Decree 76,593 and its consequences were adopted purely for economic reasons. Only in 1978 it become evident through work of university groups [2] that ethanol for sugarcane was very close of being a renewable energy source (except for the minor ingredients of pesticides, fertilizers, and some diesel oil needed for its pro­duction). All the energy for the process of crushing the sugarcane, fermenting and distillation originated in the bagasse of the sugarcane. The ratio of the energy con­tained in a 1 L of ethanol to the energy of fossil origin used in the process was approximately 4.53 to 1 when the first evaluation was carried out [3]. Today, evalu­ations are showing that the rate is even better (8 to 1) due to the significant agricul­tural and industrial efficiency improvements [4, 5]. Impressive productivity gains of 3% per year over 30 years have been achieved. As an example, Fig. 4 gives the growth of sugarcane agriculture productivity in different regions of Brazil, from 1977 to 2009, indicating an increase of 51% in the period.

The second oil shock in 1979 led the Government to the drastic move to introduce cars with motors designed to operate exclusively with hydrated ethanol in order to increase ethanol consumption [2] .

A few years earlier President Ernesto Geisel had visited the Air Force Technological Center in Sao Jose dos Campos, Sao Paulo, and was very impressed by the work being done there by engineers, led by Urbano Ernesto Stumpf, on ethanol-fueled cars using hydrated ethanol (95.5% pure ethanol and 4.5% water). Important changes in the engine were needed to use that fuel, which required a compression ratio of 12:1, compared to 8:1 for regular gasoline. The higher com­pression ratio meant higher efficiency, which partly compensated for ethanol’s lower energy content. Combining all these factors, 199 L of pure (anhydrous) eth­anol replace one barrel of gasoline (159 L). This change to engines meant a drastic change in auto manufacture, but under Government pressure, local carmakers adapted and nationalistic elements in the Government saw ethanol as an instru­ment of national independence. In addition to that Brazilian auto manufacturers could no longer export their cars since hydrated ethanol was not available in other countries. It was also a problem to drive Brazilian cars in neighboring countries (and even some states in Brazil) that did not have service stations selling hydrated ethanol. Despite that the production of these cars began in earnest at the end of the decade; between 1979 and 1985, they accounted for 85% of all new car sales [2]. Over this same period, the percentage of ethanol in gasoline reached approxi­mately 20% [1].

Two fleets of automobiles were circulating in the country: some running on gasoline, using a blend of up to 20% anhydrous ethanol and 80% gasoline, and others running on hydrated ethanol. In 1985, the scenario changed dramatically, as petroleum prices fell and sugar prices recovered on the international market. Subsidies were reduced and ethanol production could not keep up with demand. The production of ethanol leveled off but the total amount being used remained more or less constant because the blend was increased to 25% and more cars were using the blend. Thus, by 1990 a serious supply crises occurred and due to a shortage of the appropriate fuel. The government tried to mitigate the shortage importing ethanol and methanol. Methanol was blended with gasoline and ethanol yielding another fuel that could be used in gasoline cars, freeing more ethanol for the neat ethanol powered ones. But, the shortage crisis lasting 1 year scared consumers and the sales of neat ethanol cars dropped rapidly: by the year 2000, it was lower than 1% of total new cars sold.

Then, after 2003, ethanol consumption rose again, as flexible-fuel engines were introduced in the cars produced in Brazil. These cars are built to use pure ethanol with a high compression ratio (approximately 12:1) but can run with any proportion of ethanol and gasoline, from zero to 100%, as they have sensors that can detect the proportion and adjust the ignition electronically. Flex-fuel cars were an immediate hit; today, they represent more than 95% of all new cars sold because they allow drivers to choose the cheapest blend on any given day. Approximately 50% of the gasoline that would otherwise be used in Brazil today was replaced by ethanol. The production of pure ethanol driven cars is being discontinued because of the success with the flexible-fuel engines.

In the 30 years since 1976 ethanol substituted 1.51 billion barrels of gasoline which correspond to savings of US$ 75 billion (in dollars of 2006) taking into account the amount of gasoline saved each year at the world market price [6] .

