JEE651 Biomass for Heat and Power Semester 1/2006 Thermal conversion technologies Gasification

Harmen, S.T., M.T.

Thermo-chemical conversion

Gasification
Gasification involves devolatilisation and conversion of biomass in an atmosphere of steam or air, carried out at elevated temperatures (i.e. 500-1400C) and atmospheric or elevated pressures Gasification produces a medium or low calorific gas, called Synthesis Gas

 Synthesis gas consists primarily of hydrogen (H2) and carbon monoxide (CO), with lesser amounts of carbon dioxide (CO2), water (H2O), methane (CH4), higher hydrocarbons (C2+), and nitrogen (N2) Different oxidant used produces gases with different heating value: Air-based gasifiers: 4 and 6 MJ/m3 (107-161 Btu/ft3) O2 and steam-based gasifiers: 10 and 20 MJ/m3 (268-537 Btu/ft3)

Producer gas contains 70-80% of the energy originally present in the biomass feedstock

 This gas can then be used for a number of applications: Used as cooking gas Burned in a diesel engine Fuelled in a combined cycle power generation cycle involving a gas turbine topping cycle and a steam turbine bottoming cycle Raw materials for chemical syntheses: methanol, DME, diesel

Syngas-to-Liquids Processes
Waxes Diesel Olefins Gasoline

MTBE
isobutylene acidic ion exchange

Fe, Co, Ru

Formaldehyde
Ag

i-C4

Isosynthesis ThO2 or ZrO2

Syngas CO + H2
Co
) os 3 ) 4 (Bu Ox CO ) 3P 3) 3 o( CO Ph HC o( )(P HC h(CO R

Cu/ZnO

ca CH rbon yla 3O H Co + C t ion ,R O h, Ni

Mixed Alcohols

Acetic Acid

Fischer-Tropsch

H2O WGS Purify

N2 over Fe/FeO (K2O, Al2O3, CaO)

hom Co ologa tion

DME M100 M85 DMFC

Graphics courtesy of Richard Bain, NREL

NH3

H2

Ethanol

Aldehydes Alcohols

Al2O3

d l 2O pe /A do nO li 3 /Z 3 ka r 2O Cu l 2O Al /C ; A O nO O/ Zn u/Z /Co C O Cu oS 2 M
3

zeolites

Methanol
MTO MTG
e Us ect Dir

Olefins Gasoline

,R h
is es

th yn

The chemistry of gasification

Principal reactions occurring during gasification step Exothermic Reactions (1) Combustion (2) Partial Oxidation (3) Methanation (4) Water-Gas Shift (5) CO Methanation Endothermic Reactions (6) Steam-Carbon reaction (7) Boudouard reaction

Volatiles/char + O2 CO2 Volatiles/char + O2 CO Volatiles/char + H2 CH4 CO + H2O CO2 + H2 CO + 3H2 CH4 + H2O

Volatiles/char + H2O CO + H2 Volatiles/char + CO2 2CO

 Directly heated gasification Pyrolysis and gasification occur in single vessel Heat produced from reaction 1&2 (about 15%) is used for all endothermic reactions (including pyrolysis) Heating value of produced gas is lower Indirectly heated gasification Need two chambers: one acts as gasifier, the other as char combustor This approach separates reaction 1 from other gasification reactions and reaction 2 is suppressed Heating value of produced gas is higher

 Indirectly-heated fast fluid-bed and Indirectly-heated bubbling fluid-bed

Typical Gas Composition

Product gas composition of wood and charcoal of low to medium moisture content (wood 20 %, charcoal 7%) operated in co-current gasifiers Component Nitrogen Wood gas (vol%) 50-54 Charcoal gas (vol%) 55-65

Carbon monoxide
Carbon dioxide Hydrogen Methane

17-22
9-15 12-20 2-3

28-32
1-3 4-10 0-2

Heating value (MJ/Nm3)

5-5.9

4.5-5.6

 Mechanism of tar formation - When biomass is heated molecular bonds break produce small molecules (gas) and larger molecules (known as primary tar)

- These primary tars, which are always fragments of the original materials, can react to secondary tars by further reactions at the same temperature and to tertiary tars at high temperature
- Tar formation pathway can be visualised as follows: Mixed oxygenates Phenolic ethers Alkyl phenolics (400 C) (500C) (600 C) Heterocyclic ethers PAH Larger PAH

(700C)

(800 C)

(900C)

