Biomass Fundamentals Module 2: Definitions of Biomass A capstone course for BioSUCCEED: Bioproducts Sustainability: a University Cooperative Center of Excellence in EDucation The USDA Higher Education Challenge Grants program gratefully acknowledged for support

This course would not be possible without support from: USDA Higher Education Challenge (HEC) Grants Program www.csrees.usda.gov/funding/rfas/hep_challenge.html

What is biomass? Quiz M2.1 According to the US Department of Energy: Biomass is any organic material made from plants or animals. Domestic biomass resources include agricultural and forestry residues, municipal solid wastes, industrial wastes, and terrestrial and aquatic crops grown solely for energy purposes. In general, it is a carbon- containing substance or material that has a biological origin, is renewable, has little to no impact on green house gases, and is degradable Quiz M2.1 1. Which of the following cannot be considered biomass according to the DOE definition: (a) corn stover; (b) poultry; feathers; (c) clay; (d) human hair 2. Which of the following can be considered a biomass according to the general definition: (a) petroleum; (b) carbon dioxide; (c) diamond; (d) none of the above 3. What can potentially be another name for biomass: (a) biomaterial; (b) biochemical; (c) bioenergy; (d) all of the above From the US DOE: Biomass can be converted to other usable forms of energy and is an attractive petroleum alternative for a number of reasons. First, it is a renewable resource that is more evenly distributed over the Earth's surface than are finite energy sources, and may be exploited using more environmentally friendly technologies. Agriculture and forestry residues, and in particular residues from paper mills, are the most common biomass resources used for generating electricity and power, including industrial process heat and steam, as well as for a variety of biobased products. Use of liquid transportation fuels such as ethanol and biodiesel, however, currently derived primarily from agricultural crops, is increasing dramatically. Please see: http://www1.eere.energy.gov/biomass/index.html

Origins of biomass Where does it come from? HIGHLIGHT: AMBER Biomass comes from plants and animals Generally a whole component byproduct of their metabolism, or some modification It has been useful for the development of civilization It is part of a cycle of biosynthesis (manufacture) and biodegradability (death) The English word amber stems from the old Arabic word anbargris and refers to an oily, perfumed substance secreted by the sperm whale. Middle English ambre > Old French ambre > Medieval Latin ambra (or ambar). It floats on water and is washed up on the beaches. Due to a confusion of terms (see: http://www.geocities.com/pieterderideaux/abu_zaid.html, it became to be the name for fossil resin or tree sap. Amber is fossilized tree resin; resin is the semi-solid, amorphous biomass secreted in wood cells.

Why is it important? Quiz M2.2 1. Which of the following aspects of civilization did not benefit in some way from biomass? (a) housing construction; (b) food cultivation; (c) clothing; (d) all of the above 2. Where does ethanol come from? (a) wood; (b) wheat; (c) corn; (d) all of the above 3. Does biomass contribute to green house gas accumulation? (a) yes; (b) no Biomass is a source of materials (food, wood, paper, rubber, leather) Biomass is a source of fuel (ethanol, wood, biodiesel, oil) Biomass is a source of chemicals (rosins, detergents, sugars, terpenes) A recent article on ethanol from wood (believe it or not) can be found at: http://www.renewableenergyworld.com/rea/news/story?id=22228 The green house effect or green house gases: The "greenhouse effect" is the heating of the Earth by greenhouse gases.  It is named this way because of the trapping of heat by the panes (analogous to the gases) of a greenhouse.  Short-wavelength radiation from the sun passes the earth's atmosphere, is absorbed by the surface of the Earth, causing it to warm.  Part of the absorbed energy is radiated back to the atmosphere as long wave radiation.  Little of this long wave radiation escapes back into space because it cannot pass through the greenhouse gases located in the atmosphere. The greenhouse gases selectively transmit the radiation, trapping some and allowing some to pass. The greenhouse gases absorb this energy and reemits the waves downward, causing the lower atmosphere to warm. Trees can produce some really fascinating chemicals such as aspirin (anti-inflammatory), taxol (cancer drug), and quinine (malaria drug); see: http://www.treedictionary.com/DICT2003/shigo/TREECHEM.html

