Biohydrogen production fundamentals and technology advances

Biohydrogen Production Fundamentals and Technology Advances Debabrata Das Namita Khanna Chitralekha Nag Dasgupta Tai Lieu Chat Luong Biohydrogen Production Fundamentals and Technology Advances Biohydrogen Production Fundamentals and Technology Advances Debabrata Das Namita Khanna Chitralekha Nag Dasgupta CRC Press Taylor & Francis Group 6000 Broken Sound Parkway NW, Suite 300 Boca Raton, FL 33487-2742 © 2014 by Taylor & Francis Group, LLC CRC Press is an imprint of Taylor & Francis Group, an Informa business No claim to original U.S Government works Version Date: 20131021 International Standard Book Number-13: 978-1-4665-1800-1 (eBook - PDF) This book contains information obtained from authentic and highly regarded sources Reasonable efforts have been made to publish reliable data and information, but the author and publisher cannot assume responsibility for the validity of all materials or the consequences of their use The authors and publishers have attempted to trace the copyright holders of all material reproduced in this publication and apologize to copyright holders if permission to publish in this form has not been obtained If any copyright material has not been acknowledged please write and let us know so we may rectify in any future reprint Except as permitted under U.S Copyright Law, no part of this book may be reprinted, reproduced, transmitted, or utilized in any form by any electronic, mechanical, or other means, now known or hereafter invented, including photocopying, microfilming, and recording, or in any information storage or retrieval system, without written permission from the publishers For permission to photocopy or use material electronically from this work, please access www.copyright com (http://www.copyright.com/) or contact the Copyright Clearance Center, Inc (CCC), 222 Rosewood Drive, Danvers, MA 01923, 978-750-8400 CCC is a not-for-profit organization that provides licenses and registration for a variety of users For organizations that have been granted a photocopy license by the CCC, a separate system of payment has been arranged Trademark Notice: Product or corporate names may be trademarks or registered trademarks, and are used only for identification and explanation without intent to infringe Visit the Taylor & Francis Web site at http://www.taylorandfrancis.com and the CRC Press Web site at http://www.crcpress.com Contents Foreword .xv Preface xvii Authors xix Introduction 1.1 Introduction 1.1.1 Global Environmental Issues 1.2 Nonconventional Energy Resources 1.2.1 Solar Energy 1.2.2 Wind Energy 1.2.3 Hydropower .8 1.2.4 Tidal Energy 1.2.5 Geothermal Energy 1.2.6 Biomass Energy .9 1.2.7 Hydrogen Energy and Fuel Cell 11 1.3 Conventional Hydrogen Technologies and Limitations 12 1.4 Biological Hydrogen Production Technology 15 1.5 Properties of Hydrogen 19 1.5.1 Fuel Properties of Hydrogen 19 1.6 Book Overview 20 References 21 Microbiology 23 2.1 Introduction 23 2.2 Dark Fermentative Bacteria 25 2.2.1 Adaptation to Temperature 25 2.2.1.1 Thermophiles 30 2.2.1.2 Mesophiles 30 2.2.1.3 Psychrophiles 31 2.2.2 Tolerance to Oxygen 31 2.2.2.1 Obligate Anaerobes 31 2.2.2.2 Facultative Anaerobes 33 2.2.2.3 Aerobes 35 2.2.3 Fermentative End Products 35 2.2.3.1 Lactic Acid Fermentation 36 2.2.3.2 Mixed Acid Fermentation 36 2.2.3.3 Butyric Acid Fermentation 36 2.2.3.4 Butanol−Acetone Fermentation 36 2.3 Photosynthetic Fermentative Bacteria 36 2.3.1 Purple Bacteria 37 v vi Contents 2.3.1.1 Sulfur Bacteria 37 2.3.1.2 Nonsulfur Bacteria 38 2.3.2 Green Bacteria 39 2.3.2.1 Sulfur Bacteria 39 2.3.2.2 Gliding Bacteria 39 2.4 Cyanobacteria 40 2.4.1 Anabaena 41 2.4.2 Nostoc 41 2.4.3 Synechocystis 41 2.5 Green Algae 42 2.5.1 Chlamydomonas 42 2.6 Concept of Consortia Development 43 2.7 Synthetic Microorganisms—Are They the Future? 44 Glossary 45 References 45 Hydrogen Production Processes 55 3.1 Introduction 55 3.2 Photobiological Hydrogen Production 57 3.2.1 Basic Principles of Photobiological Hydrogen Production 57 3.2.1.1 Photoautotrophic Production of Hydrogen 57 3.2.1.2 Photoheterotrophic Production of Hydrogen 58 3.2.2 Fundamentals of Photosynthesis and Biophotolysis of Water 58 3.2.3 Biophotolysis 60 3.2.3.1 Direct Biophotolysis 60 3.2.3.2 Indirect Biophotolysis 65 3.2.4 General Considerations and Advancements Made in Biophotolysis 68 3.2.4.1 Explosive Hydrogen–Oxygen Mixture 68 3.2.4.2 Oxygen Sensitivity of the Enzymes Involved in Hydrogen Production 68 3.2.4.3 Inefficiency of Biophotolysis Process Due to Large Antennae Size 69 3.2.4.4 Quantum Efficiency 70 3.2.4.5 Availability of More Reductant 70 3.2.4.6 Natural Coupling of Photosynthetic Electron Transport to