- Example of tar formed

 Biomass gasification for the heat application has generally been successful, but much less success has been realized for power applications, where gas quality is of prime importance. The amount of compounds that occur in biomass gasification tars can be as high as several hundreds or even several thousands for low temperature tars. The amount and composition depend on: - Type and properties of the biomass (moisture, particle size) - Gasification conditions (P, T, residence time) - Type of gasifier (reactor configuration)

Biomass Gasifiers
Fixed bed gasifiers: updraft and downdraft

 A typical design for a fixed-bed gasification plant for the generation of electricity will include Biomass receiving and storage Drying Gasification Particulate removal Generator system

Drying Carried out in a rotary flue gas dryer Hot flue gases from the engine exhaust will be used to evaporate water from the biomass feed. The final moisture content of biomass fed to the gasifier should be <15%.

 In gasifier, the product gases flow through the hot part of the bed and heavy tars produced in pyrolysis crack to form more combustible gas components. For gas cleaning, fuel gas is led through a cyclone to the air pre-heater, where gasification air is heated to 300C cooled to approximately 40C, and part of water vapour present in gas will condense finally filtered through a fabric filter to remove the remaining solid particulates. In dual fuel (engine) operation carried out by VTT Energy in 1995, approximately 15% of the energy fed into the diesel engine is supplied with diesel oil while the rest of the requirement was provided by fuel gas from a fixed-bed gasifier.

 Fluidized-bed gasifier: Bubbling and Circulating

 Atmospheric-pressure fluidised bed gasification is commercially proven technology for coal, peat and wood wastes. A fluidised-bed gasification system for power generation consists of the following major units: biomass receiving and storage milling and drying gasification and tar cracking water wash of the raw gas generator system

Biomass CFB GasifierDemonstration Project

(K Y M I J R V I P O W E R S TAT I O N, L A H T I , F I N L A N D)

Parameter Plant size Technology type Moisture after dryer Carbon conversion Wood feed rate (dry basis)

Unit MW % % kg/s

Value 0.1 Fixed-Bed Gasification 15.0 98.0 0.024

Value 5.8 Fluidised-Bed Gasification 15.0 99.5 0.958

Air to wood ratio

Raw gas LHV Fuel gas temperature Fuel gas LHV Fuel gas flow Diesel Engine power Plant power consumed Net output power Wood input (LHV basis) 1 Wood input (HHV basis)1

kg/kg
MJ/kg C MJ/kg kg/s MW MW MW MW MW

1.95
4.59 40 4.72 0.07 0.1 0.1 0.45 0.54

1.76
5.00 40 4.59 2.99 5.9 0.1 5.8 17.2 20.9

Overall efficiency (LHV)

Overall efficiency (HHV)

%
%

22.5
18.6

33.8
27.9

Gasifier types: Advantages & Disadvantages

Integrated gasification combine cycle (IGCC)

This system uses simple Brayton gas cycle (generally associated with the gas turbine) and is essentially a combined cycle

 The biomass-based IGCC electric generating plants normally consist of the following process sections: Fuel receiving, sizing, preparation, and drying Gasification and gas cleaning (Gasification Island): Wood feeding unit, Gasifier, Char combustion and air heating, Primary cyclone, Tar cracker, Gas quench, Particulate removal Power Island Gas turbine and generator Heat Recovery Steam Generator (HRSG) Steam turbine and generator Condenser, cooling tower, feed water and blowdown treating unit General plant utilities and facilities

 The products of gasification are burnt in a combustor to drive a gas turbine while the heat in the exhaust flue gases is recovered in an HRSG that in turn drives a steam turbine This results to high overall efficiencies with the prospect of even higher efficiencies if high temperature turbines and hot gas cleanup systems were developed

 Preferred Gasification Technologies at Different Scales

Downdraft Updraft Bubbling Fluidised Bed Circulating Fluidised Bed Pressurised Fluidised Bed

1 kW

100 kW

1 MW

10 MW

100 MW

1000 MW

Fuel capacity

 Preferred Gasification-Based Electricity Technologies vs. Scale

Gas engine Dual fuel diesel engine

(more robust than gas engine)

Dual fuel diesel engine + steam cycle IGCC

Fuel cell (not yet commercial)

10

15

20

25

95

100 MWe

 Product gas cleanup

Contaminant Particulates Alkali vapors NH3, HCN H2S, HCl Tars and oils

Potential problem Erosion Corrosion Emissions

Treatments Cyclones, filters Cool/condense/remove Capture, scrubbing

Corrosion, emissions

Capture, scrubbing

Deposition, equipment Cracking, scrubbing, clogging; waste water filtering, combusting treatment (including catalytic tar converter

