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Biomass Characterization and

Gasification
CHEN 4470: Process Design Practice

Sushil Adhikari, Ph.D.

Biosystems Engineering Department

January 24, 2013

Biomass Properties

• Physical Properties
– Density, size, shape, area
• Chemical Properties
– Heating value, proximate analysis, ultimate
analysis
• Biomass Constituents
– Hemicellulose, cellulose and lignin

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Proximate Analysis

• Proximate Analysis (weight percentage)

– Moisture Content (wet basis/dry basis)–
ASTM E871
– Ash Content—ASTM D1102
– Volatile Matters-- ASTM E872
– Fixed Carbon

Ultimate Analysis (contd.)

• Ultimate Analysis (ASTM D 5373-02)

– Carbon (E 777)
– Hydrogen (E 777)
– Nitrogen (E 778)
– Oxygen
– Other elements-S, Cl..
• Carbon, hydrogen and nitrogen are
converted into carbon dioxide, water vapor,
nitrogen, respectively for quantification.
• Usually, oxygen is calculated from the
difference (100-C-H-N).

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Heating Value
• Heating value represents the heat released
when the chemical compound is
stoichiometrically combusted.

• Heating value is expressed in terms of higher

(gross) heating value (HHV) or lower (net)
heating value (LHV).

• While measuring HHV, the products of

combustion are cooled to the initial
temperature of the compound. In LHV, the
water produced during combustion is not
condensed.

Table: Proximate, ultimate and heating value analyses (dry weight basis) of selected biomass 
feedstocks
Switchgrass Hybrid Pine Sugar cane Wyoming Elkol
poplar woodchipsb bagasse coal

Proximate Analysis
Fixed Carbon 14.34 12.49 18.01 11.95 51.4
Volatile Matter           76.69 84.81 81.71 85.61 44.4
Ash 8.97 2.70 0.28 2.44 4.2

Ultimate Analysis
Carbon 46.68 50.18 49.33 48.64 71.5
Hydrogen 5.82 6.06 5.03 5.87 5.3
Nitrogen 0.77 0.60 0.53 0.16 1.2
Oxygen‡ 37.38 40.43 44.70 42.82 16.9
Sulfur 0.19 0.02 0.13 0.04 0.9
Chlorine 0.19 0.01 0.003 0.03 n/a

HHV, MJ/kg 18.06 19.02 19.40 18.99 29.50

‡calculated from difference. n/a= not available.

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Enthalpies of Formation
• Enthalpies of formation is quite useful for
thermodynamic calculations such as Gibbs
free energy of minimization.
• The standard enthalpy of formation of a
particular biomass sample is equal to the
sum of heats of formation of the products on
combustion minus the HHV. If you use the minus sign, then you
should use “-” for the HHV because of exothermicity. Otherwise, you can use “plus” sign without
worrying any sign for the HHV.

• It is assumed that ash is inert.

• Standard enthalpies of formation at 298 K of
the combustion products are as follows:
CO2 = -94.05; H2O =-68.37; NO2 =8.09; SO2
=70.95 in kcal/g-mol

Biomass Gasification

Biomass: Gasification: Products:

High Syngas:
Temperature
(800-900oC) H2
CO
CO2

CH4
Small solid or
CH1.44O0.66 liquid fractions
Insufficient
Oxidizing agent
(Air, O2, H2O and CO2)

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Biomass Gasification

• Partial oxidation of biomass to produce a low

calorific-value fuel called syngas or producer gas.

• Main components of the producer gas are CO, H2,

CO2, CH4, N2, and H2O.

• Chemical transformation can take place in fixed,

moving, or fluidized bed or entrained flow gasifiers
at temperatures of 1400 to 1800°F with pressures
from 1 to 30 atmospheres.

Syngas Potential

Source: Jenny B. Tennant. NETL Overview of DOE’s Gasification Program

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Conversion of Syngas to Fuels

Power

Gasification Steps

1. Drying (>150 oC)

2. Pyrolysis or Devolatilization (150-700 oC)
3. Combustion (700-1500 oC)
4. Reduction (800-1100 oC)

Processes 1, 2, and 4 absorb heat whereas

step 3 releases heat.

Source: Prabir Basu, 2006. Combustion and Gasification in Fluidized Beds

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Drying

• Every kg of moisture in the biomass takes

away a minimum of 2260 kJ to vaporize
water (Basu, 2010).
• Typical moisture content of freshly ranges
from 30 to 60% and for some biomass it
can exceed 90%.
• For the production of a fuel gas, most
gasification system use dry biomass with a
moisture content of 10 to 20%.

Pyrolysis

• Complex physical and chemical processes

occur during the pyrolysis process.
• It starts slowly at 350 oC, accelerating to an
almost instantaneous rate above 700 oC.
• During pyrolysis process, large compounds
are broken down and evaporate with other
volatile components.