To assess a new energy technology before considering its implementation, it is essential to perform a life-cycle analysis on its total energy efficiency and environ­ment impact, including both its potential benefits and risks. A viable energy tech­nology should have a significant net energy gain or a carbon footprint reduction based on its objective life-cycle analysis. Chapter 30 reports the process economics and greenhouse gas audit for microalgal biodiesel production. Chapter 31 discusses the sustainability considerations about microalgae for biodiesel production while Chap. 32 reports a life-cycle assessment for algae-to-energy systems.

To emulate the successful Ethanol Program of Brazil, which is clearly an instrument to reduce CO2 emissions from gasoline, a number of countries have adopted ethanol mandates to introduce ethanol in their automotive fleets. As a consequence, it is necessary to subsidize producers at a rate of approximately 11 billion dollars per year mainly in the United States where ethanol is produced from corn.

Table 1 shows the existing mandates in a number of countries and projections of the amount of ethanol that will be needed by 2020/2022.

Present gasoline consumption in these countries is 943.2 billion liters, 82% of present gasoline consumption.

The potential demand for 2020/2022 on the basis of existing mandates [7] is

178.7 billion liters.

Clearly, an enormous effort will have to be made to meet the projected demand for 2020 in the basis of either first — or second-generation technologies.

aSource: From [11] bSource: From [7]

2 Summary

A discussion is made of the policies adopted by the Brazilian government in the mid 1970s of last century to increase the production of ethanol from sugarcane. The suc­cess of such policies can be assessed by the enormous increase in production (from

0. 6 billion liter in 1975/1978 to 27.6 billion in 2009/2010) as well as the sharp decline in production costs which turned this renewable fuel competitive with gasoline.

The aim of this book is to provide the current status and development in the biomass energy research field and report new and highly innovative technology concepts to provide green/clean energy and control climate change. It will point out the poten­tial benefits of these new technology concepts and the technical challenges that we need to overcome to achieve the mission. This book could be helpful to a wide audi­ence including not only energy and environmental scientists and engineers but also industry and academia, teachers and students, and the general public including the policy makers across the world. The book will address a variety of topics and tech­nology concepts ranging from the latest development in smokeless biomass pyroly­sis, Fischer-Tropsch hydrocarbons synthesis for biomass-derived syngas to liquid transportation fuels, catalytic and selective pyrolysis of biomass for production of fuels such as biodiesels and special chemicals such as levoglucosan and phenolic compounds, biomass hydrothermal processing, biomethane and naturally occurring hydrocarbon gas hydrates, to “cellulosic biofuels,” “electrofuels,” and photobiological production of advanced biofuels (e. g., hydrogen, lipids/biodiesel, ethanol, butanol, and/or related higher alcohols) directly from water and carbon dioxide. Advanced bioproducts such as biochar that could bring significant benefits in helping control climate change and sustainable economic development will also be covered. Each chapter typically will describe a specific technology including its fundamental concept, potential benefits, current status, and technical challenges. Therefore, this BioEnergy sciences book will enable readers to quickly understand the up-to-date technical opportunities/challenges so that the readers may also be able to somehow contribute to this mission, since currently energy and environment (climate change) are such huge and urgent issues to human civilization on Earth. Together, we can help over­come the challenges and build a sustainable future with clean renewable energy of tomorrow.

Norfolk, VA, USA James Weifu Lee

Acknowledgments

The editor, James Weifu Lee, would like to thank all of the nearly 100 authors and a number of peer reviewers across the world for their wonderful contributions in sup­port of this book project. The editing work of this book series was accomplished using significant amounts of the editor’s spare time including his family time. Therefore, the editor also wishes to thank his family for their understanding and wonderful support.

Yil

Use of biomass technology can produce high-value products also. For example, cer­tain cyanobacteria and green algae have been used as human foods, sources for vita­mins, proteins, fine chemicals, and bioactive compounds. Chapter 33 reports fed-batch cultivation of Spirulina platensis, which can be used as high-value health nutrient supplement. Chapter 34 discusses the bioprocess development for Chlorophyll extraction from microalgae while Chap. 35 reports the screening methods for bioac­tive compounds from algae. Fermentation of biomass for methane production repre­sents another important bioresource for biofuel production and waste management. Chapter 36 provides a comprehensive review on algae/biomethane production. Methane hydrates created from biomass at the bottom of the vast oceans and in certain permafrost regions may represent another significant resource that could hopefully be explored for utilization in the future as well. Chapter 37 reports methane hydrates on its current status, resources, technology, and potential.

