Aqueous phase (water-soluble organics)

Factors Affecting Liquefaction:

• Feedstock type (cellulose, hemicellulose, lignin content).

• Solvent properties (e.g., polarity, stability).

• Catalysts for deoxygenation and cracking.

• Temperature and reaction time.

Effects of catalysts

Saqib Sohail Toor, Lasse Rosendahl, Andreas Rudolf, Hydrothermal liquefaction of biomass: A review of subcritical water technologies,
Energy, Volume 36, Issue 5, 2011
Effect of temperature
Effect of temperature
Review of different processes
PERC Process

• Pittsburgh Energy Research Center (PERC) Process (1970s), demonstrated in a pilot

plant.

• Converting dried-wood flour in an anthracene oil at 300–370 °C in the presence of a

catalyst (Na2CO3: 4–8% dried-wood weight basis) and reducing gas (CO/H2,
operating pressure 20 MPa).

• Anthracene oil was progressively replaced by recycling the oil produced.

• However, serious technical problems, caused by undissolved solids and an increase of

medium viscosity, prevented the pilot unit from operating after 1981.

• However, whilst in operation, the unit produced 5000 kg of oil on a continuous basis.
Review of different processes
Review of different processes
Lawrence Berkely Laboratory (LBL) Process

• Introduced a pretreatment of wood prior to its liquefaction.

• A mild acid hydrolysis (pH 1.8) at 180 °C for 45 min and weakened the lignocellulosic
material.

• A water/wood slurry was then prepared and the pH was adjusted to 8 using Na2CO3.

• The subsequent wood slurry liquefaction lasted for 10–60 min at a temperature of
340 °C.

• Research was halted in the early 1980s as the price of petroleum dropped and
interests shifted to fuel additives, such as ethanol.
Review of different processes
Review of different processes
UDES-S process
• Combines a pretreatment step and solvolysis, with high shear effects
taking place in an organic solvent (e.g. creosote oil or ethylene glycol).

• Feed:1 kg min-1 semi-continuous development unit

• Consists of a pretreatment section, where a wood-solvent suspension

(18-24% weight of wood), is preheated up to 150-240°C, and then
forced across the defibrilation valve through repeated passages until a
pumpable and homogeneous suspension is obtained.

• Residence time varies between 4 and 6 min. The operating temperature

and pressure are respectively 320-350°C and 3-4.7 MPa.
UDES-S process
Compiegne University of
Technology
• Pretreatment of lignocellulosics with combined autohydrolysis and
shear taking place in a twin-screw extruder

• Solvolysis of the pretreated wood in phenolic solvents (phenol, oil from

liquefied wood) with identification of optimal operating conditions
(temperature, residence time, wood/solvent ratio, and pH)

• Upgrading the phenolic solution using conventional refining processes.

Compiegne University of
Technology
HTU® (Hydrothermal Upgrading)
process
• The biomass was suspended and pumped into the reactor using a high-
pressure pump.

• At temperatures of 300–350 °C, pressure between 12 and 18 MPa and a

residence time of 5–20 min, a bio-crude, gases (>90% CO2), organic
compounds (alcohols and acids) and water were produced.

• The heating value of bio-oil was 30–35 MJ/kg.

Other processes
• DoS (direct liquefaction of organic substances) process. A direct one-step liquefaction
process for lignocellulosic biomass (e.g. wood, straw). It runs at a pressure of about
8.0 MPa and at temperatures between 350 and 500 °C.

• CatLiq technology and operates a 20 L/h capacity pilot plant in Copenhagen, Denmark. In
the CatLiq® process organic waste is converted to oil in the presence of a homogeneous
(K2CO3) and a heterogeneous (Zirconia) catalyst, at subcritical conditions (280–350 °C and
22.5–25 MPa).

• Sludge-to-oil reactor system (STORS) capable of processing undigested municipal sewage

sludge with 20% solids at a rate of 30 L/h. Approximately 73% of the energy content of the
feedstock was recovered as combustible products (oil and char), suitable for use as a
boiler fuel. The oil product had a heating value of around 36 MJ/kg.
Review of different processes
Review of different processes
Comparison of Bio-crude by HTL
and Pyrolysis

Gollakota ARK, Kishore N, Gu S. A review on hydrothermal liquefaction of biomass. Renewable and Sustainable Energy Reviews 2018;81
Energy efficiency & Benefits of
HTL process
Process Efficiency:
• Consumes only 10–15% of the energy in biomass.
• Achieves 85–90% energy efficiency.
• Recovers >70% of feedstock carbon, aiding carbon capture.

Economic & Environmental Benefits:

• Algal HTL enables nutrient recycling, CO₂ utilization, and wastewater reuse.
• By-products: Fertilizer, bio-crude, treated water, and nutrient-rich residues.

HTL vs. Pyrolysis:

• HTL bio-crude has higher carbon and hydrogen content.
• Lower oxygen and moisture content, requiring minimal upgrading.
• Higher energy yield, making it a more efficient conversion process.
Bio-oil properties
Properties of Bio-Oil (Ranges):

1. Density: 1.0–1.2 g/cm³

2. Viscosity: 10–1000 cP (varies with feedstock and process conditions)

3. Water Content: < 5 wt.%

4. Oxygen Content: 10–25 wt.% (less than pyrolysis oil)

5. Heating Value: 30–40 MJ/kg

6. pH: 2–4 (acidic)

7. Carbon Content: 60–75 wt.%

Biochar properties
Properties of Biochar (Ranges):

1. Carbon Content: 50–85 wt.%

2. Porosity: Surface area ~5–30 m²/g

3. Heating Value: 20–35 MJ/kg (higher than raw biomass)

4. Oxygen content: 10-40 wt.%

*These ranges are approximate and depend on the feedstock, solvent,

catalysts, and process conditions used during liquefaction.
Bio-oil usage
Bio-char usage
Current commercial status
• Hydrofraction Technology developed by Steeper
Energy
• Cat-HTR technology developed by Licella
Cat-HTR technology by Licella
Hydrofraction by Steeper Energy
Kinetic modeling
Kinetic modeling
Kinetic modeling

• xi(t)= Actual yield of the ith component

• xi,m(t)=Model-predicted yield of the ith component

• The set of ordinary differential first solved simultaneously using the 'ode45' solver
available in MATLAB.

• After obtaining the model calculated yields (xi), the sum of squared residuals was
minimized using the nonlinear optimization function “fmincon” available in MATLAB.

• The “fmincon” function requires defining the upper and lower bound of the input
variable which is the rate constant here.
Kinetic modeling
Kinetic modeling
MATLAB code
MATLAB code
MATLAB code
References
• J. M. Bouvier, M. Gelus & S. Maugendre , Wood Liquefaction an Overview ,
Applied Energy 30 (1988) 85-98

• Gollakota ARK, Kishore N, Gu S. A review on hydrothermal liquefaction of

biomass. Renewable and Sustainable Energy Reviews 2018;81(1378-1392,
doi:https://doi.org/10.1016/j.rser.2017.05.178

• Ni J, Qian L, Wang Y, et al. A review on fast hydrothermal liquefaction of

biomass. Fuel 2022;327(125135, doi:https://doi.org/10.1016/j.fuel.2022.125135

• Sheshanarayana, R., Kumar, S. A kinetic model for the direct thermal

liquefaction of pine wood. Biomass Conv. Bioref. (2023).
https://doi.org/10.1007/s13399-023-04095-y