Module 6

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Renewable Energy Engineering: Solar, Wind
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and Biomass Energy Systems
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Module - 06
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Lecture – 01 (Part I)
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Prof. Vaibhav V. Goud and Dr. R. Anandalakshmi
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Department of Chemical Engineering

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Indian Institute of Technology Guwahati

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Guwahati – 781039, Assam (India)

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Module Module name Lecture Content
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Bioconversion of Bioconversion of substrates into alcohol
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06 substrates into 01 (Part I) Basic principles of bioconversion
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alcohol and Thermo-
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chemical conversion
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of biomass to solid,
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liquid and gaseous
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fuels
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Bioconversion of substrates into alcohol (Ethanol production)
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Ethanol production is based on two major techniques
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a. Chemical synthesis:
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Acid-catalyzed hydration of ethylene forms ethanol which is referred to as a chemical process.
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Phosphoric acid is the most commonly used catalyst in the chemical process (Baeyens et al., 2015).
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b. Fermentation:
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Production of ethanol through fermentation process by using different microbial strains is called as
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biological process. Under anaerobic conditions, certain species of yeast (e.g., Saccharomyces
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cerevisiae) and bacteria (e.g. Zymomonas mobilis) metabolizes the sugars into ethanol and carbon
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dioxide (Zabed et al., 2017)

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Zabed, H. et al. (2017). Renewable and Sustainable Energy Reviews. Elsevier Ltd, pp. 475–501. doi: 10.1016/j.rser.2016.12.076.
Baeyens, J. et al. (2015). Progress in Energy and Combustion Science. Elsevier Ltd, 47, pp. 60–88. doi: 10.1016/j.pecs.2014.10.003.
Comparison of Biochemical and Thermochemical Routes for Biomass Conversion into
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Ethanol
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Process Biochemical Route Thermochemical Route
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(Sugar Fermentation)
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Feedstock Sugarcane/Starch/Corn Cellulosic Stock/Wood/MSW
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Reactor Type Batch Continuous
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Reaction Time Days Minutes
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Water Usage 3.5 – 170 L/L ethanol < 1 L/L ethanol
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By-products Distiller’s dried grain Syngas/Electricity
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Yield* ~ 400 L/ton
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Technology Maturity > 100 plants in the United States Pilot Plant
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The fermentation of syngas from biomass gasification is another possible route for ethanol
production from woody biomass.
* Courtesy: Biomass gasification, pyrolysis and torrefaction, by P. Basu, 2nd edition, 2013, Publisher AP
• Saccharomyces cerevisiae, is poisoned by C2H5OH concentrator greater than 10%, and so higher
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concentrations upto 95% are produced by distilling and fractionating.
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• Production of bioethanol from sugars like Sucrose, Glucose, and Fructose is an industrially well-
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established process and it is found to be a safest and eco-friendly process as well (Vohra et al., 2014).
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However, the first usage of ethanol blended gasoline as a fuel occurred in the 1920s and 1930s and was in
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high demand during World War II because of fuel shortages.
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• Several renewable resources like rice, wheat, corn, sorghum grains, sugarcane, cassava, and sugar
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beet are generally used for the production of bioethanol.

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Vohra, M. et al. (2014). Journal of Environmental Chemical Engineering. 2(1), pp. 573–584. doi: 10.1016/j.jece.2013.10.013.
Bioethanol production from edible sources
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• Sugarcane and sugar beet containing
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sucrose is much easier to extract, therefore,
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the production cost of ethanol from sugarcane
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and sugar beet is lower than that of rice,
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wheat, corn, sorghum grains, and cassava
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derived ethanol
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•
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Because it does not require hydrothermal
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treatment (domestically known as cooking)
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and subsequent enzymatic hydrolysis for the
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gelatinization of starch and it’s conversion

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into sugars, respectively

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Bioethanol production from (a) sugar crops and (b) starchy

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materials
Naik, S. N. et al. (2010). Renewable and Sustainable Energy Reviews, 14(2), pp. 578–597. doi: 10.1016/j.rser.2009.10.003.
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• But, production of bioethanol from edible sources like rice, wheat, corn, sorghum grains, sugarcane and its
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usage in the transportation sector can impose food insecurity to the world population.
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• Due to the high demand of ethanol as a fuel in the transportation sectors may eventually increases the prices of
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the aforementioned edible feedstocks.
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• Therefore, the interest of modern research has been switched to non-food based ethanol (second generation
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biofuels) (Naik et al., 2010).
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• Among many widely available feedstock, inedible agriculture residues such as wheat straw, corn stover,
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sorghum stalks, rice straw, sugarcane bagasse are the potential and promising feedstocks for the
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bioethanol production.
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The amount of major agricultural crops residues burned in the year 2016 and their CO 2 emissions
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Million
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Agriculture crop residues (Million dry ton/year)
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ton/year
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Country Corn Rice Wheat Sugarcane CO2 emission
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USA 35.11 0.07 7.10 0.24 3.73
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India 10.20 23.63 12.09 3.22 4.25
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China 38.98 16.75 9.74 1.09 5.75
Brazil 14.96us is c 1.07 0.87 6.65 2.03

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Due to the structural rigidity, bioethanol production from lignocellulosic biomass is difficult than that of
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sucrose (sugarcane) and starch-containing materials (corn, wheat, rice, sorghum grains, and cassava).
Several processes are investigated for the efficient hydrolysis of lignocellulosic biomass for the production of
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fermentable sugars and their conversion into bioethanol. Among them, pretreatment and subsequent enzymatic
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hydrolysis of lignocellulosic biomass are found to be more efficient and most widely used process
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Several pretreatment techniques such as
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• steam explosion,
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• ionic liquid,
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• dilute acid,
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• biological,
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• hydrothermal, be al
• organo-solvent,
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• concentrated acid and alkali

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Conversion of Lignocellulosic biomass into bioethanol

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Ethanol is produced by the action of microorganisms on carbohydrates (alcoholic fermentation).
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Carbohydrates (saccharides) can be divided into three major classes in order of increasing complexity.
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Monosaccharides (simple hydrocarbons, which cannot be hydrolyzed into simpler compounds),
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glucose and fructose.
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• More precisely, glucose and fructose can be represented by the formulae HCO-(HCOH)4,-CH2OH
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and CH2OH-CO-(HCOH)3-CH2OH, respectively.
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Oligosaccharides (Yield few but definite numbers (2-10) of monosaccharide molecules on hydrolysis).
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• For example, a disaccharide (such as sucrose and malltose, both having the formula (C12H23O11)
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produces two monosaccharide molecules on hydrolysis.

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• Sucrose (common sugar) occurs naturally in sugarcane and beetroot. Maltose (malt sugar) is derived
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from starch.
* Courtesy: Non-conventional energy resources, by B H Khan, 2nd edition, 2009, Publisher, TMH
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Polysaccharides (high-molecular mass carbohydrates, which yield a large number of monosaccharide
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molecules on hydrolysis).
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• Examples are starch and cellulose; both having the general formula (C6H10O5)n. Large numbers (few
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hundreds to few thousands) of glucose units are joined together in a complex chain.
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• Starch occurs naturally in all plants, particularly in seeds. The main sources are maize, barley, rice,
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wheat, potato, cassava and sorghum.
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• Cellulose is the main constituent of cell walls of the plants. Wood contains 45-50% while cotton
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contains 90-95% cellulose. be al
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The hexose (glucose and/or fructose) required for ethanol fermentation is derived from (i) sucrose,
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(ii) starch; or (iii) cellulose as explained below.
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i. Sucrose:
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• Sucrose is the most common disaccharide and can be produced from sugarcane or beetroot.
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Usually, commercial sucrose is separated from cane juice, and the remaining molasses; which has low
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commercial value, is used for ethanol production.
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• The molasses itself has about 55% sugar content and serves as very good raw material for ethanol
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production.
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• On hydrolysis with dilute acids or enzymes, it gives equal amounts of glucose and fructose.
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C12 H 22O11 ( Sucrose ) 

hydrolysis
 C6 H12O6 ( Glucos e )  C6 H12O6 ( Fructose )
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• Sucrose are readily available in a fermentable form, require least expansive preparation, but are generally
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most expensive to obtain.

ii. Starch:
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On hydrolysis with dilute H2SO4 or enzymes, Starch breaks down to maltose and finally to glucose.
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2 ( C 6 H 10O5 )n  n H 2O  n C12 H 22O11  n H 2O  2n C 6 H 12O6
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( starch ) ( Maltose ) ( Glu cos e )
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Starch bearing materials are often cheaper, but require processing to solubilise and convert starch to sugars.
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iii. Cellulose
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• Cellulose is not hydrolyzed so easily as starch, but on heating with dilute sulphuric acid under pressure
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yields glucose.
( C 6 H 10O5 )n  n H 2O  n C 6 H 12O6
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( Cellulose ) ( Glu cos e )

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Cellulosic materials are readily available organic compound, but require most expensive and costly
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preparation. Finally, ethanol is obtained from fermentation of hexose sugars.

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Several pretreatment techniques such as
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• steam explosion,
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• ionic liquid,
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• dilute acid,
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• biological,
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• hydrothermal,
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• organo-solvent,
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• concentrated acid and alkali
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lignocellulosic biomass conversion into bioethanol
Fermentation Systems (Cellulosic material)
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The conversion of cellulose, starch and sugars to ethanol (C2H5OH):
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(C6H10O5)n + n H2O → n C6H12O6
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(Cellulose) (Glucose)
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C12H22O11 + H2O → 2C6H12O6 Thermal properties of ethanol
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glucose
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Parameters Temperature (°C)
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C6H12O6 → 2C2H5OH + 2CO2
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Boiling point 78.22
ethanol
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Flash point 16.45
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Auto-ignition temperature 424.85

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Heat of combustion 26800 kJ/kg
Ethanol production from various types of biomass
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Various steps involved in the production of ethanol from the three types of biomass resources are shown
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in the following schematic
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Natural sugars
Process heat, by
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(cane, beet, fruit) Crush Residue
products
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Starches Hydrolysis
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(Grains: barley, maiz (easy) Sugars Yeast fermentation 10% ethanol
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roots: cassava)
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Fractional 95% ethanol
distillation Commercial ethanol
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Cellulose Hydrolysis
Petroleum substitute
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(wood, straw) (difficult)

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Azeotropic
distillation
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99.7% ethanol
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anhydrous ethanol
Petroleum additive
Steps involved in ethanol production from edible sources
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Water
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95% ethanol
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Commercial ethanol
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Sugar, Corn Petroleum substitute
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Feedstock
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Ethanol
Sugar
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Fermented
Distillation Column
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Yeast to Aqs.
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Alcohol
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Aqueous
Alcohol
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Residues Animal Feed

Steps involved in ethanol production from cellulosic materials
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Acid and Water Enzymes and Water
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Cellulosic Hemicellulose
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Syrup for
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Feedstock
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Pentose
Acids Break
Fermentation
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Biomass
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into Base Cellulosic
Sugars and
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Fibers
Ethanol
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Distillation Column
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Cellulose and Lignin Fibers
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Cellulose
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Enzymes Solids for
and Hydrolysis and
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Ethanol
Water
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Aqs. Alcohol
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Boiler to
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Lignin Generate Steam

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for Process
• Pruvate serves as a key branching point in fermentations.
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• In an ethanolic type of fermentation, pyruvate is metabolized to acetaldehyde and carbon dioxide, and acetaldehyde
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is then reduced to ethanol
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• Thus, in this process, it is theoretically possible to achieve 2 moles of ethanol for each mole of glucose converted, or
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on a weight basis, a 51 % conversion of glucose into ethanol.
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•
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In practice only 90-95% of the theoretical amount of ethanol is produced as some of the pyruvate is consumed for
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cellular material during culture growth and is not available to serve as an electron acceptor.
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Also, low levels of higher alcohols are produced as metabolic waste products.
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Type of fermentation End products Microorganisms
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Ethanolic Ethanol, Carbon dioxide
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Mixed acid Lactic acid, Formic acid, Acetic acid Zymomonas
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Carbon dioxide, Hydrogen, Ethanol Clostridium and many

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enteric bacteria
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Butanediol As in mixed acid and 2,3-butanediol Bacillus and other

bacteria
Theoretical ethanol yield
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C6H12O6  2C2H5OH  2CO2
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3C5H10O5  5C2H5OH  5CO2
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TEY (kg / ton)  CS (kg / ton)  0.51 kg ethanol
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Mass (kg)
V (L/ton) =
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 (kg/L)
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Where, TEY represents the theoretical ethanol yield, Cs is the concentration of sugars (C6 or C5) present in
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the lignocellulosic biomass, 0.51 is theoretical ethanol yield (gp/gs) constant, V, volume (L); and ρ, is ethanol
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density (0.789 kg/L at 20 ºC).