What is petroleum? FUEL & MATERIALS!!! Drilling for fuel Thought to be the decomposition product of animal and/or plant matter after protracted periods of time Needs to be “refined” to obtain usable chemicals for energy and materials (plastics, resins, composites, tars, asphalts, waxes, etc.) However, difficult to ascertain exactly how formed US uses 25% or more of world supply to support its infrastructure The above molecule is a representation of octane, the basic molecule that provide energy rich gasoline for liquid transportation needs in the US and the world. For a simple primer on petroleum, please see: http://www.need.org/needpdf/infobook_activities/ElemInfo/PetroE.pdf Geologists view crude oil and natural gas as the product of compression and heating of ancient organic materials (i.e. kerogen) over geological time. Formation of petroleum occurs from hydrocarbon pyrolysis, in a variety of mostly endothermic reactions at high temperature and/or pressure.[9] Today's oil formed from the preserved remains of prehistoric zooplankton and algae, which had settled to a sea or lake bottom in large quantities under anoxic conditions (the remains of prehistoric terrestrial plants, on the other hand, tended to form coal). Over geological time the organic matter mixed with mud, and was buried under heavy layers of sediment resulting in high levels of heat and pressure (known as diagenesis). This caused the organic matter to chemically change, first into a waxy material known as kerogen which is found in various oil shales around the world, and then with more heat into liquid and gaseous hydrocarbons in a process known as catagenesis. Geologists often refer to the temperature range in which oil forms as an "oil window"—below the minimum temperature oil remains trapped in the form of kerogen, and above the maximum temperature the oil is converted to natural gas through the process of thermal cracking. For more on the origins: http://kk.org/ct2/2008/06/the-unclear-origins-of-oil.php

What are the similarities between biomass and petroleum? Quiz M2.3 Petro-economy vs. bio-economy Petroleum is believed to be the result of biomass being compressed under high pressure and a long time in an anoxic environment However, petroleum is richer in energy by approximately 40% on a gal/gal basis, it is not renewable, and contributes to green house gas pollution 1. For which of the following does petroleum not contribute in a petro-economy: (a) gasoline; (b) candles; (c) PVC piping (d) cotton 2. Where does ethanol come from? (a) wood; (b) wheat; (c) corn; (d) all of the above 3. Does biomass contribute to green house gas accumulation? (a) yes; (b) no Petroleum and biomass contribute to the manufacture of almost everything that you can think of. What is the difference? Oh, well, it’s just that biomass conversion was considered to be too expensive to compete with “cheap,” “abundant” oil! Well, we all know that THAT is not the case anymore! The following website contains some very nice background information on petroleum, what is in a barrel of “crude,” what chemicals can be made, and the environmental implications. A wonderful review by Ralph Hardy was written on the subject of the bio-based economy which can be found at: http://www.hort.purdue.edu/newcrop/ncnu02/v5-011.html To obtain newsletters on the future economy, go to: http://www.bio-economy.net/ To see a wonderful video on the future world and how it may appear, go to: http://www.youtube.com/watch?v=hSwnSW5308U

What is bioenergy? ESSAY You and me are bioenergy! It is a natural form of energy that does not depend on non- renewable sources, like petroleum; referred to as a biofuel Ethanol, biodiesel, pyrolysis oil, and butanol are typical bioenergy stock fuels We consider solar, wind, ocean currents, geothermals, nuclear, and others are alternative energy sources not to be confused as bioenergy ESSAY At this point, describe in a page or less, how bioenergy contributes to your lifestyle or how you would like it to. Or if that is too difficult, discuss how alternative fuels are incorporated into your life or how you would like to include them. A photo of a sugarcane is shown above – the traditional source of easily fermentable starting material for ethanol production Biodiesel is the most common biofuel in Europe. In the US, biodiesel is not practical because we rely almost exclusively on gasoline, especially for light 'First-generation biofuels' refer to biofuels made from sugar, starch, vegetable oil, or animal fats using conventional technology.duty vehicle needs (the bulk of our transportation needs). More will be discussed in the “bioenergy” course in the BioSUCCEED series.