Biomass + Heat  Char + Gases+

Vapors/liquid (tar or PAHs)

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Combustion

• Oxidation or combustion is one of the

most important reactions in the
gasification.
• All the thermal energy needed for
endothermic reactions are provided during
this step.
• Oxygen supplied to the gasifier reacts with
combustible products, resulting the
formation of CO2 and H2O.

Gasification Chemistry

Biomass

Oxygen
Syngas

Steam

Source: Jenny B. Tennant. NETL Overview of DOE’s Gasification Program

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Reactions

• Combustion Reactions
• Boudouard Reaction
• Water-Gas Reaction
• Methanation Reaction
• CO shift Reaction (Water-Gas Shift
Reaction)
• Methane Steam Reforming Reaction

Source: Prabir Basu, 2006. Combustion and Gasification in Fluidized Beds

Reactions (cont.)

• Combustion Reactions

C+1/2 O2 CO (H = -111 MJ/kmol)

CO+1/2 O2  CO2 ( H = -283 MJ/kmol)
H2 + ½ O2  H2O ( H = -242 MJ/kmol)

• Boudouard Reaction
C+CO2  2CO ( H = +172 MJ/kmol)

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Reactions (contd.)

• Water-gas Reaction

C+H2O  CO+H2 ( H = +131 MJ/kmol)

• Methanation Reaction

C+2H2  CH4 ( H = -75 MJ/kmol)

• Methane Steam Reforming Reaction

CH4+H2O  CO + 3H2 ( H = +206 MJ/kmol)

Reactions (contd.)

• Water-gas Shift Reaction

CO+H2O  CO2 + H2 ( H = -41 MJ/kmol)

• For real fuel, the overall reaction can be

written as:

CnHmOp + ??O2  CO +CO2+H2+CH4+H2O+tar

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Heating Value of Syngas

The higher heating value of the syngas can be calculated by the
volumetric fraction and the higher heating values of gas
components, which is given by

Types of Gasifier

Downdraft Crossdraft
Updraft
Gasifier Gasifier
Gasifier
Source: Olofsson et al., 2005.

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Mobile BIOMAX
• Features
• Field deployable.
• Self contained and doesn’t
need grid connection.
• 25 kWe generating capacity.
• 50 lbs biomass consumed
per hour.

Mobile BIOMAX (contd.)

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Biomax control system

 64 control points (temps, pressures,
flows, motors, engine, generator, etc.)
 30 auto alarms with text messaging or
email.
 Auto remote start up and shut down.
 Full data logging – downloadable.
 Remote trouble diagnosis / software
upgrades.
 Manual on-site push button start-stop.

Fluidization Regimes

Source: Introduction to Fluidization Technology by Dr. Karl V. Jacob and Dr. Ray Cocco on April 13, 2011 at ChemE on Demand

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Types of Gasifier (cont.)

Bubbling Fluidized Bed Entrained Flow Gasifier

Gasifier
Source: Olofsson et al., 2005.

Fig. Gas conditioning system

Fig. Auburn University’s bubbling fluidized bed gasifier and biomass feeder

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Advantages/ Disadvantages

• Updraft Gasifier
– Size, shape and moisture content of biomass
particles are less critical than with a downdraft
gasifier.

– Design is simple and results in a fairly high

heating value of the gas.

– The quality of the syngas is generally quite low.

– High temperature near the reactor grate can

cause blocking due to ash fusion

Source: Olofsson et al., 2005.

Advantages… (cont.)
• Downdraft Gasifier
– Produced gas is generally of relatively good
quality and has low level of tars.
– Up to 99.9% of the formed tar is consumed
minimizing tar cleanup.
– Syngas contains relatively high levels of CO2
since a large portion of the biomass is
oxidised.
– Heating value is low.
– Size and shape and low moisture content of
biomass particles must be controlled within
close limits.
Source: Olofsson et al., 2005.

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Advantages/ Disadvantages (cont.)

• Crossdraft Gasifier
– Design is simple.

– Quality of syngas is generally poor.

– Heating value of the syngas is low and the tar

content is high.

Source: Olofsson et al., 2005.

Advantages/ Disadvantages (cont.)

• Bubbling Fluidized Bed Gasifier
– Reactor allows high rates of throughput, higher
than fixed beds.
– Results in good mixing, optimized kinetics,
particle/gas contact and heat transfer as well as
long residence time.
– High carbon conversion rates and, consequently,
high yields.
– Sand bed makes it possible to use in-bed catalytic
processing.
– Syngas is rich in particulates

Source: Olofsson et al., 2005.

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Advantages/ Disadvantages (cont.)

• Entrained Flow Gasifier
– Almost tar free syngas
– Leach-resistant molten slag
– A high percentage of energy is converted into
sensible heat.
– Production of biomass powder is an extra
cost.