To emulate the successful Ethanol Program of Brazil, which is clearly an instrument to reduce CO2 emissions from gasoline, a number of countries have adopted ethanol mandates to introduce ethanol in their automotive fleets. As a consequence, it is necessary to subsidize producers at a rate of approximately 11 billion dollars per year mainly in the United States where ethanol is produced from corn.

Table 1 shows the existing mandates in a number of countries and projections of the amount of ethanol that will be needed by 2020/2022.

Present gasoline consumption in these countries is 943.2 billion liters, 82% of present gasoline consumption.

The potential demand for 2020/2022 on the basis of existing mandates [7] is

178.7 billion liters.

Clearly, an enormous effort will have to be made to meet the projected demand for 2020 in the basis of either first — or second-generation technologies.

aSource: From [11] bSource: From [7]

2 Summary

A discussion is made of the policies adopted by the Brazilian government in the mid 1970s of last century to increase the production of ethanol from sugarcane. The suc­cess of such policies can be assessed by the enormous increase in production (from

0. 6 billion liter in 1975/1978 to 27.6 billion in 2009/2010) as well as the sharp decline in production costs which turned this renewable fuel competitive with gasoline.

James Weifu Lee

Abstract The field of advanced biofuels and bioproducts may play an increasingly significant role in providing renewable energy and ensuring environmental health for a sustainable future of human civilization on Earth. This chapter as an introduc­tion for the book provides a quick overview of advanced biofuels and bioproducts by highlighting the new developments and opportunities in the bioenergy research & development (R&D) arena in relation to the global energy and environmental challenges. The topics include: (1) Brazil’s sugarcane ethanol as an early and still encouraging example of biofuels at a nationally significant scale, (2) smokeless biomass pyrolysis for advanced biofuels production and global biochar carbon sequestration, (3) cellulosic biofuels, (4) synthetic biology for photobiological production of biofuels from carbon dioxide and water, (5) lipid-based biodiesels,

(6) life-cycle energy and environmental impact analysis, (7) high-value bioproducts and biomethane, and (8) electrofuels.

Use of biomass technology can produce high-value products also. For example, cer­tain cyanobacteria and green algae have been used as human foods, sources for vita­mins, proteins, fine chemicals, and bioactive compounds. Chapter 33 reports fed-batch cultivation of Spirulina platensis, which can be used as high-value health nutrient supplement. Chapter 34 discusses the bioprocess development for Chlorophyll extraction from microalgae while Chap. 35 reports the screening methods for bioac­tive compounds from algae. Fermentation of biomass for methane production repre­sents another important bioresource for biofuel production and waste management. Chapter 36 provides a comprehensive review on algae/biomethane production. Methane hydrates created from biomass at the bottom of the vast oceans and in certain permafrost regions may represent another significant resource that could hopefully be explored for utilization in the future as well. Chapter 37 reports methane hydrates on its current status, resources, technology, and potential.

James Weifu Lee and Danny M. Day

Abstract Smokeless (emission-free, clean, and efficient) biomass pyrolysis for biochar and biofuel production is a possible arsenal for global carbon capture and sequestration at gigatons of carbon (GtC) scales. The world’s annual unused waste biomass, such as crop stovers, is about 3.3 GtC y_1. If this amount of biomass (3.3 GtC y-1) is processed through the smokeless pyrolysis approach, it could pro­duce biochar (1.65 GtC y-1) and biofuels (with heating value equivalent to 3,250 million barrels of crude oil) to help control global warming and achieve energy independence from fossil fuel. By using 1.65 GtC y-1 of biochar into soil and/or underground reservoirs alone, it would offset the 8.5 GtC y_1 of fossil fuel CO. emissions by 19%. The worldwide maximum capacity for storing biochar carbon into agricultural soils is estimated to be about 428 GtC. It may be also possible to provide a global carbon “thermostat” mechanism by creating biochar carbon energy storage reserves. This biomass-pyrolysis “carbon-negative” energy approach merits serious research and development worldwide to help provide clean energy and con­trol climate change for a sustainable future of human civilization on Earth.