Proton Gradient 71 3.2.4.7 Photobioreactors 71 3.3 Photofermentation 72 3.3.1 General Considerations and Advancements Made in Photofermentation 77 3.3.1.1 Immobilization Approaches 77 3.3.1.2 Scale-Up Considerations 79 Contents vii 3.4 Dark Fermentation 81 3.4.1 Anaerobic Fermentation 81 3.4.2 General Considerations to Commercialization of the Technology 84 3.4.2.1 Low Yield and Rate of Production 85 3.4.2.2 Processing of Some Biomass Feed Stock Is Too Costly 85 3.4.2.3 Incomplete Substrate Degradation 85 3.4.2.4 Lack of Robust Industrial Strain 86 3.4.2.5 Engineering Issues 86 3.4.2.6 Sensitivity of Hydrogenase to Oxygen 86 3.4.2.7 Mixed Consortia Have Methanogens: Suppression of Methanogen Activity 88 3.4.2.8 Low Gaseous Energy Recovery 88 3.4.2.9 Biomass and End Metabolite Formation Compete with Hydrogen Production 89 3.4.2.10 Thermodynamic Limitations 89 3.4.2.11 Integration of Processes 89 3.4.3 Progress Made in the Field of Dark Fermentation 90 3.4.3.1 Overcoming Techno-Engineering Barriers .90 3.4.3.2 Molecular Advancements 90 3.4.3.3 Modeling and Optimization of the Process 90 3.4.3.4 Pilot Scale Demonstration of the Technology 91 3.5 Hybrid Processes 92 3.5.1 Integration of Dark Fermentative Process with Photofermentation 92 3.5.1.1 Lactic Acid Fermentation Integrated with Photofermentation 93 3.5.1.2 Acetic Acid Fermentation Integrated with Photofermentation 94 3.5.1.3 Mixed Acid Fermentation 94 3.5.2 Integration of Biophotolysis with Dark Fermentative Process and Photofermentation 95 3.5.3 Integration of Biophotolysis with Photofermentation 95 3.5.4 Biohydrogen Production Integrated with Anaerobic Methane Production 96 3.6 Microbial Electrolysis Cell 97 3.7 Thermodynamic Limitations 98 Glossary 100 References 100 Biohydrogen Feedstock 111 4.1 Introduction 111 4.2 Simple Sugars as Feedstock 111 4.3 Complex Substrates as Feedstock 123 viii Contents 4.4 4.5 4.6 4.7 Biomass Feedstock 123 Organic Acids 124 Waste as Feedstock 125 Assessment of Cost Components for Several Feedstocks for Dark Hydrogen Fermentation 125 4.8 Conclusion 126 Glossary 126 References 126 Molecular Biology of Hydrogenases and Their Accessory Genes 133 5.1 Introduction 133 5.2 Occurrence of Hydrogenase in Nature 134 5.3 Classification of Hydrogenases 138 5.3.1 [Fe-only] Hydrogenases 138 5.3.2 [NiFe] Hydrogenase: Structure and Location 140 5.3.2.1 Group 1: [NiFe] Uptake Hydrogenase 141 5.3.2.2 Group 2: Cyanobacterial Uptake Hydrogenases and Hydrogen Sensors 142 5.3.2.3 Group 3: Multimeric Soluble Hydrogenases 142 5.3.2.4 Group 4: Escherichia coli Hydrogenase 143 5.3.2.5 Structural Organization of the GenesEncoding [NiFe] Hydrogenases and Their Physiological Role in the Organism 143 5.3.2.6 Biosynthesis of [NiFe] Hydrogenases 147 5.3.2.7 Transcriptional Regulation of [NiFe] Hydrogenases 151 5.3.3 [FeFe]-Hydrogenase: Structure and Location 154 5.3.3.1 [FeFe]-Hydrogenase Active Site 156 5.3.3.2 [FeFe]-Hydrogenase Maturation Machinery 157 5.4 Problems Associated with Oxygen Sensitivity of Hydrogenases and Plausible Solutions 160 5.4.1 Reasons for Oxygen Insensitivity of Hydrogenase 162 5.4.1.1 Blocking of the Active Site by Partial or Complete Reduction Product of Attacking Oxygen 162 5.4.1.2 Protective Role of FeS Clusters Surrounding the Active Site 163 5.4.1.3 Role of Conformation of Gas Channels in Delivering Oxygen Tolerance 163 5.4.2 Possible Solutions to Overcome Oxygen Insensitivity of Hydrogenase 164 5.4.2.1 Change in the Amino Acid Residues of the Gas Channels 164 Contents ix 5.4.2.2 Overexpression of Oxygen-Tolerant Hydrogenases 164 5.4.2.3 Nano-Technology to the Rescue: Creating Anoxic Environments within the Organism to Enhance Hydrogen Production 165 5.4.2.4 Gene Shuffling for Rapid Generation of Hydrogen 165 5.5 Evolutionary Significance of Hydrogenase 167 5.5.1 Role of Hydrogenase during Nitrogen Fixation 167 5.5.2 Role of Hydrogenase during Methanogenesis 168 5.5.3 Role of Hydrogenase in Bioremediation 169 5.6 Conclusion 169 Glossary 169 References 170 Improvement of Hydrogen Production through Molecular Approaches and Metabolic Engineering 179 6.1 Introduction 179 6.2 Molecular Approaches 179 6.2.1 Improvement of Biomass Production 179 6.2.1.1 CO2-Concentrating Mechanisms (CCMs) 188 6.2.1.2 Cell Cycle 189 6.2.2 Enhancing the Uptake of External Substrate 190 6.2.3 Improvement of Photoconversion Efficiency 190 6.2.4 Improvement of Hydrogen-Producing Enzymes 193 6.2.4.1 Improvement of Hydrogenase 193 6.2.4.2 Improvement of Nitrogenase 194 6.2.4.3 Overexpression of Enzymes 196 6.2.5 Introduction of Foreign Hydrogenase 196 6.2.6 Deletion of Hydrogen Uptake Genes 200 6.2.7 Other Approaches 202 6.2.7.1 Generation of Anaerobic Condition 202 6.2.7.2 ATP