 Product gas cleanup requirement for different applications

Extent of Gas Cleanup Required Little Direct burning IC engine Gas turbine Modest Higher Highest

Fuel cells
Fuel synthesis

China Small-Scale Biopower Case Study

Characteristics:

- China produces > 700 million t/year of agricultural residues, most of which is used for cooking and heating by direct combustion in rural areas
- Several hundred small biomass gasifiers are currently operating in China to provide cooking gas in rural villages, which helps reduce terrible indoor air pollution problems - But cooking and heating demands alone are too small and unsteady to result in good economics. Adding power generation allows increased scale and greater capacity utilization more favorable economics.

 If used in combined heat and power production, half of total residues produced in China could provide clean cooking gas for 230 million people (27% of rural population) and generate 270 TWh of electricity Case study project: Hechengli Village, Jilin Province - A 200 kWe Gasifier/Engine + Cooking Fuel - Construction and commissioning completed in Aug 2004, but due to institutional problems - no commercial operation yet

Clean Gas CO H2
Gas Clean Up

20 15 2 10 53

CH4
Gas Storage

Biomass Storage Gasifier

CO2 N2

Blower

Btu/ft3 (hhv)

133

Households & Factories

Gas Distribution for Cooking, Heating & Process heat

Gross Output

Engine Generator

Engine Exhaust

Electricity to Households & Factories

Utility Grid

Electricity to Grid

Auxiliary Power for CHP plant

Diesel engines preferred over spark-ignition: more efficient, durable, reliable, simpler maintenance. But requires dual fueling: typically 70% diesel replacement.

200 kWe Gasifier/Engine + Cooking Fuel in Hechengli Village

Hechengli Plant Design

Planned 1800 Nm3/hr gasifier capacity 200 kW engine-generator 224 cooking and heating customers 500 Nm3 gas storage 60 yuan/ton biomass cost 0.2 yuan/Nm3 gas price 0.5 yuan/kWh electricity price Actual 1800 Nm3/hr gasifier capacity 200 kW engine-generator 125 cooking customers with 0 heating customers 300 Nm3 gas storage 90 yuan/ton biomass cost 0.2 yuan/Nm3 gas price 0.58 yuan/kWh electricity price

* Producer gas cooking-only projects in Jilin have not been economically viable without subsidy Electricity generation is essential for commercial viability

Impact of Capacity Factor on Cost

15.0

Power Generating Cost (1997 US cents/kWh)

14.0 13.0 12.0 11.0 10.0 9.0

Calculated Power Generating Cost for 100 kWe BiG/ICE System as Function of Capacity Factor
Biomass @ $1/GJ; diesel @ $0.26/liter; 25-year investment; 12% internal rate of retun

Total Lifecycle Capital Investment, 1997 US$/kW

1200

8.0
800

7.0 6.0 5.0 0% 10% 20% 30% 40% 50% 60% 70% 80% 90% 100%

Capacity Factor

Source: E.D. Larson, Small-scale gasification-based biomass power generation, Proceedings of the Workshop on Small-Scale Biomass Power Generation, Changchun, Jilin Province, China, 12-13 January 1998.

Issues of tar: Small Gasifier-ICEs

Tar content must be < 30-50 mg/Nm3 in gas to IC engine Wood chip gasifiers: Ankur gasifier (Imbert type) cracks tar with high temperatures at throat and catalytic action of charcoal in reduction zone to give ~5 mg/Nm3 at gasifier exit with subsequent water scrubbing and filtration aimed primarily at particulate removal IISc gasifier (stratified, open-top type) cracks tars thermally with long residence times to give ~100 mg/Nm3 tar in raw gas. Tar levels are further reduced to 10-30 mg/Nm3 with water scrubber and sand-bed filter.