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Theoretical bioethanol potential analysis
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LCB Structural
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TEY (kg/Ton) TEY (L/Ton)
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Carbohydrate (kg/Ton)
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Rice straw 599 305.5 387
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Wheat straw 616 314 398
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Sugarcane bagasse 599 305.5 387
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Corn Stover 596 304 385
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Liquid fuel characteristics of alcohols, diesel and gasoline
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Characteristic Gasoline Diesel Methanol Ethanol Butanol
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Boiling point °C 32-210 204-343 65 78 118
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Lower heating
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Value (MJ/kg) 44.5
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MJ/lit. 31.9 38.9 15.4 21.1 26.7
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Non conventional energy resources, by Rai, 4th edition, 2010, Khanna Publisher
Uses of Ethanol
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• Hydrous ethanol (95% by volume) or commercial ethanol is used as fuel in specially designed IC engines
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with 25% mileage penalty compared to conventional vehicles.
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• Up to 22% blend of anhydrous ethanol (99.7% by volume) with petrol require no engine modification and
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incurring no mileage penalty and is being used by a large number of automobiles in the world.
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• Anhydrous ethanol is required for the purpose of blending of petrol.
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• The ethanol additive has antiknock properties and is preferred to the more commonly used tetraethyl lead,
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which produces serious air pollution.
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• The excellent combustion properties of ethanol enables an engine to produce up to 20% more power as
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compared to that of petrol.
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(Overview of next lecture)
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Module 06
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(Bioconversion of substrates into alcohol and Thermo-
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chemical conversion of biomass to solid, liquid and gaseous
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fuels)
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Lecture 01 (Part II)
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Content Thermo Chemical Conversion of Biomass to Solid, Liquid and
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Gaseous Fuels
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Thank you
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For queries, feel free to contact at : vvgoud@iitg.ac.in

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Module - 06
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Lecture – 01 (Part II)
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Bioconversion of Thermo Chemical Conversion of Biomass to
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06 substrates into 01 (Part II) Solid, Liquid and Gaseous Fuels
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alcohol and
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Thermo-chemical
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conversion of
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biomass to solid,
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liquid and gaseous
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fuels
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Thermo chemical conversion of biomass, conversion to
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solid, liquid and gaseous fuels
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• Number of technological options available to make use of a wide variety of biomass types as a
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renewable energy source.
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• Conversion technologies may release the energy directly, in the form of heat or electricity, or may
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convert it to another form, such as liquid biofuel or combustible gas (producer gas or bio-gas).
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• Depending on its source, these processes include: combustion, pyrolysis, gasification, and
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liquefaction.
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• Thermo-chemical processes convert biomass into higher-value or more convenient products.
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 The process releases a gas (~6 MJ/kg), a liquid (~17-22 MJ/kg) and/or a char (~18MJ/kg), and
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depending on the technology one of these is the final product.

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 In thermo chemical processes heat is the dominant mechanism to convert the biomass into another chemical
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 The basic alternatives are separated principally by the extent to which the chemical reactions involved are
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allowed to proceed:
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 Thermochemical conversion usually represents such concepts as
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Thermal
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conversion
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• Combustion Excess air Partial air No air
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• Gasification
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• Pyrolysis, and
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Pyrolysis &
• Liquefaction Combustion
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Gasification Hydrothermal
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be al liquefaction
Heat
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All of which involve the high-temperature

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(and occasionally high-pressure) processing of biomass Fuel Gases Liquids

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(CO + H2)
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Starting with a general lignocellulosic biomass of composition (CH20)n, schematic presents alternative
thermochemical processing routes
Thermo chemical conversion processes
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The following schematic represents the thermochemical conversion of biomass to other, more useful
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products.
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 Thermal conversion technologies are robust, and they efficiently convert a wide range of biomass
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feedstocks
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 Addresses seasonal and regional variability issues
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 Utilizes the entire biomass feedstock
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 Thermal conversion provides range of fuel opportunities
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 Ethanol, mixed alcohols, oxygenates

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 Hydrocarbons including gasoline, diesel.

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Drying
Combustion Steam Generation
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T>700°C Heat Process Heat
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Excess oxygen Power
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Oxidant
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H2, CO
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Low or intermediate Btu gas
Gasification
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Fuel or Additional CH4
Catalytic (500-750ºC)
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Non-catalytic (up to synthetic gas processing* CH3OH
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900ºC)
NH3
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Steam
Steam
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Pretreatment
Drying FT products
(CH2O)n
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Size reduction
Densification
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Gas** Combustion
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Liquid Catalytic Fuels &
Pyrolysis (300-700ºC)
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Upgrading Chemicals
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Char Solid fuel, Sorbent &
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Soil enhancer
CO2
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Liquefaction (200- * - Only intermediate-Btu gas is typically processed

CH2O0.3
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400ºC) **- H2, CO,CO2,H2O,CH4,C2H4,C3H6

CO
FT- Fischer Trposch
Thermo chemical conversion processes

A brief description of reactions that take place in different thermal conversion processes of biomass are as
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follows
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1. Torrefaction:
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It is a process of production of carbon-rich solid fuels from biomass. So, gas and liquid parts of the
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conversion do not form a part of the product. Torrefaction has some similarity with the process of
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carbonization, but there are some important differences as mentioned below.
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𝐶𝑛 𝐻𝑚 𝑂𝑝 + heat → Char + CO + CO2 + H2 O + condensable vapors
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Torrefaction Carbonization
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Torrefaction retains most of it, driving away only the Carbonization drives away most of the volatiles
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early volatilized low energy dense compounds &
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chemically bound moistures be al
The torrefaction process on the other hand tries to avoid Carbonization takes place at higher temperatures with a certain
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oxygen as well as combustion level of oxygen that allows sufficient combustion to supply the
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heat for the process

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Torrefaction is a thermal decomposition that takes place • Carbonization is a high temperature (300 to 600 C)
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at low temperature & within a narrow temperature range destructive distillation process
of 200 to 300 C • Carbonization produces more energy dense fuel than
torrefaction, but it has a much lower energy yield
A brief description of reactions that take place in different thermal conversion processes of biomass are as
follows
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2. Pyrolysis:
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In pyrolysis, heavier hydrocarbon molecules of biomass are broken down into smaller hydrocarbon
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molecules, non condensable gases like CO, CO2, and solid carbon as char.
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𝐶𝑛 𝐻𝑚 𝑂𝑝 + heat → ෍ 𝐶𝑎 𝐻𝑏 𝑂𝑐 + ෍ 𝐶𝑥 𝐻𝑦 𝑂𝑧 + ෍ 𝐶
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𝑙𝑖𝑞𝑢𝑖𝑑 𝑔𝑎𝑠 𝑠𝑜𝑙𝑖𝑑
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3. Combustion:
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To explain the conversion process, consider the carbon as the feedstock and write the chemical reaction of
ed op
the process as:
us is c
𝐶 + O2 → CO2 − 393.77 𝑘 𝐽Τ𝑚 𝑜𝑙 of 𝑐𝑎𝑟𝑏𝑜𝑛
be al
ot eri
The positive sign on the right side (+ Q kJ/kmol) of the reaction equations implies that heat is absorbed in
nn at
the reaction. A negative sign ( - Q kJ/kmol) means that heat is released in the reaction.
ca m
It is
Th
When 1 mol of carbon is burnt completely in adequate air or oxygen, it produces ~ 394 KJ heat and CO2
4. Gasification of carbon:
d
ou
In restricted oxygen supply, carbon can be gasified into carbon monoxide. The carbon then produces 72%
G
less heat than it would have in complete combustion, but the partial gasification reaction as shown below
.
on V
produces a combustible gas, CO
si .
is . V
1
𝐶+ O2 → CO − 110.53 M 𝐽Τ𝑚 𝑜𝑙 of 𝑐𝑎𝑟𝑏𝑜𝑛
m of
2
er Pr
r p er
The product of above reaction (gasification), CO, when burnt subsequently in adequate oxygen, then it
rio nd
releases the remaining 72% (283 MJ) of the heat. Thus, the CO retains only 72% of the energy of the
tp du
carbon.
ou te
ith h
w yrig
Apart from that, for complete gasification of a biomass the energy recovery is 75 to 88% due to the
ed op
presence of hydrogen and other hydrocarbons.
us is c
be al
The producer gas reaction is an example of gasification reaction, which produces H2 and CO from
ot eri
nn at
carbon. This product gas mixture is also known as synthesis gas or syngas.
ca m
It is
𝐶 + H2 O → CO + H2 + 131.00 𝑀 𝐽Τ𝑘 𝑚𝑜𝑙

Th
5. Liquefaction
d
ou
G
Liquefaction of solid biomass into liquid fuel can be done through pyrolysis, gasification, and through
.
on V
si .
hydrothermal process.
is . V
m of
In the latter process, biomass is converted into an oily liquid by contacting the biomass with water at
er Pr
elevated temperatures (300 – 350 C) and high pressure (12 – 20 MPa) for a period of time. There are
r p er
rio nd
several other means including the supercritical water process for direct liquefaction of biomass.
tp du
ou te
Pyrolysis:
ith h
w yrig
A pyrolysis process produces pyrolytic oil and gas. When the emphasis is on an oil rather than a gas
ed op
yield, the process may be termed a liquefaction process.
us is c
be al
• Pyrolysis liquids can be sued directly as heating oil.
ot eri
• They have high water content

nn at
ca m
• The low pH of pyrolysis liquids make the liquid highly corrosive

It is
Th
• The HHV value of a pyrolysis liquid ranges from 17 to 20 MJ/kg.

Liquefaction through gasification:
It involves the production of methanol from mixture of H2 and CO (producer gas). The reaction
d
ou
takes place at 330o C and 150 atm.
. G
on V
si .
is . V
2𝐻2 + CO → CH3 𝑂𝐻
m of
• The H2 and CO required for the process can be produced by gasifying biomass.
er Pr
• CO2 and H2S present in produce gas re removed prior to methanol reactor.
r p er
rio nd
• Methanol yield from woody biomass expected to be in the range 480-568 liters/tons.
tp du
• Methanol can be used as liquid fuel in petrol engines with an energy density of 23 MJ/kg.
ou te
ith h
w yrig
Thermochemical conversion—hydrothermal liquefaction (HTL):
ed op
HTL is a unique thermal conversion process that utilizes biomass and water slurries. This makes HTL
us is c
particularly well suited for high water content material, such as algae, municipal solid wastes, or
be al
grasses into bio-based oils.
ot eri
nn at
• HTL bio-oils tend to be higher quality than pyrolysis oils

ca m
• HTL oils have less oxygen.