Bioethanol Ethanol-producing corn plants in the The second simplest alcohol on the planet (C2H6OH); also known as grain alcohol (primary origin) as opposed to methanol, simplest alcohol (wood alcohol) Ethanol or ethyl alcohol as we have known it for thousands of glorious, fun-filled years! It has within the last 10 years been mandated as a fuel additive to replace MTBEs (methyl tertiary butyl ether, an oxygenation chemical) to continue clean burning of fuel and thus improve air quality It currently supplies about 3% of our total liquid fuel needs We consider solar, wind, ocean currents, geothermals, nuclear, and others are alternative energy sources not to be confused as bioenergy Ethanol-producing corn plants in the Midwest of the USA (the bread basket). Space filling molecular model of ethanol; black = carbon atoms, white = hydrogen atoms, and red = oxygen atom A methanol economy was proposed several years ago: Beyond Oil and Gas: The Methanol Economy , George A. Olah, Angewandte Chemie International Edition Volume 44, Issue 18, Pages 2636-2639, 2005; If you cannot access this article, please write us at biosucceed@NCSU.edu and we will be glad to send it to you free of charge. The oldest organic reaction is probably the fermentation of sugar into ethanol.

Biodiesel Another incredibly useful form of liquid fuel However, it is a vegetable oil and fatty acid product (an ester) Made from the transesterification of vegetable oil using an alcohol such as methanol (most common): the three fatty acids on the glycerol residue are esterified to 3 molecules of methanol leaving behind glycerin (a tri-alcohol) Prof. Chavanne of Belgium invented biodiesel in 1937 Generally used ast B99 blends (1% petrodiesel is added) to avoid molding of fuel Quiz M2.4 1. Which has a higher energy value: (a) gasoline; (b) methanol; (c) ethanol; (d) butanol 2. What common oils can make biodiesel: (a) soybean; (b) corn; (c) rapseed; (d) all of the above 3. What is an ester: (a) a female’s name; (b) an organic product also known as an ether; (c) an alcohol-fatty acid compound; (d) all of the above Approximate Heating Value of Common Fuels Natural Gas 1,030 Btu/cu ft 100,000 Btu/therm Propane 2,500 Btu/cu ft 92,500 Btu/gal Methane 1,000 Btu/cu ft Landfill gas 500 Btu/cu ft Butane 3,200 Btu/cu ft 130,000 Btu/gal Methanol 57,000 Btu/gal Ethanol 76,000 Btu/gal Fuel Oil Kerosene 135,000 Btu/gal #2 138,500 Btu/gal #4 145,000 Btu/gal #6 153,000 Btu/gal Waste oil 125,000 Btu/gal Biodiesel – Waste vegetable oil 120,000 Btu/gal Gasoline 125,000 Btu/gal Wood Softwood 2-3,000 lb/cord 10–15,000,000 Btu/cord Hardwood 4-5,000 lb/cord 18–24,000,000 Btu/cord Sawdust – green 10-13 lb/cu ft 8-10,000,000 Btu/ton Sawdust – kiln dry 8-10 lb/cu ft 14-18,000,000 Btu/ton Chips – 45% moisture 10-30 lb/cu ft 7,600,000 Btu/ton Hogged 10-30 lb/cu ft 16-20,000,000 Btu/ton Bark 10-20 lb/cu ft 9-10,500,000 Btu/ton Wood pellets – 10% moisture 40-50 lb/cu ft 16,000,000 Btu/ton Hard Coal (anthracite) 13,000 Btu/lb 26,000,000 Btu/ton Soft Coal (bituminous) 12,000 Btu/lb 24,000,000 Btu/ton Rubber – pelletized 16,000 Btu/lb 32-34,000,000 Btu/ton Plastic 18-20,000 Btu/lb Corn – shelled 7,800-8,500 Btu/lb 15-17,000,000 Btu/ton cobs 8,000-8,300 Btu/lb 16-17,000,000 Btu/ton Electricity 3412 Btu/kilowatt hour Prepared by: John W. Bartok, Jr., Agricultural Engineer University of Connecticut, Storrs CT 06269-4087 December 2004