Commercialization
Economic viability requires reasonably high capacity factors. Unit capital costs must be reduced to insure competitiveness (especially for smaller systems): Standardize system design to lower cost of manufacture, installation, servicing, etc. Aggregate the market to lower transaction, maintenance, and others costs for suppliers. R&D and commercialization of advanced technologies that reduce costs (e.g., microturbine), especially as biomass costs rise. Two major activity areas with particular relevance for Thailand: Small-scale systems for crop residue utilization, e.g. in China Larger-scale systems for sugarcane residue utilization, e.g. in Brazil

Two synthetic liquid fuels of interest

Fischer-Tropsch Fuels (straight-chain CnH2n , CnH2n+2) F-T fuels of interest include high-cetane, low-aromatic, no-sulfur diesel substitute and naphtha as chemical feedstock upgradable to gasoline blendstock. F-T fuels production is commercially established, and growing rapidly. From coal: Since 1950s in South Africa, 175k bbl/day (bpd) total capacity 20k bpd, Inner Mongolia (2007) 120k bpd, China letter of intent signed 5k bpd demo, Gilberton, Pa (2008) 33k bpd, Wyoming (in planning) 57k bpd, Wyoming (proposed) From stranded natural gas: From 1990s in Malaysia: 13k bpd Planned: Qatar, 2005: 34k bpd Nigeria, 2006: 34k bpd Qatar, 2009: 140k bpd Qatar, 2011: 154k bpd Dimethyl Ether (CH3OCH3) Ozone-safe aerosol propellant, chemical feedstock. Current global production ~150,000 tons/year by drying methanol (CH3OH). Similar to LPG mild pressure needed to keep as liquid. Good diesel-engine fuel: high cetane #, no sulfur, lower NOx, near-zero soot. Rapidly expanding production worldwide to supply (initially) markets for cooking and heating fuel (LPG substitute). 110,000 tpy (from NG) facility to start in China, 2005 800,000 tpy (from NG) facility to start in Iran, 2006 At least two 800,000 tpy (from coal) facilities in planning in China. Sweden bio-DME activities at Varnamo gasification pilot-plant facility aiming at heavy-vehicle applications.

Catalytic synthesis of fuels from CO+H2

Basic overall reactions:
CO + 2H - CH - + H O 2 2 2

Fischer-Tropsch liquids

3CO + 3H CO + 2 H

CH OCH + CO Dimethyl ether 2 3 3 CH OH 3

Methanol

Three reactor designs:

Fuel product (vapor) Fixed-bed (gas phase): low one-pass + unreacted syngas (vapor) Fischer-Tropsch liquids CO + 2H - C HFuel - + product HO conversion, difficult heat removal 2 2 2 + unreacted syngas Disengagement Fluidized-bed (gas phase): better 3CO + 3H CH OCH + CO2 zone Dimethyl ether CONDITIONS TYPICAL 2 3 Disengagement 3 TYPICAL REACTION CONDITIO conversion, more complex operation P= atm. Steam zone P 50-100 = 50-100 atmospheres Catalyst oC T 200-300 = 200-300 C Slurry-bed (liquid phase): much higher T= CO + 2 H CH OH powder Methanol 2 3 slurried single-pass conversion (e.g., 80%Steam vs. Catalyst in oil 40% for F-T) Once-through designs powder catalyst CH OCH slurried CO favored when electricity can be sold CH OH Cooling waterin oil
o 3 3 3

Liquid phase FT reactors are commercial LP-MeOH commercially demonstrated Cooling water LP-DME near commercial

CnH2n+2 Synthesis gas (CO + H2)

CO H2

H2 catalyst

Synthesis gas Focus here on OT process designs with (CO + H2) LP synthesis.

CH3OCH3 (depending on catalyst CH3OH CnH2n+2 (depending on catalyst)

Liquid Phase Reactor

Summary of Key Characteristics

Gasification Only fully commercial for direct gas combustion applications Gasifiers need uniform size and composition of feed with low moisture Gasifiers are relatively simple technologies, but considerable investment is needed in gas cleanup for highvalue uses of the gas Clean gas can meet stringent air emissions limits Comparatively favorable economics at smaller scales (e.g., < 10 MWe)

Advantages of gasification
(compared to conventional combustion technologies)
The combined heat and power generation via biomass gasification techniques connected to gas-fired engines or gas turbines can achieve significantly higher electrical efficiencies between 22 % and 37 % compared to biomass combustion technologies with steam generation and steam turbine (15 % to 18 %).

Due to the improved electrical efficiency of the energy conversion via gasification, 1. the potential reduction in CO2 is greater than with combustion. 2. The formation of NOx compounds can also be largely prevented, although the NOx advantage may be partly lost if the gas is subsequently used in gas-fired engines or gas turbines. 3. Significantly lower emissions of NOx, CO and hydrocarbons can be expected when the produced gas is used in fuel cells.