It is
Th
• But the oil yields for HTL are lower than pyrolysis and
• Oxygen content is still higher than crude oil.
Comparison of some major thermochemical conversion processes
d
ou
. G
on V
si .
is . V
Process Temperature (°C) Pressure (MPa) Catalyst Drying
m of
250 – 330 5 – 20
er Pr
Liquefaction Essential Not required
r p er
300 – 600 0.1 – 0.5
rio nd
Pyrolysis Not required Necessary
tp du
Combustion 700 – 1400 ≥ 0.1 Not required Not essential, but may
ou te
ith h
w yrig
help
ed op
Gasification 500 – 1300 ≥ 0.1 Not required Necessary
200 – 300 us is c
be al
Torrefaction 0.1 Not required Necessary
ot eri
nn at
ca m
It is
Th
d
ou
. G
on V
si .
is . V
Module 06
m of
er Pr
r p er
rio nd
fuels)
tp du
Lecture 02 (Part I)
ou te
ith h
w yrig
Content Thermo-chemical conversion processes combustion,
ed op
gasification, pyrolysis, chemical conversion processes
us is c
be al
Thank you
ot eri
nn at
ca m

It is
Th
d
ou
. G
on V
si .
is . V
m of
er Pr
r p er
rio nd
tp du
Module - 06
ou te
Lecture – 02 (Part I)
ith h
w yrig
ed op
us is c
be al
ot eri

nn at

ca m

It is
Th
d
ou
. G
on V
si .
is . V
m of
er Pr
r p er
rio nd
Bioconversion of Thermo-chemical conversion processes
tp du
06 substrates into 02 (Part I) combustion, gasification, pyrolysis, chemical
ou te
alcohol and Thermo- conversion processes
ith h
w yrig
chemical conversion
ed op
us is c
liquid and gaseous
be al
fuels
ot eri
nn at
ca m
It is
Th
Torrefaction:
d
ou
G
Torrefaction is a thermochemical process carried out in an inert or limited oxygen environment. In this process
.
on V
si .
is . V
biomass is slowly heated to within a specified temperature range and retained there for a stipulated time such
m of
that it results in near complete degradation of its hemicellulose content while maximizing mass and energy
er Pr
r p er
yield of the solid product.
rio nd
tp du
ou te
• Typical temperature range for this process is between 200 oC and 300 oC.
ith h
w yrig
• Temperature above this would result in extensive devolatilization and carbonization of the polymers both
ed op
us is c
of which are undesirable for torrefaction.
be al
• Also, the loss of lignin in biomass is very high above 300 oC. This loss could make it difficult to form
ot eri
nn at
pellets from torrefied products.

ca m
• Moreover, fast thermal cracking of cellulose causing tar formation starts at temperature 300 – 320 oC.
It is
Th
• Thus, upper limit of torrefaction temperature fixed as 300 oC.

Difference between carbonization, pyrolysis, and torrefaction
d
ou
The most important difference between pyrolysis, carbonization, and torrefaction lies in their product motivation
. G
on V
Torrefaction Carbonization Pyrolysis
si .
is . V
Maximize energy and mass yields with Maximize FC and minimize HC content Maximize its liquid production
m of
er Pr
reduction in (O/C) and of the solid product
(H/C) ratios
r p er
rio nd
Torrefaction retains most of it, driving Carbonization Complete devolatilization
tp du
away only the early volatilized low drives away most of the volatiles
ou te
energy dense compounds and
ith h
w yrig
chemically bound moistures
ed op
Torrefaction require relatively slow Carbonization require relatively slow Pyrolysis relies on fast pace of heating
us is c
rates of heating rates of heating
be al to maximize the liquid yield
The torrefaction process tries to avoid Carbonization takes place at higher Pyrolysis takes place at higher
ot eri
oxygen as well as combustion temperatures with a certain level of temperature and utilizes partial oxygen
nn at
oxygen to provide the thermal energy needed

ca m
for this process

It is
Narrow temperature range of 200 – 300 High temperature (> 300 – 600 oC) Thermally decomposes sample by
Th
oC destructive distillation process heating above 300-400 oC

Carbonization produces more energy dense fuel than torrefaction, but it has a much lower energy yield
Degree of Torrefaction
d
ou
The degree of torrefaction depends on the reaction temperature as well as on the time the biomass is subjected
G
to torrefaction
.
on V
si .
is . V
1. Light torrefaction: Occurs at a temperature of 200-240 oC or at 230 oC, when only hemicellulose is
m of
er Pr
degraded leaving lignin and cellulose unaffected.
r p er
2. Medium torrefaction: Occurs at a temperature of 240-260 oC or at about 250 oC, when cellulose is
rio nd
mildly affected.
tp du
ou te
3. Severe torrefaction: Occurs at a temperature of 260-300 oC or at 275 oC characterized by
ith h
w yrig
depolymerization of lignin, cellulose, as well as hemicellulose.
ed op
us is c
Solid
Liquid
be al Gas
Torrefaction
ot eri
products Water Original and H2, CO, CO2,

nn at
Organics modified sugar CH4, CxHy,

ca m
Lipids structure, toluene and

It is
New polymeric benzene

Th
structure,
Ash, char
Combustion
d
ou
G
What is Combustion?
.
on V
si .
is . V
• Oxygen of air reacts with the combustible substances (fuel) resulting in the formation of
m of
er Pr
CO2 and H2O with release of heat,
r p er
rio nd
tp du
𝐶 + 𝑂2 ⇔ 𝐶𝑂2 + 393.77 𝑘 𝐽Τ𝑚 𝑜𝑙 𝑐𝑎𝑟𝑏𝑜𝑛
ou te
ith h
w yrig
• The other combustion reaction is the oxidation of hydrogen in fuel to produce steam
ed op
1
us is c
H2 + 𝑂2 ⇔ 𝐻2 O + 742 𝑘 𝐽Τ𝑚 𝑜𝑙 H2
2
be al
ot eri
nn at
ca m
 Complete oxidation of the fuel takes place with release of heat

It is
Th
 Air requirement is more than stoichiometric amount

Combustion of Biomass
d
ou
Chemically, combustion is an exothermic reaction between oxygen and hydrocarbon in biomass.
. G
on V
si .
is . V
m of
er Pr
𝑝ℎ𝑜𝑡𝑜𝑠𝑦𝑛𝑡ℎ𝑒𝑠𝑖𝑠
r p er
x 𝐶𝑂2 + y H2 𝑂 + sun light C𝑥 (H2 O)𝑦 + x O2
rio nd
(𝑐𝑎𝑟𝑏𝑜𝑛 dioxide) (water) (radiant energy) (glucose) (oxygen)
tp du
ou te
Stored chemical energy
ith h
w yrig
ed op
us is c
Conversion of stored energy to thermal C𝑥2 O)𝑦
C𝑥 (H
energy, radiant, kinetic energy
be al
ot eri
nn at
combustion
x CO2 + y H2 O + 𝑯𝒆𝒂𝒕 C𝒙 𝑯𝟐 𝑶 𝒚 + x O𝟐 + Ignition temp.
ca m
(+ gases + Char + ash)

It is
Th
Direct combustion
d
ou
. G
on V
 In the past combustion of biomass has been widely used to generate heat.
si .
is . V
m of
– At present, it is making a comeback in many industrial applications including generation of
er Pr
r p er
electricity,
rio nd
tp du
 Straightforward conversion of thermal energy into mechanical or electric power results in
ou te
ith h
w yrig
considerable losses
ed op
us is c
– It is not possible to raise the ratio of thermal to mechanical power above 60%.
be al
– However, if the low temperature waste heat can be used productively, for instance for drying
ot eri
nn at
ca m
or heating purposes, much higher overall efficiencies can be obtained.

It is
Th
Courtesy: Biomass Conversion Processes for Energy and Fuels, by S. S. SOFER and O. R. ZABORSKY, 1981, PP, NY
Direct combustion Heat
d
Energy
ou
Fuels and Combustion
. G
on V
Combustion Combustion
si .
is . V
Air and Fuel unit Products
m of
er Pr
Radiant
r p er
Energy
Fuel + Oxidizer → Products of Combustion + Energy
rio nd
tp du
Conductive heat
Biomass
ou te
to surrounding
ith h
Combustion
w yrig
Hot Flue gas
Flame front
ed op
us is c
Radiation
to surrounding
be al
ot eri
Volatile
matter
nn at
Radiation Entrained air

ca m
to wood
It is
Th
Conduction to wood
Burning char
Ash
Wood
Direct combustion
d
ou
. G
on V
Air
si .
is . V
m of
er Pr
Volatile Flaming
Flue Gas
r p er
matter combustion Heat Conduction
Air
rio nd
tp du
Light Convection
Heat Radiation
ou te
to Fuel Glowing Infrared
ith h
Fuel Flue Gas Radiation
w yrig
combustion radiation
ed op
Heat Conduction to
Fuel
us is c
Heat Fixed carbon
be al
(char)
ot eri
nn at
ca m
It is
Air
Th
Combustion
d
ou
Properties of Fuels
. G
– Solid
on V
si .
is . V
 Density
m of
 Moisture content
er Pr
Flaming combustion Glowing combustion

r p er
Volatile matter and Fixed carbon
rio nd
 Sulfur
tp du
 Ash content
ou te
 Calorific value
ith h
w yrig
ed op
Fuel Volatile Matter Fixed Carbon Ash
us is c
Paddy Husk be al 63.3 14.0 22.7
Bagasse 74.0 19.3 6.7
ot eri
nn at
Wood 77 - 87 13 - 21 0.1 - 2.0

ca m
Lignite 43.0 46.6 10.4

It is
Th
Anthracite Coal 5.0 80 15

Combustion of biomass
d
ou
G.
Volatiles and fixed carbon
on V
si .
is . V
m of
 Volatiles: Flaming combustion
er Pr
 Fixed carbon: Glowing combustion
r p er
rio nd
tp du
ou te
ith h
w yrig
ed op
us is c
be al
ot eri
nn at
ca m
Flaming combustion of wood volatiles Glowing combustion of wood char

It is
Th
d
ou
G
 Biomass combustion is a complex process that consists of consecutive heterogeneous and homogeneous
.
on V
si .
reactions.
is . V
m of
 The main process steps are drying, devolatilization, gasification, char combustion, and gas phase oxidation.
er Pr
 The time used for each reaction depends on the fuel size, properties, temperature, and combustion
r p er
rio nd
conditions.
tp du
 Different types of pollutants can be distinguished from the combustion process:
ou te
ith h
w yrig
Complete combustion Incomplete combustion
ed op
At the end of complete combustion, it gives off non- Uncombusted pollutants such as, Carbon dioxide,
us is c
toxic by-products. (Pollutants from complete COC and polycyclic aromatic hydrocarbons (PAH),
be al
ot eri
combustion such as NOX (NO and NO2), CO2, and soot, carbon, H2, HCN, NH3, and N2O.
nn at
H2O)
ca m
It is
Th
Ash and contaminants such as ash particles, SO2, HCl, Cu, Pb, Zn, Cd etc.
d
ou
G
Processes and temperatures in a burning piece of wood
.
on V
si .
is . V
m of
er Pr
Gaseous-phase combustion
Flame (D) Diffusion flame, mostly turbulent- a ‘free’ fire
r p er
rio nd
T >1000o C
tp du
ou te
Heat flow
Simultaneous heat and mass transfer with chemical reaction

Gas flow
ith h
Char (C)
Surface combustion (slow process)
w yrig
500 o C < T < 800 o C
ed op
us is c
Pyrolytic
be alSame problems as in zone “A” but with sources due to
zone (B) pyrolytic reactions
ot eri
200 o C < T < 500 o C

nn at
ca m
Virgin Heat conduction in a medium with moving boundary Mitigation of

It is
wood moisture and gases

Th
(A) T < 200 o C

Combustion reactions
d
ou
 During combustion, molecules undergo chemical reactions.
. G
on V
si .
 The reactant atoms are rearranged to form new combinations (oxidized).
is . V
m of
er Pr
 The reaction equations above represent initial and final results and do not indicate the actual path of the
r p er
rio nd
reaction, which may involve many intermediate steps and intermediate products.
tp du
 This approach is similar to thermodynamics system analysis, where only end states and not path
ou te
ith h
w yrig
mechanism are used.
ed op
Some fundamental reactions of combustion:
 us is c
C + O2  CO2 + 33.8 MJ/kg-C
be al
ot eri
 2H2 + O2  2H2O + 121.0 MJ/kg-H

nn at
S + O2  SO2 + 9.3 MJ/kg-S

ca m

It is
 2C + O2  2CO + 10.2 MJ/kg-C

Th
Combustion reactions
d
ou
G
However, in fuels, the combustion reactions are more complex than above:
.
on V
 In general, air is used in combustion than pure oxygen
si .
is . V
Fuels consists of many elements such as C, H, N, S, and O
m of

er Pr
 In addition to complete combustions, fuels undergo incomplete combustions too.
r p er
rio nd
The composition of air
tp du
 On a molar (or volume) basis, dry air is composed of:
ou te
ith h
w yrig
– 20.9% oxygen O2
ed op
– 78.1% nitrogen N2
– us is c
0.9% CO2, He, H2, and others
be al
ot eri
 A good approximation of this by molar or volume is: 21% oxygen, 79% nitrogen
nn at
ca m
 Thus, each mole of oxygen is accompanied 0.79/0.21 = 3.76 moles of nitrogen

It is
Th
d
• The theoretical air required to complete combustion of fuel results from the equation of stoichiometry
ou
G
of oxygen/fuel reaction.
.
on V
si .
• If combustion of a stoichiometric mixture is complete, then flue gas cannot have neither fuel nor
is . V
m of
er Pr
oxygen.
r p er
rio nd
Stoichiometric equation for biomass:
tp du
C6H10O5+ 6 (O2 + 3.76 N2) → 6 CO2+ 5 H2O + 22.56 N2
ou te
ith h
w yrig
Considering 21% of air is O2 and rest 79% is N2
ed op
Coal Combustion with O2 Gas Composition (vol%)
us is c
CO2 : 13.5
C + O2 --> CO2 H2O : 9.8
be al
For complete combustion to occur, air is always SO2 : 0.4
ot eri
½ O2 + H2 --> H2O
allowed in excess of the stoichiometric N2 : 73.2
nn at
O2 : 3.2
ca m
(theoretical) air requirement.