J. W. Lee (*)

Department of Chemistry and Biochemistry, Old Dominion University,

Physical Sciences Building 3100B, 4402 Elkhorn Avenue, Norfolk, VA 23529, USA

Whiting School of Engineering, Johns Hopkins University,

118 Latrobe Hall, Baltimore, MD 21218, USA e-mail: jlee349@jhu. edu; jwlee@odu. edu

D. M. Day

Eprida Power and Life Sciences, Inc. ,

6300 Powers Ferry Road, #307, Atlanta, GA 30339, USA

J. W. Lee (ed.), Advanced Biofuels and Bioproducts, DOI 10.1007/978-1-4614-3348-4_3, © Springer Science+Business Media New York 2013

1 Introduction

This approach of smokeless (emission-free, clean, and efficient) biomass pyrolysis with biochar application as soil amendment and carbon sequestration agent was initiated through our joint 2002 US provisional patent application followed by a PCT application [1] . One of the key concepts here is to use a biomass-pyrolysis process to produce certain biofuels and more importantly to “lock” some of the unstable biomass carbon, such as dead leaves, waste woods, cornstovers, and rice straws, into a stable form of carbon—biochar, which could be used as a soil amendment to improve soil fertility and at the same time, to serve as a carbon sequestration agent, since biochar can be stable in soil for thousands of years and can help retain nutrients in soil to reduce the runoff of fertilizers from agriculture lands that would otherwise pollute the rivers and water bodies. The general philosophy or the “idea roots” of this approach can trace back to Lee’s early work in 1998 at Oak Ridge National Laboratory (ORNL) in developing the method for reducing CO2, CO, NOx, and SOx emissions, which subsequently resulted in a US Patent that laid a framework of solidifying carbon dioxide and placing it into soil and/or subsoil earth layers for win-win benefits on carbon sequestration, environmental health, and agricultural productivity [2, 3]. In 2002, when Day of Eprida visited Lee’s lab at ORNL, we shared our visions and together extended this approach with the process of smokeless biomass pyrolysis and using biochar fertilizer as soil amendment and carbon seques­tration agent [4, 5].

When this approach of smokeless biomass pyrolysis and using biochar fertilizer as soil amendment for carbon sequestration was fitst proposed, we encountered various skepticisms from our peers, some of them with very good/tough questions, such as “how stable is biochar when used as carbon sequestration agent in soil?” and “how long would your envisioned biochar fertility effect last in soil?” In our minds, there were no doubts that biochar material and its fertility effects (such as cation exchanging capacity) could be stable for hundreds and perhaps thousands of years. However, to provide an absolutely clear answer to this type of questions, it would require a long-term biochar-soil experiment that lasts hundreds of years, which would be practically impossible to complete in our life time. We presented our findings first at the USDA Carbon Sequestration Conference in November of 2002 and included references to the “black carbon” in the prehistoric (pre-Columbian) “Terra Preta” soils in Amazonia [6, 7]. Subsequently, one of us (Day) organized and sponsored the first two US biochar scientific meetings and held briefings around the world to educate and further the use of biochar. The first US biochar and energy production scientific meeting which was sponsored by Eprida (Day) held in June 2004 at the University of Georgia at Athens with about 60 participants from across the world, including Brazil, Austria, Germany, New Zealand, Japan, and the USA. Since then, the approach of smokeless biomass pyrolysis and biochar soil application gradually became a hot research and development topic across the world.

Because biochar is not completely digestible to microorganisms, a biochar-based soil amendment could serve as a permanent carbon-sequestration agent in soils/ subsoil earth layers for thousands of years. As indicated by the recent discovery of biochar particles in “Terra Preta” soils formed by pre-Columbian indigenous agriculturalists in Amazonia, biochar materials could be stored in soils as a means of carbon sequestration for hundreds and perhaps thousands of years. The longest lifetime of biochar material that has been reported with scientific evidence is about

38,0 years, according to the carbon isotope dating of a prehistoric Cro-Magnon man’s charcoal painting discovered in the Grotte Chauvet cave [8]. The black car­bon in a “Terra Preta” soil at the Acutuba site has been dated about 6,850 years ago [9]. At the Jaguariuna soil site in Brazil, some high abundance of charcoal found in the summit soil was dated to occur about 9,000 years ago [10]. These carbon-isotope dating results all indicate how stable and permanent the biochar carbon sequestration can be. Through a 14C-labeling study, the mean residence time of pyrogenic carbon in soils has now been estimated in the range of millennia [11].

