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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 ContentASTM 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,ultimateandheatingvalueanalyses(dryweightbasis)ofselectedbiomass feedstocks
Switchgrass Proximate Analysis FixedCarbon 14.34 VolatileMatter 76.69 Ash 8.97 Ultimate Analysis Carbon Hydrogen Nitrogen Oxygen Sulfur Chlorine Hybrid poplar 12.49 84.81 2.70 Pine woodchipsb 18.01 81.71 0.28 Sugar bagasse 11.95 85.61 2.44 cane Wyoming Elkol coal 51.4 44.4 4.2

46.68 5.82 0.77 37.38 0.19 0.19

50.18 6.06 0.60 40.43 0.02 0.01

49.33 5.03 0.53 44.70 0.13 0.003

48.64 5.87 0.16 42.82 0.04 0.03

71.5 5.3 1.2 16.9 0.9 n/a

HHV, MJ/kg
calculated

18.06

19.02

19.40

18.99

29.50

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: High Temperature (800-900oC) Products: Syngas: H2 CO CO2 CH4 CH1.44O0.66 Insufficient Oxidizing agent
(Air, O2, H2O and CO2) Small solid or liquid fractions

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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 1800F with pressures from 1 to 30 atmospheres.

Syngas Potential

Source: Jenny B. Tennant. NETL Overview of DOEs 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 Vapors/liquid (tar or PAHs) + Gases+

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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 DOEs 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 CO+1/2 O2 CO2 H2 + O2 H2O (H = -111 MJ/kmol) ( H = -283 MJ/kmol) ( 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

Updraft Gasifier
Source: Olofsson et al., 2005.

Downdraft Gasifier

Crossdraft Gasifier

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Mobile BIOMAX

Features

Field deployable. Self contained and doesnt 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 Gasifier

Source: Olofsson et al., 2005.

Entrained Flow Gasifier

Fig.Gasconditioningsystem

Fig. AuburnUniversitysbubblingfluidizedbedgasifierandbiomassfeeder

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

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 ashmelting/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 (N2 balance)

25.0 Peanut hulls Saw dust Poultry Litter Wood chips

Higher Heating Value

6.0

20.0

5.0

15.0 %vol. MJ/m3 O2 CO CO2 CH4 H2

4.0

3.0

10.0

2.0 5.0 1.0

0.0

0.0 Peanut Saw dust Poultry hulls Litter Wood chips

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

Gasification Processes and Methanol Production

Process Condition Circulating fluidized bed Feedstock (wood), t/d Steam, t/t dry feed Oxygen, t/t dry feed Air, t/t dry feed Gas. Temp., oC Gas. Press., psi Exit gas (dry) H2 (vol.%) CO (vol.%) CH4 (vol.%) CO2 (vol.%) H2/CO
Source: Klass (1998).

Gasifier Type Bubbling fluidized bed 1650 0.3 0.3 0 982 507 Entrained 1650 0.03 0.5 0 1045 357

1650 0.31 0 1.46 927 14.8

21.1 46.8 14.9 11.3 0.45

30.7 22.2 12.0 35.2 1.38

33.9 50.7 0.2 14.9 0.66

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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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