Synthase Modification for Enhanced Hydrogen Production 202 6.2.7.3 Linking of Hydrogenase to Cyanobacterial Photosystems 203 6.2.7.4 Engineering of Heterocyst Frequency 204 6.3 Metabolic Engineering 205 6.3.1 Proteomic Analysis 205 6.3.2 Redirecting the Electron Pull toward Hydrogen Production 206 6.4 Conclusion 209 Glossary 210 References 211 Biohydrogen Production Process 357 vehicles and electric power plants are significant contributors to the nation’s air quality problems (Figure 11.3) Most nations are now developing strategies for reaching national ambient air quality goals and bringing their major metropolitan areas into attainment with the requirements of the clean air act The introduction of hydrogen-based commercial bus fleets is one of the approaches that states are considering to improve air quality THE NEGATIVE SIDE OF HYDROGEN! On the negative side of the hydrogen production technology, some scientists are of the view that hydrogen is not as eco-friendly as it is proposed to be! In fact, it interferes with the environment and causes global warming thought at a lower level, as compared to fossil fuels British scientists have recently reviewed current understanding of the fate and behavior of hydrogen in the atmosphere and characterized its major sources and sinks They have showed that contrary to the common belief that hydrogen is an environmentally benign fuel, it has an indirect potential for global warming The scientists are of the opinion that with the manufacture of hydrogen its large-scale leakage into the atmosphere is inevitable They showed that the released hydrogen would react with tropospheric OH−radicals, which would disrupt the distribution of methane and ozone, the second and third most important greenhouse gasses Limitations to the distribution of methane and ozone would further increase their burden on the earth leading to further global warming Therefore, hydrogen can be considered as an indirect greenhouse gas with the potential to increase global warming Further, the group compared the potency of hydrogen as a contributor to global warming to that of CO2 emanating from fossil-based fuel to that of hydrogen The group found that the potency of hydrogen as a contributor to global warming was far less as compared to the present-day fossil fuel-based energy systems However, such impacts will depend on the rate of hydrogen leakage during its synthesis, storage, and use The researchers have calculated that a global hydrogen economy with a leakage rate of 1% of the produced hydrogen would produce a climate impact of 0.6% of the fossil fuel system it replaces If the leakage rate was 10%, then the climate impact would be 6% that of the fossil fuel system Thus, the study suggests that the future hydrogen-based economy would not be completely free from climate disturbance, although this may be considerably less pronounced than that caused by the current fossil fuel energy systems Thus, it is important to control hydrogen leakage at all stages from production to storage to conversion to minimize the effect of such indirect climatic disturbances 358 Biohydrogen Production Recent research regarding air pollution effects on human health describes serious lung damage sustained from fossil fuel combustion Substituting hydrogen for fossil fuel will result in improved physical health (Zweig, 1995) The combustion of hydrogen does not produce CO2, CO, SO2, volatile organic carbon (VOC), and particles However, it entails the emission of vapor and NOx The formation of NOx is a function of flame temperature and duration Considering the wide flammability range of hydrogen, its combustion can be influenced by the design of the engine so that the NOx emission can be reduced (Momirlan and Veziroglu, 2002) Considering the health impacts, some scientists are of the opinion that introduction of hydrogen as fuel seems almost inevitable Hydrogen introduction dramatically affects carbon dioxide in the atmosphere, which is estimated to reach the maximum before 2050 at 520 ppm Figure 11.4 illustrates what would happen if transition to the solar hydrogen system is delayed 25 years Energy consumption and economic activity would be higher than in “no hydrogen” scenario, but much lower than the case when hydrogen is introduced in the year 2000 Carbon dioxide would continue to increase until approximately 2070 reaching 620 ppm If transition starts at 2050, there would be almost no positive effects This suggests that an early transition to the hydrogen energy system would benefit the economy and the environment in the long run (Barbir et al., 1995) In view of this, in recent years, there is a new important development in automotive technology which is