It is
Th
Air
d
Stoichiometry and Air/Fuel Ratio
ou
. G
on V
si .
is . V
 The stoichiometric quantity of oxidizer is just that amount needed to completely burn a quantity of
m of
fuel or “Stoichiometric Combustion”.
er Pr
r p er
rio nd
 The amounts of fuel and air taking part in a combustion process are often expressed as the ‘air to
tp du
fuel’ ratio.
ou te
ith h
w yrig
 The stoichiometric oxidizer-(or air)-fuel ratio (mass) is determined by writing simple mole
ed op
balances, assuming that fuel reacts to form a ideal set of products. For hydrocarbon fuel given by
us is c
CxHy, the stoichiometric relation can be expressed as.
be al
ot eri
nn at
ca m
It is
Th
Combustion stoichiometry
d
ou
Cu H w + n O2  y CO2 + z H2O
. G
on V
si .
is . V
m of
C balance: y = u
er Pr
H balance: w = 2z, => z = w/2
r p er
O balance: 2n = 2y + z,
rio nd
tp du
=> 2n = 2u + w/2 => n = u+w/4
ou te
ith h
Therefore, the final reaction looks like
w yrig
ed op
w w
Cu H w  ( u  )O2  uCO2  ( )H 2O
us is c
be al 4 2
It is important that for one mole of fuel CuHw there is necessary exactly (u+w/4) moles of oxygen for
ot eri
complete combustion.
nn at
ca m
It is
Th
For simplicity, the simplified composition for air assumed as, O2 - 21% and N2 – 79% (volume basis) i.e.
d
for each mole of O2 in air, there are (79/21) 3.76 moles of N2.
ou
G
𝑤
.
on V
𝐶𝑢 𝐻𝑤 + n (O2 + 3.76 N2 ) → u CO2 + ( ) H2 O + 3.76 n N2
si .
2
is . V
m of
The stoichiometry air to fuel ratio can be found as:
er Pr
r p er
𝑚𝑎𝑖𝑟 4.76 𝑀𝑊𝑎𝑖𝑟
rio nd
𝐴ൗ
𝐹 = 𝑠𝑡𝑜𝑖𝑐 =
𝑚𝑓𝑢𝑒𝑙 1 𝑀𝑊𝑓𝑢𝑒𝑙
tp du
𝑠𝑡𝑜𝑖𝑐
ou te
ith h
Where MWair MWfuel ar ethe molecular weights of the air and fuel, respectively.
w yrig
ed op
𝐴ൗ 𝐹ൗ
𝐹
us is c
𝑠𝑡𝑜𝑖𝑐 𝐴 𝑎𝑐𝑡𝑢𝑎𝑙
The equivalence ratio Φ = 𝐴ൗ
=
𝐹ൗ
𝐹 𝐴
be al
𝑎𝑐𝑡𝑢𝑎𝑙 𝑠𝑡𝑜𝑖𝑐
ot eri
nn at
For fuel rich mixtures, Φ > 1

ca m
For fuel lean mixtures, Φ < 1

It is
Th
For a stoichiometric mixture, Φ = 1

Classification of solid fuels by H/C and O/C ratio
d
ou
Coal Combustion with O2 Gas Composition (vol%)
G
CO2 : 13.5
.
on V
C + O2 --> CO2 H2O : 9.8
si .
is . V
SO2 : 0.4
½ O2 + H2 --> H2O
m of
N2 : 73.2
er Pr
O2 : 3.2
r p er
rio nd
Air
tp du
ou te
ith h
(1) Biomass contains more oxygen with respect to carbon than in
w yrig
coal. This influences the gasification process, as gasification is
ed op
a partial oxidation, and
us is c
(2) Fuels with high O/C ratio have a smaller heating value than
be al
those with low O/C ratio.
ot eri
(3) The high oxygen and hydrogen content of biomass results in

nn at
ca m
high volatile and liquid yields, respectively.

It is
(4) High oxygen consumes a part of the hydrogen in the biomass,

Th
Van Krevelen Diagram for various solid fuels producing less beneficial water, and thus the high H/C content
does not translate into high gas yield.
Application of combustion
d
ou
G
Cooking
.
on V
si .
is . V
I. C. Engine
m of
er Pr
r p er
Steam engine
rio nd
tp du
Boiler
ou te
ith h
w yrig
Domestic heating
ed op
Steel industries
us is c
be al
Brick Kilns
ot eri
nn at
ca m
and many more………….

It is
Th
d
ou
. G
on V
si .
is . V
Module 06
m of
er Pr
r p er
rio nd
fuels)
tp du
ou te
ith h
w yrig
Content Thermo-chemical conversion processes gasification, pyrolysis,
ed op
chemical conversion processes
us is c
be al
Thank you
ot eri
nn at
ca m

It is
Th
d
ou
. G
on V
si .
is . V
m of
er Pr
r p er
rio nd
tp du
Module - 06
ou te
ith h
w yrig
ed op
us is c
be al
ot eri

nn at

ca m

It is
Th
d
ou
. G
on V
si .
is . V
m of
er Pr
r p er
rio nd
tp du
06 substrates into 02 (Part II) gasification, pyrolysis, chemical conversion
ou te
alcohol and Thermo- processes
ith h
w yrig
chemical conversion
ed op
us is c
liquid and gaseous
be al
fuels
ot eri
nn at
ca m
It is
Th
Gasification- The conversion alternative
d
ou
A wide range of technologies are available for the conversion of biomass to various forms of products
. G
on V
(energy).
si .
is . V
m of
Most of these technologies are suitable for either one or few of bio mass resources and have limitations in
er Pr
r p er
terms of total available energy and form of energy.
rio nd
tp du
• The direct use of fuel,
ou te
ith h
• Densification of the raw feedstock and its subsequent used as fuel,
w yrig
ed op
• Digestion to generate biogas,
• us is c
Gasification, incitation and steam generation
be al
ot eri
nn at
are some of the process technologies available for the conversion of biomass to energy, especially electrical
ca m
It is
and/ or heat energy.

Th
Non conventional energy resources, by Rai, 4th edition, 2010, Khanna Publisher
d
ou
Gasification History
. G
on V
• Gasification is an established technology, the first commercial application of which dates back to
si .
is . V
m of
1830.
er Pr
r p er
• In the beginning years, coal and peat were used as feedstocks. In the 1800 century, the nascent idea of
rio nd
tp du
the process was to produce town gas for lighting and cooking.
ou te
• Around 1920, the major shift came in this area, when it was used to produce synthetic chemicals.
ith h
w yrig
• During World War II, biomass gasification systems played a significant role, when due to the shortage
ed op
us is c
of petroleum, wood gas generators called Gasogene or Gazogène were used to power motor vehicles.
be al
• By 1945 heavy vehicles were powered by gasification systems.
ot eri
nn at
ca m
It is
Th
Gaseous fuels from biomass
d
ou
 Renewable energy resource are derived from the by-products of timber industry, agricultural crops, raw
. G
on V
material of the forest, household waste can be gasified using following techniques:
si .
is . V
m of
er Pr
Gaseous Fuels from Biomass
r p er
rio nd
Anaerobic digestion of biomass Biomass Clean combustible
tp du
by bacterial action. gas mix (Producer gas)
ou te
ith h
Anaerobic Digestion Gasification
w yrig
Feedstock Product Feedstock
ed op
Animal dung, Biogas CO2 : 40%
Biomass
us is c
Crops, Biomass CH4 : 60%
Partial
Combustion
be al
CV: 20 MJ/Nm3 CO :19±3 % Product
ot eri
Anaerobic
Digester H2 : 18±2 %
Producer
nn at
CH4 : 3±1 %
Gas
Nutrient rich
ca m
CO2 : 10±2 %
organic manure
N2 : balance
It is
Th
Used for Cooking

Street lightning CV: 4-5 MJ/Nm3
Run small engines
d
However, among all the alternatives, gasification is best suitable alternative in view of the following:
ou
G
• Gasification offers high flexibility in terms of various biomass materials as the feedstock.
.
on V
si .
is . V
• Thermochemical conversion efficiency of gasification is in the range of 70-90 % which is highest
m of
er Pr
among various alternatives.
r p er
• Gasification output capacity, especially in the high output ranges is controlled by availability of
rio nd
tp du
adequate feed materials rather than other technical consideration.
ou te
• The gasification unit has the highest turndown ratio compared to biogas and higher than steam
ith h
w yrig
turbine systems.
ed op
• Gasification output are suitable as a fuel to all types of internal combustion engines with capacity
us is c
derating in the range of 15% to 30%.
be al
ot eri
nn at
ca m
It is
Th
Why Gasification
d
ou
G
Gasification essentially converts a potential fuel from one
.
on V
si .
form to another. Apart from that there are other three
is . V
m of
motivations for such transformation:
er Pr
r p er
rio nd
• It increases the heating value of the fuel by rejecting the
tp du
non-combustible compounds like water and N2
ou te
ith h
• Reduces the carbon-to-hydrogen mass ratio in the fuel.
w yrig
• Biomass contains more oxygen with respect to carbon
ed op
us is c
than coal. This influences the gasification process, as
gasification is a partial oxidation.
be al
ot eri
• Fuels with high O/C ratio have a smaller heating value

nn at
ca m
than those with low O/C ratio.

It is
Th
Gasification
d
ou
G
The word gasification implies converting a solid or liquid into a gaseous fuel by thermochemical method
.
on V
without leaving any solid carbonaceous residue.
si .
is . V
m of
er Pr
 Thermal conversion of organic materials at elevated temperature and a controlled environment leads
r p er
rio nd
to virtually all the raw material being converted to gas.
tp du
 This takes place in two stages.
ou te
ith h
w yrig
 In the first stage, the biomass is partially combusted to form producer gas and charcoal.
ed op
 In the second stage, the C02 and H2O produced in the first stage is chemically reduced by the
us is c
charcoal, forming CO and H2.
be al
ot eri
 The composition of the gas is 18 to 20% H2, an equal portion of CO, 2 to 3% CH4, 8 to 10% CO2,
nn at
ca m
and the rest nitrogen. {Makunda, 1992}. These stages are spatially separated in the gasifier, with
It is
Th
gasifier design very much dependant on the feedstock characteristics.

