Alternative Energy Methods

Renewable Energy Resources
BIOMASS
Introduction
Definitions:
Different materials of biological origin that can be used as a primary source of energy Plant materials and animal waste used especially as a source of fuel
Exploited by humans for a very long time Used to provide warmth Late 1700s approximately 2/3 of the volume of wood removed from the American forest for energy generation 1800s a single households consumes 70 to 145 m3 of wood annually for heating and cooking Still used by US and Finland to supplement their total energy usage
Source: Lee, S., Speight, J. G., Loyalka, S. K., Handbook of Alternative Fuel Technologies, CRC Press, 2007
Introduction
Biomass utilization for energy in various countries:
Country Austria Belgium Canada Denmark Ireland New Zealand Norway Sweden Switzerland U.S. Energy from Biomass Utilization (%) 4.0 0.2 3.0 1.0 13.0 0.4 4.0 13.0 1.6 2.8
Biomass Composition
Energy stored in the form of:
Carbohydrates Hydrocarbons Esters
Carbohydrates:
Most common components of biomass Sugars or condensation polymers of simple sugars Can be stored in:
Sap (sugar cane) Tubers (sugar beets) Fruits
Source: Rosa, A.V., Fundamentals of Renewable Energy Processes, Elsevier Inc., 2005
Biomass Composition
Hydrocarbons:
Generally polyisoprenes (terpenes) polymers of the alkyne hydrocarbon, (isoprene, C5H8) Found in some euphorbia such as the rubber tree
Esters (oils):
Result of a reaction of an acid (frequently of carboxylic acid) and an alcohol liberating a molecule of water Oil from the pulp of the fruit of a different nature from that obtained from the seed of kernel Oil of interest: Oil from the castor bean; insoluble in gasoline and can be used to lubricate gasoline pumps Palm oil, originally used by Rudolf Diesel in his engine, is of major interest as fuel
Source: Rosa, A.V., Fundamentals of Renewable Energy Processes, Elsevier Inc., 2005
Biomass Feedstock
Categories of biomass feedstock:
Vegetable oil Pure carbohydrates (e.g. sugar and starch) Heterogeneous woody materials lignocelluloses
Factors taken into consideration a large-scale biomass program:

Short- and long-term land availability Productivities, species involved, and mixtures Environmental sustainability Social and socioeconomic factors Economic feasibility Ancillary benefits Disadvantages and perceived problems
Photosynthesis
Utilizes CO2 and water to produce simple sugars in the presence of solar energy, chlorophyll and other plant ingredients Photosynthesis chemical reaction: 6CO2 + 6H2O C6H12O6 + 6O2 480 kJ/mol Primary selling point of biomass potential use of CO2 to produce fuel (energy) and O2 a win-win situation
Source: Hodge, B. K., Alternative Energy Systems and Applications, John Wiley & Sons, Inc., 2007
Biomass Resources
Agricultural crops - corn, soybeans and wheat that yield sugar and oils Agricultural crop residues residues, such as stalks and leaves, of agricultural crops that are not harvested for commercial use Herbaceous energy crops perennials that are harvested annually after reaching maturity (grasses: switchgrass, miscanthus, bamboo, fescue) Woody energy crops hardwood trees harvested within 5 to 7 years of planting (poplar, willow, maple, cottonwood, sweetgum)
Biomass Resources
Forestry residues biomass not harvested or removed during logging, and materials removed during forest management operations Aquatic crops kelp, seaweed and algae Industrial crops developed to produce specific chemicals or feedstocks (e.g. Kenaf) Animal waste result from farm and processing operations Municipal waste result from residential, commercial and industrial sectors; can contain significant biomass with energy content
Biomass Resources
Source: www.genomocs.energy.gov
Biomass Resources
Source: www.genomocs.energy.gov
Biomass Resources
28 %
27 %
8% 6%
31 %
Forest Resources Crop Residues Corn Other Perennial Crops
Biomass Fundamentals
Primary products: Liquid fuels:
Ethanol ethyl alcohol; used as a fuel Methanol methyl alcohol; produced as a byproduct of gaseous fuels Biodiesel chemically modified vegetable oils suitable for diesel fuel Vegetable oil oils contained in grains and seeds Pyrolysis oil a liquid fuel with a heating value of 17-20 MJ/kg
Primary products: Gaseous fuels:
Biogas a mixture of CH4 and CO2; 55-70 % methane by volume Producer gas a flammable gas containing CO, H2, CH4, N2, CO2 and higher hydrates Synthesis gas (syngas) mixture of CO and H2
Conversion Routes of Biomass