aimed toward more efficient and less polluting vehicles In view of excess pollution, several countries are promoting hydrogen-based vehicular transport to control the pollution levels In-depth analysis shows that the fuel cell drive for city buses offers significant environmental improvements compared to diesel internal combustion engines This refers to emissions of greenhouse gases as well as to local emissions of trace gases The main improvement with regard to the global warming problem can nonetheless only be achieved if renewable fuels are introduced (Wurster et al., 1998) A major advantage of the fuel cell vehicles is that they represent an inherently clean and efficient technology that can optimize the use of fuels from environmentally benign energy sources and feed stocks such as solar, wind, geothermal, and biomass In today’s world where the primary concern is energy security and a degrading environment, hydrogen seems to be the need of the hour It makes sense to use the forms of energy that are abundant, clean, and renewable 11.4 Hydrogen Policy In recognition of the reduction targets for greenhouse gas set by the Kyoto Protocol, studies have focused on hydrogen as a means of meeting the demand for clean energy In view of this, due to the wide-scale advantages 359 Biohydrogen Production Process 750 700 Carbon dioxide in the atmosphere (ppm) 650 No hydrogen scenario 600 550 500 With hydrogen introduced in 2000 450 400 Historical record 350 300 1950 1975 2000 2025 2050 2075 2100 FIGURE 11.4 Carbon dioxide in the atmosphere (base case scenario) (Reprinted from Momirlan, M and Veziroglu, T N 2002 Current status of hydrogen energy Renewable and Sustainable Energy Reviews, 6, 141–179 With permission.) of hydrogen, hydrogen policies are today under the energy policy for most countries For the smooth transition to a hydrogen-based economy, energy policy matters need to be discussed It calls for a strong co-operation between the government and industry Energy policy attributes to production, consumption (efficiency and emission standards), taxation and other public policy techniques, energy-related research and development, energy economy, general international trade agreements and marketing, energy diversity, and risk factors contrary to possible energy crisis There are two key areas to be focused: (1) research, development, and demonstration of hydrogen technologies by industries and (2) incentives to encourage investment in hydrogen infrastructure by the government In a well-planned programe, the entire 360 Biohydrogen Production CURRENT STATUS OF HYDROGEN TECHNOLOGY Presently, it is a great challenge to get an internal combustion engine running well on hydrogen because of significantly different properties of hydrogen as compared to gasoline, particularly the density and the self-ignition energy, among other things Still there were several studies undertaken for use of hydrogen in IC engines The U.S Department of Energy (DOE) undertook to test whether existing gasoline or natural gas engines could work on either pure hydrogen or hydrogen blended with other fuels Accordingly, they tested four internal combustion vehicles using hydrogen: a Dodge Ram van and a Ford F-150 with engines designed for compressed natural gas, a Ford F-150 with a gasoline engine that was modified to run on a hydrogen-natural gas blend and a Mercedes van with a gasoline engine modified to run on pure hydrogen The tests showed that engines driven on pure hydrogen or their blends were more economical and efficient as compared to the engine on natural gas or gasoline alone (Morrison et al., 2012) In another study, engine emissions from two modified passenger buses in Northern California powered by 20–80 volumetric H-CNG blends were studied (Burnham et al., 2004) It was found that constant power could be achieved while reducing NOx emissions between 85% and 91% and increasing fuel economy by 15–25% as compared to pure CNG buses Similarly, in India, Ministry of New and Renewable Energy (MNRE), Government of India has taken extensive steps and developed a hydrogen road map to initiate hydrogen research and application Hydrogen Energy Centre at BHU carried out test drives to demonstrate hydrogenfuelled road transport Their vehicles of choice were those that were used most commonly by the local population, two-wheelers, threewheelers, and small cars In view of their success, the International Cars and Motors Ltd (ICML) undertook to manufacture 10 three-wheelers These were planned to run between the Central Secretariat and Lodhi Road, New Delhi, India Similar efforts are also being made for twowheelers with the help of the Society for Indian Auto Manufacturers (SIAM), which