Makunda et al., (1992) Open-Top Wood Gasifiers, in eds., Johansson B.J., Kelly H., Reddy A.K.N. Williams R.H., Renewables for Fuels and Electricity, Island Press
Washington, D.C. pp. 699-728.
Feed
Process in Gasifier
d
DZ Drying zone
ou
PZ Pyrolysis zone
G
OZ Oxidation zone
RZ Reduction zone
.
on V
Following physical processes takes place in
si .
is . V
gasifier:
m of
er Pr
DZ (upto 200°C)
r p er
DZ: Drying upto 200 oC PZ (upto 600°C)
rio nd
Char
tp du
gases
PZ: Pyrolysis (devolatilization) upto 600 oC
Tar
Air/O2
ou te
- mainly evaporate the water and separates Air
ith h
CO2
Tar
w yrig
H2
CH4
Ash
CO
organic liquids and non-condensable gases OZ
ed op
from char and solid carbon of the fuel RZ (upto 800°C)
us is c
CO
OZ: Combustion upto 1000 oC be al H2
CO2
- oxidizes fuel constituents in an exothermic
ot eri
Syngas CH4
H2 O
reactions
nn at
Ash Tar
ca m
Ash
RZ: Reduction (800°C)
It is
Th
Typical Gasification reactions Reactions
d
Carbon reaction
ou
R1 (Bourdard) C  CO2 
 2CO  172 kJ / mol
G
Fuel
R2 (Water-gas or steam) C  H2O 
CO  H 2  131 kJ / mol
.
on V
si .
R3 (Hydrogasification) C  2 H 2 
 CH 4  74.8 kJ / mol
is . V
Drying zone
(65°C) R4 C  0.5 O2  CO 111 kJ / mol
m of
er Pr
Tar formation Oxidation reaction
Air Steam formation
r p er
+ (230°C)
water
R5 C  O2  CO2  394 kJ / mol
rio nd
vapor
R6 CO  0.5 O2  CO2  284 kJ / mol
tp du
Oxidation zone R7 CH4  2O2 
CO2  2H2O  803 kJ / mol
ou te
(1100°C)
R8 H2  0.5 O2  H2O  242 kJ / mol
ith h
+
w yrig
Primary reduction zone
Shift reaction
ed op
R9 CO  H2O 
CO2  H2  41.2 kJ / mol
Secondary reduction zone
us is c
(825°C) Methanation reaction
R10 2CO  2 H2 
 CH4  H2O  206 kJ / mol
be al
Solid residue
ot eri
and gas R11 CO  3H2 

 CH4  H2O  206 kJ / mol
nn at
(540°C)
R14 CO2  4H2  CH4  2H2O 165 kJ / mol
ca m
Steam-reforming reaction
It is
Th
R12 CH4  H2O 

CO  3H2  206 kJ / mol
The positive sign on the right side (+ Q kJ/kmol) of the reaction equations
implies that heat is absorbed in the reaction. A negative sign (-Q kJ/kmol) R13 CH4  0.5 O2  CO  2H2  36 kJ / mol
means that heat is released in the reaction.
• With the help of above reaction scheme and equilibrium constant, it is possible to predict the equilibrium
d
ou
composition of the gaseous compositions of the gaseous products.
G
• The equilibrium composition for a given solid fuel depends upon air supply per unit weight of biomass.
.
on V
si .
•
is . V
A dimensionless parameter known as the equivalence ratio (ER) is usually defined to characterize the air
m of
supply conditions as follows
er Pr
𝐴ൗ
r p er
𝐹ൗ
𝐹 𝐴 𝑎𝑐𝑡𝑢𝑎𝑙
rio nd
𝑠𝑡𝑜𝑖𝑐
The equivalence ratio Φ = =
𝐴ൗ 𝐹ൗ
tp du
𝐹 𝑎𝑐𝑡𝑢𝑎𝑙 𝐴 𝑠𝑡𝑜𝑖𝑐
ou te
ith h
•
w yrig
The denometer in above equation is the stoichiometric oxygen/air required for the process and it varies
from fuel to fuel. It is one of the important parameters in gasification.
ed op
us is c
• It is generally observed that the effective gasification an optimum ER of 0.2-0.4 is desired.
be al
ot eri
• If it is less than and level of 0.2, it results in incomplete gasification and hence, more char formation,
nn at
with a low-calorific product gas (pyrolysis predominates the process).

ca m
It is
Th
• while higher and ER value of 0.4 will alter gasification into combustion (combustion predominates).
Energy Environ. Sci., 2016, 9, 2939--2977

Classification of Gasifiers
d
Operational issues
ou
Updraft  Slagging and bed agglomeration
G
Fixed
.
on V
Downdraft  Syngas exit blockage
bed
si .
is . V
Crossdraft  Slag mobility issues
m of
and refractory degradation
er Pr
Basis: Relative direction of flow of gasifying agent
r p er
rio nd
Gasifiers Basis: Basis: Velocity of flow of gasifying agent
tp du
Gasifiers Bubbling
ou te
scheme of interaction of
ith h
Basis: scheme of Fluidized Fluidized bed
w yrig
gasifying agent and solid interaction of bed
gasifying agent
ed op
Circulating
fuels. and solid fuels
us is c Operational issues  Bed agglomeration  Ash deposition

be al
ot eri
and defluidization and fouling

nn at
ca m
It is
Entrained Operational issues

Th
bed  Slag mobility  Refractory degradation

 Syngas cooler fouling and plugging
Biomass Gasifiers: Classifications based on gas and feedstock flow path
d
ou
Down Draft Up Draft
G
Cross Draft
.
Thermal and Engine Applications Thermal Applications
on V
Thermal Applications
si .
is . V
m of
er Pr
r p er
rio nd
tp du
ou te
ith h
w yrig
ed op
us is c
be al
ot eri
nn at
ca m
It is
Th
• Old Design • Recent Design

• Reasonably Dry Wood • Reasonably Moist Wood • High Tar High Tar
• Better Gas Quality • Superior Gas Quality • Better Gas Quality High Moisture Wood
Downdraft gasifier
d
ou
Open top
G
Air
.
•
on V
The downdraft type is best suited for a variety of Biomass hopper
si .
is . V
Gas out
Wood chips
biomass.
m of
er Pr
Annular jacket Drying zone
• Due to its design the raw products are forces to pass (350°C)
r p er
Insulation
rio nd
through a high-temperature zone. Pyrolysis zone
tp du
(350 - 600°C)
ou te
As a result most of the unburnt pyrolysis products Oxidation zone
(1000 - 1200°C)
ith h
w yrig
(especially tars) can be cracked into gaseous Producer gas Air nozzle
ed op
Air
hydrocarbons, thus producing a relatively clean gas.
• us is c
In steady state operation, heat of the combustion cause Reduction zone
be al
(700 - 1000°C)
ot eri
wood chips to pyrolyze and lose 70-80% of their weight. Ash

nn at
ca m
Grate
• The downdraft Gasifier, also called the concurrent
It is
Th
Water seal
moving bed gasifier.
Updraft Gasifier Biomass hopper
d
ou
G
Gas out
• The updraft-type gasifier is also called as counter flow gasifier.
.
on V
si .
is . V
Wood chips
• In this type of gasifier, the air enters at the combustion zone
m of
Drying zone
er Pr
and the producer gas leaves near the top of the gasifier.
r p er
rio nd
• This type of gasifier is easy to build and operate. Insulation
tp du
Pyrolysis zone
• The updraft gasifier achieves highest efficiency as the hot gas
ou te
ith h
w yrig
Reduction zone
passes through the fuel bed and leaves the gasifier at a low
ed op
temperature.
us is c
Oxidation zone
(Hearth zone)
• The gas produced has practically no ash but contains tar and
be al
ot eri
Air
water vapour because of passing of gas through unburnt fuel.
nn at
Grate
ca m
Ash
• The updraft gasifiers are suitable for tar-free feed stock (fuels
It is
Th
like charcoal) and are not suitable for high volatile fuels.
Crossdraft Gasifier
d
ou
Biomass
G
hopper
• This type of gasifier, air enters the gasifier through a
.
on V
si .
Wood chips
water-cooled nozzle mounted on one side of the firebox.
is . V
m of
Drying zone
er Pr
• Gasifier operates at a very high temperature and confines Insulation
r p er
rio nd
its combustion and reduction zone near the air nozzle.
tp du
Pyrolysis zone
ou te
Hearth
• zone Reduction zone
ith h
Due to short path length for gasification reactions, this type
w yrig
of gasifier responds most rapidly for change in gas Air Gas out
ed op
production.
us is c
Burning
be al char
Ash
ot eri
• The high exit temperature of the gas and low CO2

nn at
reduction results in poor quality of gas and low efficiency.

ca m
It is
Th
• Therefore, this type of gasifier is not in common use.

Fluidized-bed Gasifier Dirty Fuel Gas
d
ou
G
• Fluidised bed gasifier is most versatile and can operate
.
on V
si .
is . V
on any biomass form.
m of
• It takes the advantage of excellent mixing characteristics
er Pr
and high reaction rates of gas-solid mixture. Biomass Inert Bed
r p er
Feed Fluidized
rio nd
• A fluidized bed gasifer is a chamber with a bed of -inert
tp du
Refractory
particles such as sand -supported by a distributor plate. Lining
ou te
•
ith h
The velocity of the air is progressively increased till the Solids Grating
w yrig
and Gas
upward drag of air on bed particles supports the entire
ed op
weight of the bed.
•
us is c
The moving mass of solid is called a fluidized bed.
be al
ot eri
• The turbulence of the bed increases with velocity above Fluidized

nn at
Air or O2
the minimum fluidization velocity.
ca m
It is
Th
The availability of high area in F.B. and constantly moving mass results in good conversion efficiency and lower
operating temperature compared to fixed beds.
Circulating fluidized bed gasifier
d
ou
Fuel gas
G
• High throughput
.
on V
Cyclone
•
si .
Fuel flexibility
is . V
m of
• Tolerates reasonably high moisture
er Pr
• Gasifier
r p er
Less pollution (no Nox and SOx, less CO2) due to low temperature
rio nd
operation
tp du
ou te
• But, complex process -for gas-solids multiphase flow, chemical reactions,
ith h
Biomass
w yrig
heat & mass transfer
ed op
• Complex operation, precision control of operating parameters is
us is c
Feeder
essentially needed
be al
ot eri
• Unequal pressure distribution across bed Fan

nn at
Air
ca m
• Hot spots, agglomeration, slugging in bed

It is
Th
• Elutriation of solid fines, loss of un-burnt fuel particles from bed CFB Gasifier
• Fuel gas cleaning
BFB Gasifier
d
ou
G
• Compact design and very high throughput Fuel gas
.
on V
• Inferior quality fuels can be used for fuel gas generation
si .
is . V
•
m of
High energy conversion ratio: Intense gas-solids mixing and re-
er Pr
Cyclone
circulation of un-burnt or partially burnt solid particles Gasifier
r p er
rio nd
• Less pollution: (no Nox and SOx, less CO2) due to low temperature
tp du
operation
ou te
ith h
• Complex gas-solids flow phenomena.
w yrig
Biomass Ash
• Maintaining pressure balance in the loop and overall solids
ed op
us is c
circulation. Ash
•
be al
Solids movement through loop seal for continuous operation. Feeder
ot eri
• Maintaining uniform temperature along the height of fast bed reactor.

nn at
Air
ca m
• Fuel gas cleaning, ash disposal etc

It is
Th
Advantages of fluidised bed gasifier
d
ou
G
• Fuel flexibility and type of fuel with calorific value ranging from 800-800kcal/kg can be used.
.
on V
si .
is . V
• Good heat storage capacity to always ensure combustion.
m of
•
er Pr
Quick start up.
r p er
• High combustion efficiency
rio nd
tp du
• High output rate
ou te
•
ith h
Consistent rate of combustion
w yrig
• Usages of fuel with high moisture content
ed op
us is c
• Rapid response to fuel input changes
be al
• Because of low temperature, corrosion caused by alkali compounds in ash significantly reduced.
ot eri
nn at
• Uniform temperature throughout the furnace volume

ca m
It is
• Reduced emission of harmful nitrous oxide

Th
• Sulphur dioxide emission can be reduced to be acceptable level with less expense
Comparison of Combustion and Gasification
d
ou
G
Criteria Combustion Gasification
.
on V
si .
Amount of flue
is . V
More Less
gas
m of
er Pr
Concentration of
Lower Higher
r p er
CO2
rio nd
SO2 emission Higher Lower
tp du
ou te
NOx emission Higher Lower
ith h
w yrig
Generation of
Higher Lower
solid waste
ed op
Mode of
us is c
Difficult Easy
transportation
be al
Value added
ot eri
No Yes
products
nn at
ca m
Application Narrow range Wider range