What are the uses of biomass? Housing/Shelter Food Clothing Plastics/Composites Drugs/Medicines Books/Media Carbon sequestration Carbon credits Using biomass to achieve a carbon balance The combustion (direct or indirect) of biomass as a fuel also returns CO2 to the atmosphere.  However this carbon is part of the current carbon cycle: it was absorbed during the growth of the plant over the previous few months or years and, provided the land continues to support growing plant material, a sustainable balance is maintained between carbon emitted and absorbed. (a) As trees in the energy plantation grow, they absorb carbon dioxide from the atmosphere. (b) During photosynthesis the trees store carbon in their woody tissue and oxygen is released back to the atmosphere. (c) At harvest, woodfuel is transported from the plantation to the heat or power generating plant. (d) As the wood is burned at the heat or power generating plant the carbon stored in the woody tissue combines with oxygen to produce carbon dioxide, this is emitted back to the atmosphere in the exhaust gases.  Permission to reproduce obtained from copyright@hmso.gov.uk

Examples of biomaterials Typical Renewable-based Dental implants Artificial joint Mammary gland implants Artificial skin False eye Prosthetic joint Cadaver implant Wood & associated biopolymers Plants & extractives Forest residues Modified wood/agro- biopolymers Renewable natural material for specific function

Photosynthesis  Biomass 1g fixed absorbed R = CHO Chlorophyll a R = CH3 Chlorophyll b

CO2 Emissions One Driver for New Economy Mark A. Paisley, “Biomass Energy”, Kirk-Othmer Encyclopedia of Chemical Technology, John Wiley & Sons, Inc. (2002)

Alternate Feedstock: Biomass Biomass: Organic matter available on a renewable basis. Advantages: Naturally abundant Sustainable Reduce dependence on petroleum Productive use of wastes Lower emissions Growth in rural communities

The Composition of Biomass Starch (Glucose) Lignocellulosic Biomass Oils and Proteins

Lignocellulosic Biomass Cellulose Hemicelluloses Lignin

Cellulose

Lignin Biosynthesis II Anselme Payen 1838: Reacts wood with nitric acid and then sodium hydroxide. Remaining material he names Cellulose. Schulze 1857: Names dissolved material Lignin from the latin lignum meaning wood. Phenolic Polymer - The Glue that Holds the Fibers Together 3 Dimensional Crolinked Network Branched Polymer/Polydisperse (Large and Small Polymers) Lignin Biosynthesis II

Hemicelluloses Gymnosperm hemicelluloses Approximately 20% of the total carbohydrate content Alternating Glucose & Mannose along the main chain; Galactose branches off; Random acetates at C5 & C3 of main chain Galactoglucomannans Softwood Hemicelluloses (major) The principle hemicellulose of softwoods is the galactoglucomannans (~ 20% of woody material) They are subdivided as : High Galactose content: Galactose 1/Glucose 1/Mannose/4 Low Galactose content Galactose 0.1/Glucose 1/Mannose/3

Chitin 2nd most plentiful polysaccharide on earth Can form chitosan Usually not fully deacetylated. Deactylation value has striking effect upon solubility and crystallinity Can form cationic site (as ammonium salt) Rare in nature This is the “acetyl” group (CH3C=O) that characterizes chitin; once removed, it makes chitosan, the de-acetylated by-product

Biorefinery