has access to various two-wheeler manufacturers in India (Leo et al., 2009) transition can be divided into four phases: the technology development phase, initial market establishment phase, infrastructure investment phase, and the last phase of a well-developed open market (Figure 11.5) In accordance, Department of Energy, the USA has developed a four-stage road-map for implementation of the hydrogen technology According to the plan, in phase one, private organizations will research, develop, and demonstrate technologies prior to major investment in infrastructure During this phase, 361 Biohydrogen Production Process ADVANTAGES AND DISADVANTAGES OF HYDROGEN AS TRANSPORT FUEL Hydrogen as a future fuel has a number of advantages, provided the technical hurdles can be overcome regarding its implementation One of hydrogen’s primary advantage is that it can be produced from a variety of primary resources such as biomass and water Another important advantage of hydrogen over other fuels is that on combustion it produces water vapor as the only by-product This can significantly limit the greenhouse gas emissions Another property that makes it advantageous is that hydrogen can be used as a transportation fuel whereas neither nuclear nor solar energy can be used directly It has good properties as a fuel for internal combustion (IC) engines in automobiles including a rapid burning speed, a high effective octane number, and no toxicity or ozone-forming potential It has much wider limits of flammability in air (4–75% by volume) than methane (5.3–15% by volume), and gasoline (1–7.6% by volume) Moreover, in countries that face extreme cold winter, hydrogen may prove to be the ideal fuel as it remains in a gaseous state until it reaches a low temperature such as 20 K This may be important to maintain the longevity of the engine Phase IV Realization of the H2 Expansion to the market and infrastructure Phase III Transition to the market place Phase II Phase I IV III II Commercialization decision RD&D 2000 Basic R&D contd 2010 2020 2030 I 2040 FIGURE 11.5 Roadmap for hydrogen research (Adapted from U.S Department of Energy (USDoE), National Energy Technology Laboratory 2004 Hydrogen Infrastructure Delivery Reliability R&D Needs Pittsburgh, Pennsylvania.) 362 Biohydrogen Production public awareness and education would also be focused in concurrence to the ongoing research In the next Phase II of the technology mission, the technology will be made available on wide-scale basis in the market However, it remains to be seen which technology would penetrate the market However, by this time, sufficient public awareness is required to purchase these products as end consumers Here, the role of the government will be required to provide incentives to the end consumers Such incentives could be justified by the long-term social economic and environmental benefits They could be in the form of favorable taxation, carbon penalties, and so on all of which would favor hydrogen Governments will also need to work with fuel providers, equipment manufacturers, car makers, and standard setting bodies for designing, building testing, and ultimately marketing hydrogen-related equipment As the markets become established, government can continue to foster their further growth in Phase III by patronizing the technology to stimulate the market There are plenty of precedents in which proactive government action has caused a shift in the pattern of energy use For example, in central Europe, government used preferential taxes to encourage the development of natural gas transmission and distribution network In the fourth phase (Phase IV) of the roadmap, with the realization of a hydrogen market, the product can be integrated into the national infrastructure Further, to the benefit of the industry and stake-holders, policy interest in moving toward a hydrogen-based economy is rising However, presently, due to some technological and economic consequences, practical experiences of hydrogen energy not have wide applications either in the richest countries or in the poorest countries In most countries, research is still in the R&D phase The developed countries are ahead and are working through collaborative international programs, to facilitate the introduction of new hydrogen technologies as they become competitive Investment in research has already led to significant developments in hydrogen-related technologies in countries such as member states of the European Union (EU), the USA, Canada, and Japan These countries account for about two-thirds of total public hydrogen R&D spending However, international organizations should extend their support to the developing countries for the transition