It is
Th
d
ou
. G
on V
si .
is . V
Module 06
m of
er Pr
r p er
rio nd
fuels)
tp du
Lecture 02 (Part III)
ou te
ith h
w yrig
Content Thermo-chemical conversion processes gasification, pyrolysis,
ed op
chemical conversion processes
us is c
be al
Thank you
ot eri
nn at
ca m

It is
Th
d
ou
. G
on V
si .
is . V
m of
er Pr
r p er
rio nd
tp du
Module - 06
ou te
Lecture – 02 (Part III)
ith h
w yrig
ed op
us is c
be al
ot eri

nn at

ca m

It is
Th
d
ou
. G
on V
si .
is . V
m of
er Pr
r p er
rio nd
tp du
06 substrates into 02 (Part III) pyrolysis, liquefaction and chemical
ou te
alcohol and Thermo- conversion processes
ith h
w yrig
chemical conversion
ed op
us is c
liquid and gaseous
be al
fuels
ot eri
nn at
ca m
It is
Th
Pyrolysis
d
ou
G
The term “pyrolysis” means thermal decomposition or chemical change brought about by heat.
.
on V
si .
is . V
Although, the term could cover torrefaction, carbonization, and pyrolysis processes. But, generally the
m of
term “pyrolysis” is more constraining to thermal process for production of liquid extracts from biomass.
er Pr
r p er
rio nd
tp du
The process is performed at temperatures from 300 to 650 °C and often includes a catalyst with the aim
ou te
ith h
of increasing the energy density of the product by removing oxygen (as water and volatiles).
w yrig
ed op
us is c
be al
ot eri
nn at
ca m
It is
Th
Important milestones in the development and use of PYROLYSIS
d
ou
. G
•
on V
The practice of carbonizing wood to manufacture char has existed for as long as human history has
si .
is . V
been recorded.
m of
er Pr
r p er
rio nd
• At first, production of char was the sole objective of wood carbonization.
tp du
ou te
ith h
w yrig
• In fact, char is the first synthetic material produced by humankind.
ed op
• us is c
However, new byproducts (tars, acetic acid, methanol, acetone) were obtained from wood as
be al
ot eri
civilization progressed and new reactors and bio-oil recovery systems were designed.
nn at
ca m
It is
Th
DOI: 10.1021/acs.energyfuels.7b00641; Energy Fuels 2017, 31, 5751−5775

Important milestones in the development and use of PYROLYSIS
d
ou
. G
• Technologies to recover and utilize condensable pyrolysis products were relatively well developed.
on V
si .
is . V
• This resulted in brick kilns to recover the condensable gases that were normally lost in the pits
m of
end of the 18th
• Iron retorts (vessels) followed brick kilns.
er Pr
Century
r p er
rio nd
• The “acid-wood industry”, also known as the “wood distillation industry”, was established to produce charcoal and
tp du
liquid by-products (e.g., acetic acid, methanol, and acetone).
ou te
ith h
19th Century • The hardwood distillation industry is frequently considered to be the precursor of the modern petrochemical
w yrig
industry.
ed op
us is c
• The rise of the petroleum industry at the beginning of the 20th century, with cheaper products, caused the decline of the
be al
pyrolysis industry.
ot eri
beginning of
nn at
the 20th
• However, the oil crisis during the 1970s forced a reconsideration of biomass pyrolysis as a technology that could
ca m
Century contribute to reducing dependence on fossil fuel.

It is
Th
DOI: 10.1021/acs.energyfuels.7b00641; Energy Fuels 2017, 31, 5751−5775

Thermochemical conversion: Pyrolysis
d
ou
G
• Unlike combustion, pyrolysis carried out in the total absence of O2, except in cases where partial
.
on V
si .
is . V
combustion is allowed to provide the thermal energy needed for this process.
m of
• In pyrolysis, large hydrocarbon components of biomass are broken down into smaller molecules
er Pr
r p er
• Pyrolysis is a promising technique for conversion of waste biomass into useful liquid fuels.
rio nd
tp du
• The composition of the products,
ou te
ith h
w yrig
f (T, P, rate of heating and gas composition during devolatilization)
ed op
us is c
• This process thermally decomposes biomass into gas, liquid, and solid by rapidly heating the biomass
be al
ot eri
above 300-400 oC.

nn at
ca m
- Fast pyrolysis product: mainly liquid fuel (bio-oil)

It is
Th
- Slow pyrolysis products: some gas and solid bio-char

Representation of pyrolysis process using ternary diagram
d
ou
G
• The ternary diagram is useful for representing biomass
.
on V
si .
is . V
conversion processes (pyrolysis).
m of
• The corners of the triangle represent pure carbon, oxygen, and
er Pr
r p er
hydrogen (i.e. 100%) concentration.
rio nd
tp du
• Points within the triangle represent ternary mixtures of these
ou te
ith h
three substances.
w yrig
• The side opposite to a corner with a pure component (C, O, or
ed op
us is c
H) represents zero concentration of that component.
be al
ot eri
nn at
ca m
• Slow pyrolysis (i.e. carbonization) moves the product toward “C” through the formation of solid char.
It is
Th
• Fast pyrolysis moves the product toward “H” and away from “O”, which implies higher liquid product.
Classical Pyrolysis Process
d
ou
Biomass
G
Combustion
Products Feed Alternate Path
.
on V
for Fuel Gas
si .
is . V
m of
Refractory Lined
er Pr
Combustion Chamber
r p er
(Outer Shell)
io d
Combustion
t Combustion
pr un
Drying
d
ou te
ith h
w yrig
Metallic
ed op
Pyrolysis
Gasifier Shell
us is c
be al
Fuel for
ot eri
Fuel Gas Combustion

nn at
Char/Ash Chamber
ca m
It is
Th
Classical Pyrolysis Process (Indirectly Fired, Vertical Flow, Packed Bed)
Pyrolyzer
d
ou
Non-condensable
gases
. G
Cyclone
on V
si .
is . V
Biomass
m of
er Pr
r p er
Gas
rio nd
condenser
tp du
ou te
Char Oil
ith h
collection
w yrig
Bio-oil
ed op
storage
us is c
Screw feeder Gas
burner
be al
ot eri
nn at
ca m
It is
Th
Simplified schematic of a pyrolysis process
Types of pyrolysis
d
ou
G
Pyrolysis process are generally classified into four categories based on heating rate as:
.
on V
• Slow pyrolysis,
si .
is . V
m of
• Fast pyrolysis,
er Pr
•
r p er
Flash pyrolysis and
rio nd
•
tp du
Isothermal pyrolysis.
ou te
ith h
w yrig
Based on the environment or medium in which the pyrolysis is carried out is classified into two types,
ed op
us is c
viz. be al
• High pressure pyrolysis and
ot eri
nn at
• Hydrous pyrolysis
ca m
It is
Th
Slow Pyrolysis
d
ou
G
• The biomass is heated slowly in the absence of oxygen to a relatively low temperature (~ 400 oC) over
.
on V
si .
an extended period of time.
is . V
m of
er Pr
r p er
• It is the oldest form of pyrolysis, which is in use for several years.
rio nd
tp du
ou te
• The process is not used for traditional pyrolysis, where liquid is the main product
ith h
w yrig
ed op
us is c
• Slow pyrolysis is used primarily for char production
be al
ot eri
nn at
• Carbonization and Torrefaction are the types of slow pyrolysis process, in which the production of
ca m
It is
charcoal or char is the primary goal

Th
Fast Pyrolysis
d
ou
G
• The biomass is heated so rapidly that it reaches the peak (pyrolysis) temperature before it decomposes.
.
on V
• In fast pyrolysis, the vapor residence time is in the order of seconds or milliseconds.
si .
is . V
m of
er Pr
r p er
• The primary goal of fast pyrolysis is to maximize the production of liquid or bio-oil.
rio nd
tp du
• The heating rate can be as high as 1000 to 10,000 oC/s, but the peak temperature should be below 650
ou te
oC, if bio-oil is the product of interest.
ith h
w yrig
ed op
us is c
• However, the peak temperature can be up to 1000 oC, if the production of gas is of primary interest.
be al
• Flash and Ultrarapid are the types of fast pyrolysis process and used primarily for the production of
ot eri
nn at
bio-oil and gas.

ca m
It is
Th
Flash Pyrolysis
d
ou
G
• In flash pyrolysis, biomass is heated rapidly in the absence of oxygen to a relatively modest
.
on V
si .
temperature range of 450 -600 oC.
is . V
m of
er Pr
r p er
• The product, containing condensable and non-condensable gas, leaves the pyrolyzer within a short
rio nd
tp du
residence time of 30-1500 ms.
ou te
ith h
w yrig
• Upon cooling, the condensable vapor is then condensed into a liquid fuel known as “bio-oil.” Such
ed op
us is c
an operation increases the liquid yield while reducing the char production.
be al
ot eri
nn at
• A typical yield of bio-oil in flash pyrolysis is 70-75% of the total pyrolysis product.
ca m
It is
Th
d
ou
Pyrolysis in the Presence of a Medium
G
.
on V
si .
In general pyrolysis is carried out in the absence of a medium such as air, but some are performed in a
is . V
m of
medium such as water or hydrogen.
er Pr
r p er
rio nd
Hydropyrolysis
tp du
ou te
ith h
• In this thermal decomposition of biomass takes place in an atmosphere of high-pressure hydrogen.
w yrig
ed op
• Hydropyrolysis can increase the volatile yield and the proportion of lower-molar-mass hydrocarbons.
us is c
• It is different from hydrogasification of char.
be al
ot eri
• Hydropyrolysis can produce bio-oil with reduced oxygen.

nn at
ca m
It is
Th
Hydrous pyrolysis
d
ou
G
• In this process thermal cracking of biomass is carried out in a high temperature water.
.
on V
si .
is . V
• It could convert, raw material into light hydrocarbon for production of fuel, fertilizer, or chemicals.
m of
er Pr
• In a two-stage process, the first stage takes place in water at 200 – 300 oC under pressure.
r p er
rio nd
• In the second stage, the produced hydrocarbon is cracked into lighter hydrocarbon at a temperature of
tp du
around 500 0C.
ou te
ith h
w yrig
• High oxygen content is an important shortcoming of bio-oil.
ed op
us is c
be al
ot eri
nn at
ca m
It is
Th
Approx. heating in a pyrolyzer to achieve final product of interest
d
ou
G
Production of charcoal Fast pyrolysis To Maximize Gas
through carbonization uses step (II) Production use (III)
.
on V
use (I)
si .
is . V
m of
er Pr
To Maximize To Maximize To Maximize
r p er
Char Liquid Yield Gas
rio nd
Production Production
tp du
• slow heating rate ( < 0.01 • use a moderate to slow
• Use a high heating rate
ou te
to 2.0 oC/s) heating rate,
• a moderate final temperature
ith h
Feed • a low final temperature, • a high final temperature
w yrig
and (450 – 600 oC) and (700 – 900 oC) and
• a long gas residence time • a short gas residence time • a long gas residence time
ed op
us is c
be al
I II III
ot eri
nn at
ca m
It is
Th
Char Liquid yield Gas