Here, we must point out that the practice of the pre-Columbian indigenous agriculturalists may or may not be applicable to achieving our envisioned clean energy production and global biochar carbon sequestration, although the discovery of biochar particles in “Terra Preta” soils seems to provide quite nice support for the proposed approach of smokeless biomass pyrolysis using biochar fertilizer for soil amendment and carbon sequestration. First of all, the biochar materials accumulated in the “Terra Preta” soil were probably resulted from some low-tech processes, including (1) “slash and burn,” (2) “slash and char,” and (3) wild fires. All of these three processes generate large amounts of hazardous smokes that can impact air quality. In the practice of “slash and burn,” trees, bushes, and other green plants are cut down and burned in the field to clear the land for cropland. The burning of biomass in open fields creates large amounts of hazardous smoke similar to a wild fire; the biochar formed through the slash-and-burn techniques represents only about 1.7% of the pre-burn biomass [12]. “Slash and char” is a practice to make charcoal from biomass by use of conventional charcoal kilns [11, 13] , which is better than the practice of “slash and burn,” but would still produce large amount of smoke. Use of conventional charcoal kilns for charcoal production at a gigatons of carbon (GtC) scale would produce large amounts of smoke (pollutants including soot black-carbon particles) that are not acceptable to the environment and air quality, in addition to allowing heat, energy, and valuable chemicals to escape into the atmosphere. A recent study indicates that black-carbon aerosols which can directly absorb solar radiation might have substantially contributed to the rapid Arctic warming during the past 3 decades [14, 15]. Therefore, a smokeless and efficient modern biomass — pyrolysis process is essential to achieve the mission of annually converting gigatons of biomass into biochar and biofuel. Development and deployment of a modern biomass-pyrolysis biofuel/biochar-producing process would enable collecting of the “smoke” (organic volatiles and gases) into the biofuel fraction for clean energy (e. g., hydrogen and/or liquid fuels) production. Therefore, further development and use of this type of smokeless biofuel/biochar-producing biomass-pyrolysis tech­nologies are needed for the envisioned large (GtC) scale mission of mitigating global CO2 emissions, and, at the same time, ensuring good air quality.

Furthermore, the “Terra Preta” soils in Amazonia rain forest region represent only a tiny spot on Earth. What one may learn from there may or may not be useful to the rest of the world because of the differences in climates, soil types, crops and ecological systems, and other factors. More importantly, for the envisioned modern application of biochar as a meaningful arsenal for global carbon sequestration to control global warming, it would require an operation of both biochar production and soil application at GtC scales, which have never been done in any human his­tory. Serious studies across the world are needed before this approach could be considered for practical implementation.

Therefore, in the following, we provide a quick overview of the biomass-pyrolysis “carbon-negative” energy approach and discuss its future research and development opportunities.

James Weifu Lee

Abstract The field of advanced biofuels and bioproducts may play an increasingly significant role in providing renewable energy and ensuring environmental health for a sustainable future of human civilization on Earth. This chapter as an introduc­tion for the book provides a quick overview of advanced biofuels and bioproducts by highlighting the new developments and opportunities in the bioenergy research & development (R&D) arena in relation to the global energy and environmental challenges. The topics include: (1) Brazil’s sugarcane ethanol as an early and still encouraging example of biofuels at a nationally significant scale, (2) smokeless biomass pyrolysis for advanced biofuels production and global biochar carbon sequestration, (3) cellulosic biofuels, (4) synthetic biology for photobiological production of biofuels from carbon dioxide and water, (5) lipid-based biodiesels,

(6) life-cycle energy and environmental impact analysis, (7) high-value bioproducts and biomethane, and (8) electrofuels.