Biomass
Thermal
Biological
Extraction
Direct Combustion
Gasification Liquefaction
Pyrolysis
Fermentation
Anaerobic Digestion
Oils
Biogas
Liquid Fuel
Producer Gas
Liquid fuel
Biogas
Thermal Conversion
Direct Combustion
Types:
Complete combustion - the woody components of biomass burn much more efficiently releasing less toxic gases Incomplete combustion - causes release of CO, CO2 and NOx
When conducted in a well-vented area, burning biomass can be a good substitute for combustion of conventional fossil fuel Results in lower sulfur emissions (0.05 to 0.2 wt%)
Thermal Conversion
Direct Combustion
The formation of particulates controlled at the source Large scale processes:
Biomass reduced into fine pieces for combustion in a close-coupled turbine Turbine separated from the combustion chamber by a filter 87% efficiency using lignocellulose material Process feasible for 25 to 400 MW plants
Thermal Conversion
Direct Combustion
Processed biomass is the boiler fuel that produces steam to operate a steam turbine and generator to make electricity
Source: www1.eere.energy.gov
Thermal Conversion
Direct Combustion - Example
How much wood is needed to bring 1 L of water to the boil? Data: Cp water = 4200 J/kg K mwater = 1 kg Heat value of wood, h = 15 MJ/kg wood = 600 kg/m3 Solution: Heat energy needed to heat 1 L of water from 20 oC to 100 oC: Q = h = (t2 t1)Cp water = 80 4200 = 336 kJ Heat energy released in burning of 1 cm3 of wood: Q = 15 60010-6 = 9 kJ Volume of wood required: V = 336/9 = 37 cm3
Source: Boyle, G., Renewable Energy, Oxford University Press Inc., 2004
Thermal Conversion
Gasification
Used for the conversion of biomass only for the past 30 years Product syngas Categories: Noncatalytic process requires a very high temperature of operation (1300 oC) Catalytic process operated at lower temperatures (900 oC and lower) The first system investigated at the pilot scale was a fluidized bed that incorporated dry ash-free (DAF) corn stover as the feed Corn stover has been selected as the feed since 1977 and if treated properly, has the potential to be converted into an energy source that would supply up to 2% of the US energy needs
Thermal Conversion
Gasification
Pilot plant fluidized bed for the gasification of corn stove
Operating temperatures: 840-1020 K Feed rate: 27 kg/h 0.25 x 106 Btu/h gas produced
Thermal Conversion
Gasification
Swedens VEGA gasification system: June 1991 cogeneration power plant built in order to demonstrate integrated gasification combined cycle (IGCC) technology 1992 formation of bioflow with development of pressurized air-blown circulating fluidized bed gasifier technology for biomass 1993 commission of the biomass integrated gasification combined cycle (BIGCC) Specifications:
System combines heat and power (CHP) for a direct heating system It generates 6 MW and 9 MW for district heating of the city of Varnamo, Sweden
Thermal Conversion
Gasification Vega System
Thermal Conversion
Gasification
Air-blown circulating fluidized bed gasifier with a catalytic reformer:
Most processes use closed-coupled combustion with very little or no intermediate gas cleaning Operating temperature 900 oC Products leaving the gasifier: H2, CO, CO2, H2O, CH4, C2H4, benzene and tars Uses O2 and steam to help the process conversion The effluent gas from the fluidized bed gasifier contains syngas, which can be used for further processing without major purification; the hydrocarbon content at this stage is reduced by 95% or better
Thermal Conversion
Gasification Chrisgas Plant, Varnamo, Sweden
Source: www.btltec.com
Thermal Conversion
Gasification
Indirect gasification:
Another gasification process technology Biomass used low in sulfur and ash, highly reactive and volatile Biomass heated indirectly using an external means such as heated sands in Battelles process known as FERCO SilvaGas process A typical gaseous product from a gasifier is close to medium Btu gas A commercial-scale demonstration plant constructed in 1997 at Burlington, VT
Thermal Conversion
Gasification FERCO Gasifier, Burlington, VT
Uses: stocker gate, conventional steam power cycle and electrostatic precipitator (ESP)-based particulate matter removal system Capacity: 200 tons/d Heating value of product gas: 450-500 Btu/scf
Thermal Conversion
Gasification
Process requirements of entrained flow reactor:
Very high temperature (1300 oC) No catalyst Very short residence time Very fine particle size of solid feed, required for efficient entrainment as well as for better conversion without mass transfer limitations; two processes:
Torrefaction mild thermal treatment at temperature of 250 to 300 oC, which converts solid biomass into a more brittle and easily pulverizable material called biocoal Pyrolysis takes place at 500 oC and produces liquid product called bio-oil
Thermal Conversion Liquefaction