Production Production
Physical aspects
d
ou
. G
Secondary cracking of volatiles into
on V
char and non condensable gases
si .
is . V
m of
exothermic dehydration vapor or precursor Final stage secondary char
er Pr
of biomass takes place to bio-oil is produced ( ~ 300 – 900 oC). and gases
Initial stage (100300C).
r p er
rio nd
Biomass
Biomass
Biomass
Biomass
Feed
tp du
ou te
ith h
w yrig
ed op
 primary char
us is c
oC) Initial stage primary pyrolysis
Drying (100
(100 – 300 oC) (200- 600 oC)  condensable gases
be al
and
ot eri
 non condensable
nn at
Secondary gases
ca m
Cracking zone
It is
Th
Chemical aspects
d
ou
. G
on V
produce char and non-
si .
condensable gases
is . V
m of
Reaction II
er Pr
Dehydration
r p er
Dehydration
rio nd
Decarboxylation
tp du
Carbonization
Reaction I
ou te
Cellulose
ith h
Active Cellulose
w yrig
Reaction III Reaction IV
depolymerization
Secondary cracking
ed op
Depolymerization and division
us is c
condensable Char, tar, non-
gases condensable gases
be al
ot eri
nn at
forming vapors including tar

ca m
and condensable gases

It is
Th
Thermal conversion processes, process conditions, and product distribution
d
ou
. G
on V
si .
Mode Process Conditions Product Distribution (%)
is . V
m of
Peak Temperature Vapor Residence Time Char Liquid Gas
er Pr
r p er
Slow Moderate (-500 °C) Long (5 – 30 min) 35 % 30 % (70 % water) 35 %
rio nd
tp du
Intermediate Moderate (-500 °C) Moderate (10 – 20 sec) 20 – 25 % 50 % (50 % water) 25 – 30 %
ou te
ith h
Fast Moderate (-500 °C) Short (< 2 sec) 12 % 75 % (25 % water) 13 %
w yrig
ed op
Gasification High (> 800 °C) Moderate (10 – 20 sec) 10 % 5 % tar 85 %
us is c
be al (55 % water)
ot eri
nn at
ca m
It is
Th
Thermochemical conversion (Liquefaction)
d
ou
. G
on V
Hydrothermal liquefaction involves direct liquefaction of biomass into liquid oil with a reacting
si .
is . V
temperature of lower than 400 °C and 10–25 Mpa in aqueous medium. In this process, water is an
m of
er Pr
important reactant and catalyst.
r p er
rio nd
tp du
ou te
• The product of biomass liquefaction is oil which has a much higher energy content than syngas or
ith h
w yrig
alcohol.
ed op
us is c
• If the feedstock contains a lot of water, HTL does not require drying as gasification or pyrolysis.
be al
ot eri
nn at
• The drying process typically takes large quantities of energy and time. The energy used to heat up the
ca m
It is
feedstock in the HTL process could be recovered effectively with the existing technology.
Th
• The complexity of the chemical reactions involved in HTL can be attributed to the complex
d
ou
composition of feedstocks.
. G
on V
si .
is . V
Following are the reactions that may be involved in the liquefaction of carbonaceous materials.
m of
er Pr
• cracking and reduction of polymers such as lignin and lipids,
r p er
rio nd
• hydrolysis of cellulose and hemicellulose to glucose and other simple sugars,
tp du
ou te
• hydrogenolysis in the presence of hydrogen,
ith h
w yrig
• reduction of amino acids,
ed op
• reformation reactions via dehydration, (oxygen in the biomass is removed)
us is c
be al
• decarboxylation, (oxygen in the biomass is removed)
ot eri
nn at
• C - O and C - C bond cleavage, and

ca m
It is
• hydrogenation of functional groups.

Th
The HTL products characterized by their phases are:
d
• bio-crude oil,
ou
G
• aqueous phase,
.
on V
• gaseous phase, and
si .
is . V
• solid residue.
m of
er Pr
r p er
Bio-crude oil production via HTL
rio nd
tp du
• Bio-crude oil obtained from HTL is dark brown and viscous liquid constituting 18–67% of the total
ou te
weight of the feedstock.
ith h
w yrig
• The quality and yield of bio-oil vary with the type of biomass, operating conditions and type of catalyst or
ed op
us is c
co-solvents used. be al
• The HTL bio- oil contains a large fraction of phenolic compounds, where the fraction of polar compounds
ot eri
nn at
such as acids and sugars are very less.

ca m
It is
• The produced bio-oil has energy content about 30–36 MJ/kg, and elemental composition as 64–73% of
Th
carbon, 8–10% of hydrogen, 10–25% of oxygen, 3–5% of nitrogen (Jiang et al. 2018).
The aqueous phase from HTL
•
d
Aqueous phase in HTL is considered as a useful by-product, which constitutes 20–50% of the total weight
ou
G
of feedstock, and majorly depends on the operating conditions and type of biomass.
.
on V
si .
•
is . V
Major chemicals in aqueous phase: organic acids, alcohols, ketones, and phenolic compounds.
m of
•
er Pr
HTL aqueous by-product is considered as a nutrient source (containing N, S, halogens, and minerals) and
r p er
utilized for the cultivation of biomass or can be recycled to enhance bio-oil yield.
rio nd
tp du
Gaseous products from HTL
ou te
ith h
•
w yrig
Gaseous byproducts constitute to 5–10% of the total weight of feedstock and CO2 is the main gaseous
ed op
product of HTL along with other gases such as H2, CO and CH4 in small fractions (Magdeldin et al. 2017).
us is c
be al
Solid residue via HTL
ot eri
nn at
• The solid residues from the HTL process are termed as char (bio-char), containing high fractions of C, H,
ca m
It is
and N (Basu 2013).

Th
• Generally, char from HTL is used as a potential source of nutrient for soil amendment.
Comparison of bio-oil properties
d
ou
. G
on V
HTL Pyrolysis Fossil oil
si .
is . V
Carbon (wt. %) 68–81 56–66 83.0–87.0
m of
er Pr
Sulfur + Nitrogen 0.1 0.1 0.01–5
r p er
(wt. %)
rio nd
tp du
Oxygen (wt. %) 9–25 27–38 0.05–1.5
ou te
ith h
Water (wt. %) 6–25 24–52 <1
w yrig
Density (kg L−1)
ed op
1.10–1.14 1.11–1.23 0.75–1.0
us is c
be al
ot eri
Compared to pyrolysis oil, HTL oils have almost half of the oxygen content, which makes upgrading of HTL
nn at
ca m
boil-oil much easier and less expensive

It is
Th
Furimsky E (2012), Hydroprocessing challenges in biofuels production, catalysis today

Undesirable characteristics of bio-oil and their effects
d
ou
Characteristics Effect
G
Low pH value Corrosion problems
.
on V
si .
is . V
High viscosity Handling and pumping problems
m of
Instability and temperature sensitivity Storage problems
er Pr
r p er
Phase separation
rio nd
Decomposition and gum formation
tp du
Viscosity increase
ou te
ith h
Char and solids content Combustions problems
w yrig
Equipment blockage
ed op
Hydroprocessing can be used to
us is c
Erosion
deoxygenate the oil and
be al
Alkali metals Depositions of solids in boilers, engines, and turbines
subsequently improve the
ot eri
nn at
properties of the bio-oil. This Water content Complex effect on heating value, viscosity, pH,
ca m
homogeneity and other characteristics

deoxygenating process is called
It is
Th
hydrodeoxygenation (HDO). Oxygen content Higher viscosity and lower heating value
Courtsey: Mercader et al., (2010), Production of advanced bio-fuels: Co-refning upgraded pyrolysis oil, Berlin Google Scholar
Furimsky E (2000) Review: catalytic hydrodeoxygenation. Appl Catal A 199:147–190, CrossRefGoogle Scholar
Chemical conversion processes
d
ou
G
Biomass to high added value chemicals, an emerging conversion chemistry
.
on V
si .
is . V
m of
Biomass
er Pr
r p er
rio nd
tp du
ou te
Extraction Biodiesel Sugar Thermochemical
ith h
of chemicals production fermentation conversion
w yrig
ed op
• Proteins • Ethanol
us is c
• Vitamins Glycerol • Lactic acid Bio-SNG
• Fragrances
be al
• Pharmaceuticals
ot eri
Chemicals Chemicals
nn at
ca m
It is
Th
PNNL and NREL

Cement
additive
d
Lignin
ou
Fuel
G
additive
.
on V
Lignocellulosic
si .
is . V
material
m of
Glucose
er Pr
Hemicellulose Arabinose
r p er
rio nd
Xylose
tp du
ou te
Ethanol Xylitol 2,3 Butane diol
ith h
w yrig
ed op
Cellulose
us is c
be al
CTA, HEC, Levulinic acid, Ethanol THF, MTHF, Diphenolic acid, 5-Amino
ot eri
HPMC lactic acid (biofuel) 1,4 Butane Diol, Succinic acid levulinic acid
nn at
(high-volume (platform NMP, lactones (monomers) (pesticide)

ca m
polymers) chemical) (solvents) COOH O

It is
H3C H2N
Th
O COOH
H3C COOH 5-Amino-levulinic acid

HO OH
Levulinic acid
Diphenolic acid PNNL and NREL
Glucose : Platform Chemical for Value-Added Chemicals
d
ou
G.
on V
Acid or Enzyme Hydrolysis
si .
is . V
m of
er Pr
r p er
rio nd
tp du
ou te
ith h
w yrig
ed op
us is c
be al
ot eri
nn at
ca m
It is
Th
PNNL and NREL Corma et. al, Chem. Rev. 107(6), 2411(2007
Th
It is
ca m
nn at
ot eri
be al
us is c
ed op
w yrig
ith h
ou te
Glucose : another platform via oxidation reactions
tp du
rio nd
r p er
er Pr
m of
is . V
si .
on V
. G
ou
d
PNNL and NREL
Th
It is
ca m
nn at
ot eri
be al
us is c
ed op
w yrig
ith h
ou te
tp du
rio nd
r p er
er Pr
Lactic Acid : platform chemical for value-added chemicals
m of
is . V
si .
on V
. G
ou
d
PNNL and NREL
Th
It is
ca m
nn at
ot eri
be al
us is c
ed op
w yrig
ith h
ou te
tp du
rio nd
r p er
Levulinic Acid : platform chemical for value-added chemicals
er Pr
m of
is . V
si .
on V
. G
ou
d
PNNL and NREL
Hemicellulose : platform chemical for value-added chemicals
d
ou
G
O CH2OH
.
on V
Furfuryl alcohol
si .
is . V
• Furfural is a natural precursor
m of
H2 to furan‐based chemicals.
er Pr
CHO
• It has been considered an
Bagasse,
r p er
+ important building block for the
Corn cobs, + H2O, H ( CHOH)3
rio nd
H (C5H8O4)n -3 H2O
Wheat straw,
O production of non
tp du
Rice hulls CH2OH CHO
Pentosan Pentose sugar Furfural petroleum‐derived chemicals, a
ou te
(mainly xylose) ( 2-Furancarboxyaldehyde) new generation of bioplastics,
ith h
(Polypentoside)
w yrig
(mainly xylan)
and potential biofuels or fuel
Oxide catalyst,
ed op
H2 Steam, 400 C additives.
us is c
• Sugar alcohols are important products in the food • Furfural and its derivatives
industry. For instance, xylitol is a pentose sugar have been used to make jet and
be al
CH2OH
ot eri
alcohol used as a sugar substitute in the food diesel fuel range alkanes, to
( CHOH)3
nn at
industry because of its low caloric and O serve as gasoline blend stock.
CH2OH
ca m
anticarcinogenic properties. Furan

It is
Xylitol
•
Th
In addition, xylitol is a building block for a variety

of commodity chemicals.
PNNL and NREL
d
ou
. G
on V
si .
is . V
Module 06
m of
er Pr
r p er
rio nd
fuels)
tp du
ou te
ith h
w yrig
Content Practice problems
ed op
us is c
be al
Thank you
ot eri
nn at
ca m