Source: Olofsson et al., 2005.

Composition of Gas Yield

• Fuel Composition
• Gasifying Medium
• Operating Pressure
• Temperature
• Moisture Content of the Fuel
• Mode of Bringing the Reactants into
Contact

Source: Prabir Basu, 2006. Combustion and Gasification in Fluidized Beds

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Gas Composition (cont.)

Component Composition, %
Nitrogen 50-54
CO 17-22
CO2 9-15
H2 12-20
CH4 2-3
Heating Value, 5000-5900
kJ/m3

Gas composition presented

here is from downdraft
gasifier operated at 20% MC.

Source: Wood gas as engine fuel. FAO 1986. pp.19

Effect of Operating Parameters

• Temperature
• Pressure
• Feed Characteristics
– Fuel Reactivity
– Volatile Matters
– Ash
– Moisture Content

Source: Prabir Basu, 2006. Combustion and Gasification in Fluidized Beds

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Volatile Matter

• Fuels with high volatile matter content are

easier to gasify.
• Also, char produced from gasification
process is more porous and easier to
gasify.
• Biomass has high volatile matters and
produces high tar content.
• High tar content makes gas clean-up
process difficult.

Source: Prabir Basu, 2006. Combustion and Gasification in Fluidized Beds

Ash Content
• Ash content does not have direct influence on
the gas composition.
• However, it affects the practical operation of
gasifier.
• Ash can be removed either in solid or liquid
form.
• In fixed and fluidizing beds, ash is removed in
solid form.
• If the ash is removed in the solid form,
feedstocks should have high ash-
melting/softening temperatures and the gasifier
should be operated at well below melting
temperature.

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Ash Content (cont.)

• The relationship between ash melting

temperature and composition is a complicated.
• It mainly depends on SiO2-Al2O3-Cao-FeO.
• High in silica and alumina will result high in
ash-melting temperature. But, the ratio of
silica/alumina is also equally important.
• It is reduced by the presence of CaO and FeO.
• Ash-melting temperature of coal is more than
1200 oC but biomass can have significantly lower
than 950 oC.

Ash Content (cont.)

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Syngas Composition from Different Feedstocks

Constituents Fraction
Higher Heating Value
(N2 balance)
25.0
Peanut hulls
Saw dust 6.0
Poultry Litter
Wood chips
20.0 5.0

4.0
15.0
%vol.

MJ/m3
3.0
10.0

2.0

5.0
1.0

0.0 0.0
O2 CO CO2 CH4 H2 Peanut Saw dust Poultry Wood
hulls Litter chips

Gautam et al. (2009), ASABE Annual International Meeting. June 21-June 24, 2009, Reno, NV

Gasification Processes and Methanol

Production
Process Condition Gasifier Type
Circulating Bubbling fluidized Entrained
fluidized bed bed
Feedstock (wood), t/d 1650 1650 1650
Steam, t/t dry feed 0.31 0.3 0.03
Oxygen, t/t dry feed 0 0.3 0.5
Air, t/t dry feed 1.46 0 0
Gas. Temp., oC 927 982 1045
Gas. Press., psi 14.8 507 357
Exit gas (dry)
H2 (vol.%) 21.1 30.7 33.9
CO (vol.%) 46.8 22.2 50.7
CH4 (vol.%) 14.9 12.0 0.2
CO2 (vol.%) 11.3 35.2 14.9
H2/CO 0.45 1.38 0.66
Source: Klass (1998).

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Design Consideration

• Gasifier Efficiency
– Cold gas efficiency
– Hot gas efficiency
• Carbon Conversion
• Equivalence Ratio

Cold gas efficiency = (Heating value of product

gas/Heating value of feedstocks)x100 %

It is important to specify whether the heating values are on

higher heating value or lower heating value basis.

Design Consideration (contd.)

The gas is not cooled before combustion and the

sensible heat is also useful. Therefore, sometimes,
hot gas efficiency is also used for such applications.

Hot gas efficiency = (Heating value of

product gas + Hsensible /Heating value
of feedstocks) x 100 %

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Design Consideration (contd.)

Carbon conversion = {1 –Carbon in gasification
residue/Carbon in feedstocks} x 100 %
or
{Carbon in gas composition/Carbon in
feedstocks} x 100 %

• Care is required to interpret the data. Higher

methane concentration could result in higher
cold efficiency and good for power
application but it is not the optimum choice
for a synthesis gas applications to produce
fuels and chemicals.

Design Consideration (contd.)

• Equivalence Ratio (ER):

 = (A/F)actual/(A/F)stoichiometric

• The quality of syngas depends upon the value of

ER.
• A low value of ER (<0.2) results in several
problems including excessive char formation.
• A high value of ER (>0.4) results in excessive
formation of CO2 and H2O.
• Typical range of ER is ~0.2 -0.4.

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