Mid-to-late 1980s interest began The preliminary studies utilized woody biomass, or lignocellulose material as a feedstock McGill University in Canada the first documented successful production of ethanol from the liquefaction of woody material:
Used aqueous hydrogen iodine Operating conditions: 125 oC Minimal char production
Thermal Conversion Liquefaction Combined Wood-toEthanol Process

Xylose Liquid solid separation Neutralization
Liquefaction
Fermentation
Lignin removal
Distillation
Cellulose/lignin Wood chips Cellulose production Ethanol
Thermal Conversion Liquefaction

Ethanol Fermenter Distillation Water
Water Slurry
Production of ethanol from glucose: C6H12O6 2 C2H5OH + 2 CO2

Thermal Conversion Liquefaction - Example

How much ethanol can be produced from a ton of sucrose? SOLUTION: C12H22O11 + H2O 4 C2H5OH + 4 CO2 MSucrose = 342.296 kg/kgmol MWater = 18.016 kg/kgmol MEthanol = 46.068 kg/kgmol MCO2 = 44.01 kg kgmol Therefore for 1 ton of sucrose, the water required for the reaction, and the ethanol and CO2 formed are: Water = (MWater/MSucrose) 1 t = 0.053 t = 105.3 lb Ethanol = (4MEthanol/MSucrose) 1 t = 0.538 t = 1077 lb CO2 = (4MCO2/MSucrose) 1 t = 0.514 t = 1029 lb
Thermal Conversion Liquefaction Ethanol Properties

Also called ethyl alcohol or grain alcohol The nominal heating value - 101,000 Btu/gal, about the value of gasoline (on volumetric basis) Motor vehicle that has a gas millage of 24 miles/gal of gasoline would likely have an ethanol mileage of 18 miles/gal Used to improve the octane rating and emission characteristics of gasoline and commonly used in the form of a 10% blend in gasohol called E10 (10% ethanol, 90% gasoline) The highest blend, E85, contains 85% ethanol; used in flex fuel vehicles
Thermal Conversion Pyrolysis

The exact proportion of the end products depends on the pyrolysis process used (i.e. pressure, temperature) Technology identical to that used in the petroleum industry The first biocrude produced:
At a 30 kg/h scale At operating conditions of 500 oC Residence time of 1 s The biocrude had the same oxygen and energy content as its natural crude counterpart
Canadian researchers converted woody biomass into fuel via pyrolysis in a 200 kg/h pilot plant The fuel oil substitute produced (on 1000 t/d dry basis) at approximately $3.4/GJ (the cost for light fuel oil $4.0 4.6/GJ)

ERCO (Energy Resources Company) unit:
Accepts biomass with a 10% moisture content at a rate of 100 tons/d Has a minimal net energy efficiency of 70% and produces gaseous, liquid and char products Implements cogeneration system to convert the pyrolysis gas into the electricity Small fraction of pyrolysis gas also used to dry the entering feedstock to the required 10% moisture The average heating values for the pyrolytic oil and char: 10,000 Btu/lb and 12,000 Btu/lb Pyrolysis gas (nominal heating value of 150 Btu/lb), not considered an end product - directly used in the cogeneration system
Thermal Conversion Pyrolysis ERCO Unit

Oil, Gas Char & Ash 13,538 lb/h Oil & Gas 12 12,370 lb/h Air 6758 lb/h To Dryer
Cyclone
Oil Scrubber
Gas Turbine
Generator
Pyrolyzer
Biomass 8334 lb/h
1022 lb/h Char 146 lb/h Ash Air 5204 lb/h
Oil Cooler
Oil to Storage 1292 lb/h

Hydrocarb process:
Converts a mixed biomass and natural gas feedstock into methanol, gasoline and char Basic steps:
Hydropyrolyzer - the biomass is gasified with recycled hydrogen-rich gas to form a methane-rich gas at 800 oC Methane pyrolyzer CH4 is decomposed to C and H2 at 260 oC Methanol synthesis reactor - CO is catalytically combined with H2 to form methanol at 1100 oC