It is
Th
d
ou
. G
on V
si .
is . V
m of
er Pr
r p er
rio nd
tp du
Module - 06
ou te
ith h
w yrig
ed op
us is c
be al
ot eri

nn at

ca m

It is
Th
d
ou
. G
on V
si .
is . V
m of
er Pr
r p er
rio nd
Bioconversion of
tp du
06 substrates into 03 (Part II) Practice problems
ou te
alcohol and Thermo-
ith h
w yrig
chemical conversion
ed op
us is c
liquid and gaseous
be al
fuels
ot eri
nn at
ca m
It is
Th
Basic combustion Reactants
d
Fuel: (CuHw)
ou
process Products
. G
Combustion Chamber CO2, H2O, N2, O2
on V
si .
is . V
Air: O2 + 3.76N2
m of
er Pr
r p er
rio nd
C u H w  n ( O2  3.76 N 2 )  y CO 2  z H 2O  c N 2  d O2
tp du
• n: stoichiometric coefficient for the oxidizer
ou te
•
ith h
This reaction will yield 5 unknowns (n, y, z, c, d).
w yrig
• Assumption: No excess oxygen in the products, therefore, d=0.
• By balancing number of atoms of each element, we obtain 4 equations.
ed op
us is c
Element Amount in reactants = Amount in products Reduced equation
be al
Carbon u y u=y
ot eri
nn at
Hydrogen w 2z z = w/2
ca m
Oxygen 2n 2y+z n = y+(z/2) or u + (w/4)

It is
Th
Nitrogen 2(3.76) × n 2c c = 3.76 × n

Example 1: A fuel gas fired industrial boiler operates with an O2 concentration of 3 mole percent in the flue
d
ou
gases. Determine the operating air-fuel ratio. Treat the fuel gas as ethane.
. G
on V
si .
is . V
m of
Given: Molecular weight of air = 29
er Pr
Molecular weight of fuel = 30
r p er
rio nd
O2 mole fraction = 0.03
tp du
ou te
ith h
w yrig
“assuming complete combustion” i.e. all fuel C is found in CO2 and all H is found in H2O
ed op
us is c
Reactants be al
Fuel: (C2H6)
ot eri
Products
nn at

ca m
It is
Air: O2 + 3.76N2
Th
Given: we can use O2 fraction to find the air-fuel ratio by writing overall combustion equation, assuming complete
d
ou
combustion
. G
on V
si .
is . V
C 2H 6 + n (O2 + 3.76 N2) 2CO2 + 3 H2O + d O2 + 3.76 n N2
m of
er Pr
2n = 4 + 3 + 2 d
r p er
rio nd
2n = 7 + 2d
tp du
d = n - 7/2
ou te
ith h
w yrig
NO
From mole fraction definition: 2
mole fraction of O2 =
ed op
Nmix
us is c d
be al
=
2 + 3 + d + 3.76n
ot eri
nn at
n − 3.5
ca m
=
It is
2 + 3 + d + 3.76 n
Th
n − 3.5
d
ou
0.03 =
2 + 3 + d + 3.76 n
. G
on V
0.045 + 0.1428 n = n − 3.5
si .
is . V
m of
n = 4.136
er Pr
r p er
rio nd
𝐴 𝑚𝑎𝑖𝑟 4.76 × n × MW𝑎𝑖𝑟
tp du
𝑇ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙; = =
𝐹 𝑚𝑓𝑢𝑒𝑙 1 × MW𝑓𝑢𝑒𝑙
ou te
𝑠𝑡𝑜𝑖𝑐 𝑠𝑡𝑜𝑖𝑐
ith h
w yrig
4.76 × 4.136 × 29
=
ed op
1 × 30
us is c = 19.03
𝑘𝑔𝑎𝑖𝑟
൘𝑘𝑔
be al
𝑓𝑢𝑒𝑙
ot eri
nn at
ca m
It is
Th
Example 2: Develop the combustion equation and determine the air-fuel ratio for the complete combustion
d
ou
of fuel i.e. n-ethane with a) theoretical air, and b) excess 50% air.
. G
on V
si .
is . V
m of
er Pr
Given: Molecular weight of air = 29
r p er
rio nd
Molecular weight of fuel = 30
tp du
ou te
ith h
w yrig
“assuming complete combustion” i.e all fuel C is found in CO2 and all H is found in H2O
ed op
us is c
Reactants be al
Fuel: (C2H6)
ot eri
Products
nn at

ca m
It is
Air: O2 + 3.76N2
Th
a) theoretical air (in this case product do not contain “oxygen”)
d
ou
G
overall combustion equation, assuming complete combustion
.
on V
si .
is . V
C u H w  n ( O2  3.76 N 2 )  y CO 2  z H 2O  3.76n N 2
m of
er Pr
C 2H 6 + n (O2 + 3.76 N2) 2CO2 + 3 H2O + 3.76 n N2
r p er
rio nd
tp du
equating coefficients, u = 2, z = 3, n = 2+(3/2)= 3.5
ou te
ith h
w yrig
substitute equating coefficient in the above equation,
ed op
us is c
C2H 6 + 3.5 (O2 + 3.76 N2)
be al 2CO2 + 3 H2O + 3.76 (3.5 N2)
ot eri
C2H 6 + 3.5 (O2 + 3.76 N2) 2CO2 + 3 H2O + 13.6 N2

nn at
ca m
It is
Th
d
ou
𝑇ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙; = =
G
𝑠𝑡𝑜𝑖𝑐 𝑠𝑡𝑜𝑖𝑐
.
on V
si .
4.76 × 3.5 × 29
is . V
=
1 × 30
m of
er Pr
r p er
= 16.10 ൘𝑘𝑔
rio nd
𝑓𝑢𝑒𝑙
tp du
ou te
ith h
w yrig
ed op
us is c
be al
ot eri
nn at
ca m
It is
Th
b) 50% excess air (in this case product contain “oxygen”)
d
ou
G
C2H 6 + 3.5 (O2 + 3.76 N2) 2CO2 + 3 H2O + 13.6 N2 (Stoic equation)
.
on V
si .
is . V
m of
C2H 6 + 1.5 × 3.5 (O2 + 3.76 N2) 2CO2 + 3H2O + 0.5 × 3.5 O2 + 1.5 × 3.5 × 3.76 N2
er Pr
r p er
rio nd
C2H 6 + 5.25 (O2 + 3.76 N2) 2CO2 + 3 H2O + 1.75O2 + 19.74 N2
tp du
ou te
ith h
w yrig
ed op
50% excess air; = =
us is c
be al 𝑒𝑥𝑐𝑒𝑠𝑠 𝑒𝑥𝑐𝑒𝑠𝑠
4.76 × 5.25 × 29
ot eri
=
1 × 30
nn at
ca m
It is
= 24.15 ൘𝑘𝑔
Th
𝑓𝑢𝑒𝑙
Example 3: Ethane is combusted with 50% excess air, which enters a combustion chamber at 25ºC.
d
ou
Assuming complete combustion, determine the a) air-fuel ratio and b) the percentage of carbon-dioxide by
. G
on V
volume in the product.
si .
is . V
m of
er Pr
C2H 6 + 1.5 × 3.5 (O2 + 3.76 N2) 2CO2 + 3H2O + 0.5 × 3.5 O2 + 1.5 × 3.5 × 3.76 N2
r p er
rio nd
tp du
ou te
C2H 6 + 5.25 (O2 + 3.76 N2) 2CO2 + 3 H2O + 1.75O2 + 19.74 N2
ith h
w yrig
ed op
us is c
50% excess air; = =
𝐹 𝑒𝑥𝑐𝑒𝑠𝑠
𝑚𝑓𝑢𝑒𝑙 1 × MW𝑓𝑢𝑒𝑙
𝑒𝑥𝑐𝑒𝑠𝑠
be al
ot eri
4.76 × 5.25 × 29
nn at
=
ca m
1 × 30
It is
Th
= 24.15 ൘𝑘𝑔
𝑓𝑢𝑒𝑙
NCO
d
2
ou
mole fraction of CO2 =
Ntotal (mix)
. G
on V
si .
is . V
NCO2 = 2
m of
Ntotal = 2 + 3 + 1.75 + 19.74
er Pr
= 26.49
r p er
rio nd
tp du
2
mole fraction of CO2 =
ou te
26.49
ith h
w yrig
= 0.0755 i.e. 7.5% CO2
ed op
us is c
be al
ot eri
nn at
ca m
It is
Th
BOOKS AND REFERENCES
d
ou
. G
on V
si .
is . V
1. Sukhatme S. P., Nayak J. K., Solar Energy: Principles of Thermal Collection and Storage, 3rd Ed., Tata
m of
er Pr
McGraw-Hill Education Pvt. Ltd., 2008.
r p er
rio nd
2. Twidell, J. and Tony W., Renewable Energy Resources, 2nd Ed., Taylor & Francis, 2006.
tp du
3. Khan B. H., Non-Conventional Energy Resources, 2nd Ed., Tata McGraw-Hill Education Pvt. Ltd., 2009.
ou te
ith h
4. Basu, P., Biomass Gasification, Pyrolysis and Torrefaction, Academic Press, Elsevier, 2013.
w yrig
5. S. R Turns, An Introduction to combustion concepts and Applications., 3rd Ed., MHEPL, 2012
ed op
us is c
be al
ot eri
nn at
ca m
It is
Th
Th
It is
ca m
nn at
ot eri
be al
us is c
ed op
w yrig
ith h
ou te
tp du
rio nd
r p er
er Pr
m of
is . V
si .
on V
Thank you
. G
ou
d
anandalakshmi@iitg.ac.in

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d

Department of Chemical Engineering

Indian Institute of Technology Guwahati

Guwahati – 781039, Assam (India)

dioxide (Zabed et al., 2017)

us is c ~ 265 – 492 L/ton

beet are generally used for the production of bioethanol.

gelatinization of starch and it’s conversion

into sugars, respectively

Bioethanol production from (a) sugar crops and (b) starchy

Brazil 14.96us is c 1.07 0.87 6.65 2.03

• concentrated acid and alkali

Conversion of Lignocellulosic biomass into bioethanol

produces two monosaccharide molecules on hydrolysis.

C12 H 22O11 ( Sucrose ) 

most expensive to obtain.

( Cellulose ) ( Glu cos e )

preparation. Finally, ethanol is obtained from fermentation of hexose sugars.

lignocellulosic biomass conversion into bioethanol

Auto-ignition temperature 424.85

Heat of combustion 26800 kJ/kg

(wood, straw) (difficult)

Residues Animal Feed

Lignin Generate Steam

Carbon dioxide, Hydrogen, Ethanol Clostridium and many

Butanediol As in mixed acid and 2,3-butanediol Bacillus and other

density (0.789 kg/L at 20 ºC).

For queries, feel free to contact at : vvgoud@iitg.ac.in

Department of Chemical Engineering

Indian Institute of Technology Guwahati

Guwahati – 781039, Assam (India)

depending on the technology one of these is the final product.

All of which involve the high-temperature

(and occasionally high-pressure) processing of biomass Fuel Gases Liquids

 Ethanol, mixed alcohols, oxygenates

 Hydrocarbons including gasoline, diesel.

Liquefaction (200- * - Only intermediate-Btu gas is typically processed

400ºC) **- H2, CO,CO2,H2O,CH4,C2H4,C3H6

Thermo chemical conversion processes

heat for the process

𝐶 + H2 O → CO + H2 + 131.00 𝑀 𝐽Τ𝑘 𝑚𝑜𝑙

• They have high water content

• The low pH of pyrolysis liquids make the liquid highly corrosive

• The HHV value of a pyrolysis liquid ranges from 17 to 20 MJ/kg.

• HTL bio-oils tend to be higher quality than pyrolysis oils

• HTL oils have less oxygen.

For queries, feel free to contact at : vvgoud@iitg.ac.in

Department of Chemical Engineering

Indian Institute of Technology Guwahati

Guwahati – 781039, Assam (India)

pellets from torrefied products.

• Thus, upper limit of torrefaction temperature fixed as 300 oC.

oxygen to provide the thermal energy needed

for this process

oC destructive distillation process heating above 300-400 oC

products Water Original and H2, CO, CO2,

Organics modified sugar CH4, CxHy,

Lipids structure, toluene and

New polymeric benzene

 Complete oxidation of the fuel takes place with release of heat

 Air requirement is more than stoichiometric amount

(+ gases + Char + ash)

or heating purposes, much higher overall efficiencies can be obtained.