Hydrocarb process:
For every 100 kg of biomass and 18 kg of methane fed to the gasifier, approximately 67 kg of methanol and 40 kg of char were produced Advantages:
Char produced in this process is pure carbon and it can be used as a clean fuel Conversion of CH4 to methanol in the presence of biomass decreases the CO2 emissions Potential to replace the feedstock with other materials, such as MSW (municipal solid waste), CH4 can be replaced with coal
Thermal Conversion Pyrolysis Hydrocarb Process

Biomass Natural Gas Purge
3.89% CO; 0.27% CO2 18.76% CH4; 0.06% H2O 76.11% H2; 0.91% CH3OH
Char
Gasifier
4.65% CO 1.54% CO2 39.76% CH4 12.6% H2O 41.43% H2
Methanol Methanol Converter
Pyrolysis Reactor Char
12.09% CO; 0.194% CO2 12.83% CH4; 2.17% H2O 72.12% H2
Thermal Conversion Liquefaction Pyrolysis Liquids Properties

Have a low viscosity and are dark brown in appearance Highly oxygenated and contain significant amount of water Highly unstable and highly corrosive (low pH) Difficult storage due to the corrosive nature of pyrolysis Oxygen and water content makes them incompatible with conventional hydrocarbon fuels
Thermal Conversion Liquefaction Methanol Properties

Also called wood alcohol Can be used as a fuel in modified internal combustion engines The heating value of methanol is nominally 76,000 Btu/gal, only about 58% of the value of gasoline (on volumetric basis) A motor vehicle that has a gas mileage of 24 mile/gal would likely have a methanol mileage of about 14 miles/gal
Thermal Conversion Liquefaction Methanol Properties

Advantages:
The methanol-air flame temperature is lower than that for gasoline Produces lower amount of NOx; no SOx Has limited soot and CO2 emission
Disadvantages:
Lower energy density Presents severe health hazards if ingested or absorbed Soluble in water Accidental ignitions can be hard to see, since it burns with a nearly colorless flame
Biological Conversion Anaerobic Digestion

Well known for the past 100 years Mineralizes organically bound materials to CH4 and CO2 Most of the biomass feedstock studied have produced a biogas rich in CH4 Penn State University digester:
The first anaerobic digester Utilized cow manure for biogas production Operated for a total of 450 days to treat 1200 t of manure Composition of the biogas produced: 60% CH4, 32-34% CO2, 6-8% N2, and trace amounts of H2S 44 kW - total energy generation

Biogas - also called swamp gas, landfill gas, or digester gas Involves relatively simple systems Biogas produced in stages by different types of bacteria Anaerobic digestion stages:
1. Breaking down the waste into sugars and amino acids by hydrolytic bacteria 2. Conversion of the sugars and amino acids to organic acids by fermentative bacteria 3. Conversion of the organic acids to H2, CO2, and acetate by acidogenic bacteria 4. Production of biogas from the acetic acid, H2 and CO2 by methanogenic bacteria

Takes place in an airtight chamber called a digester Digesters modes of operation:
Batch Continuous - produces a steady stream of biogas and typically associated with large-scale operation
Temperature sensitive process Required temperature - at least 68 oF, but temperatures as high as 150 oF are possible The higher the temperature, the shorter the process time and smaller digester volume

Composition of anaerobic digester:
Pre-mixing tank Digester vessel System using biogas Means of spreading or distributing the digested effluent

Biogas Collector System
Mixing Tank Mixer Biomass in
Lagoon Storage
Effluent Discharger
Digester
Extraction
Produces biodiesel from feedstock such as vegetable oils and animal fats Biodiesel - composed of fatty acid alkyl esters Oils can be extracted from seeds, nuts, and other parts Direct use of plant oils in diesel engines shortens operating life and leads to engine maintenance issues The expected 10,000 h between engine overhauls can be reduced to 600 h for sunflower oil operation or 100 h for operation on linseed oil
Extraction
The generic reaction: triglyceride + methanol methyl ester + glycerol Example of generic reaction - the simplified composition for olive oil:
(C17H33CO2)3C3H5 + 3CH3OH 3C17H33CO2CH3 + C3H5(OH)3 Where C17H33CO2 - the fatty acid component of olive oil
Extraction- Example
How much biodiesel can be produced from a 100 lb of oil? MOlive Oil = 885.402 kg/kgmol MMethanol = 96.126 kg/kgmol MBiodiesel = 889.434 kg/kgmol MGlycerol = 92.094 kg/kgmol Therefore for 100 lb of oil, the methanol required and the biodiesel, and glycerol formed are: Methanol = (MMethanolr/MOlive Oil) 100 lb = 10.85 lb Biodiesel = (MBiodiesel/MOlive Oil) 100 lb = 100.45 lb Glycerol = (MGlycerol/MOlive Oil) 100 lb = 10.40 lb
Extraction Biodiesel Properties

Has a viscosity comparable to conventional diesel fuel and a cetane number about of 50 Providers for a much longer time between overhauls compared with the use of plant oils Burns cleaner than conventional diesel fuel and significantly reduces emissions of CO, unburned and aromatic hydrocarbons, sulfates and particulate matter
Extraction Biodiesel Properties

Blends of up to 20% biodiesel with conventional fuel can be used without any engine or infrastructure (storage and distribution) modification B5, B10 and B20 are the usual biodiesel blends Sufficient biomass feedstock exists to supply 1.9 billion barrels of biodiesel, about 5% of the total use of conventional diesel fuel
Extraction
Basic process for producing biodiesel:
Base-catalyzed transesterification Direct acid-catalyzed transesterification Conversion of the oil to its fatty acids and then to biodiesel
Advantages of the base-catalyzed transesterification:

Occurs at low temperature and pressure High conversion efficiency (98%) Involves minimal side reactions Conversion to biodiesel is direct, with no intermediate compounds No special materials needed in the reactor
Cost of Bioenergy
The main factors determining the cost of energy from biomass:
Capital cost including the cost of borrowing money the main component Fuel cost Operating and maintenance costs - usually proportional to the output of the plant, and will depend on the fuel type in particular, the nature of the emissions and the residues it leaves Decommissioning costs - usually covered by the scrap value of equipment
The cost per kWh of output depends on the annual output, so it is important to maximize the load factor
Future Prospects
Two opposing factors determining future demand for biomass:
The rise in overall energy demand due to increasing population The reduction demand for bioenergy due to a shift from traditional to modern forms of energy
Biomass consumption will continue to rise during the next few decades, but at lower rate than renewables in general or total primary energy Traditional biomass will remain the sole domestic fuel for over a quarter of the worlds population in 2030 Allowing for increased food production for a growing world population, as much as 400-700 million additional hectares could be available for energy crops world-wide in the year 2050, without the loss of biodiversity. If used, this could provide of the order of 100 EJ of bioenergy per year

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Renewable Energy Resources

Factors taken into consideration a large-scale biomass program:

Forest Resources Crop Residues Corn Other Perennial Crops

Conversion Routes of Biomass

Pilot plant fluidized bed for the gasification of corn stove

Thermal Conversion Liquefaction

Thermal Conversion Liquefaction Combined Wood-toEthanol Process

Cellulose/lignin Wood chips Cellulose production Ethanol

Thermal Conversion Liquefaction

Production of ethanol from glucose: C6H12O6 2 C2H5OH + 2 CO2

Thermal Conversion Liquefaction - Example

Thermal Conversion Liquefaction Ethanol Properties

Thermal Conversion Pyrolysis

Thermal Conversion Pyrolysis

Thermal Conversion Pyrolysis ERCO Unit

Biomass 8334 lb/h

1022 lb/h Char 146 lb/h Ash Air 5204 lb/h

Oil to Storage 1292 lb/h

Thermal Conversion Pyrolysis

Thermal Conversion Pyrolysis

Thermal Conversion Pyrolysis Hydrocarb Process

Methanol Methanol Converter

Pyrolysis Reactor Char

12.09% CO; 0.194% CO2 12.83% CH4; 2.17% H2O 72.12% H2

Thermal Conversion Liquefaction Pyrolysis Liquids Properties

Thermal Conversion Liquefaction Methanol Properties

Thermal Conversion Liquefaction Methanol Properties

Biological Conversion Anaerobic Digestion

Biological Conversion Anaerobic Digestion

Biological Conversion Anaerobic Digestion

Biological Conversion Anaerobic Digestion

Biological Conversion Anaerobic Digestion

Mixing Tank Mixer Biomass in

Extraction Biodiesel Properties

Extraction Biodiesel Properties

Advantages of the base-catalyzed transesterification:

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