to a hydrogen economy as well as hydrogen production and distribution In practical advancement and proto-type demonstration of the technology, British Petroleum is providing the hydrogen delivery infrastructure for transport demonstration projects in 10 cities around the world, including the CUTE (Clean Urban Transport for Europe) bus project in London (Hughes, 2007) The aim of demonstration of the projects is to thrust hydrogen technologies from the stage of research and development to the commercialization level Current EU policies on alternative motor fuels focus on the promotion of biofuels The definition of the marginal producer depends on the policy stance on biofuels It should be applied in such a way that it does not create cross-subsidies between classes of consumers (Balat, 2007) In a proposed biofuels’ directive from 2009, a mandatory to minimum blending shares of the biofuel has been 363 Biohydrogen Production Process 25 20 15 Biofuel Natural gas 10 Hydrogen Total 2010 2015 2020 FIGURE 11.6 Share of alternative fuels in total automotive fuel consumptionin the EU under the optimistic development scenario of the EU Commison proposed (Figure 11.6) (Demirbas, 2008) However, to make hydrogen a part of the blend, concerted steps need to be taken to promote the end use A possible development path for hydrogen infrastructure includes a stepwise transition to avert high costs and address the chicken-and-egg problem Initially when demand for hydrogen energy is low, instead of laying extensive pipeline, hydrogen can be delivered by trucks from centralized plants Mobile refuel tanks might be used or alternatively hydrogen could be produced onsite The advantage of onsite production is that it avoids the cost of hydrogen distribution and allows the supply to grow incrementally with demand In the later phase, as demand increases, installation of pipelines could be considered, which would be more economical for a wider consumer The existing infrastructure is bound to affect the way hydrogen evolves in the future Therefore, the policy makers, academia, and industry need to act now to have a sustainable hydrogen future Moreover, public understanding of hydrogen will have a tremendous impact on current as well as future policy initiatives for vehicle as well as portable and stationary applications Numerous studies have been performed to analyze the public’s current perception and understanding of hydrogen Most energy-producing technologies have an attached combination of positive and negative stigmas and means of understanding by the general public For example, individuals who are aware of the environmental effects of a possible nuclear meltdown may deem nuclear power as a negative entity On the contrary, individuals who are aware of the quantities of carbon emissions being reduced by using one less fossil fuel-driven power plant may find nuclear power as a positive entity A combination of scientific understanding with common associated social themes anchored by pre-existing knowledge will have a significant impact on the future hydrogen policy 364 Biohydrogen Production 11.5 Issues and Barriers • The current yield and rates of production especially from the microbial process may not be economically feasible • For hydrogen renewables, the issue at hand is primarily the high cost of the project In particular meeting, matching supply and demand during a transition at low cost is a key issue • Strong government support to help penetrate the technology into the market • Development of a consistent energy policy to address societal problems of climate change, air pollution, and national security A strong consensus stand is required to cut carbon emissions • Public awareness must be developed about the safety and the use of hydrogen To this end, it is important to develop safety procedures and codes for use of hydrogen in energy applications • The major issues facing the fast development of a hydrogen-based economy is the lack of interaction between the developers of the technology and the large-scale buyers who can put it to end use This causes lack of hydrogen infrastructure for introduction of fuel cell vehicles • Moreover, the rates of hydrogen produced by the various biohydrogen systems are expressed in different units, making it difficult to assess and compare the rates and amounts of hydrogen synthesized by different biohydrogen technologies • Other crucial drawbacks of using hydrogen as a transportation fuel are huge on-board storage tanks, which are required because of hydrogen’s extremely low density as already discussed before However, the low-ignition temperature is one of the major advantages for hydrogen to be used directly as a fuel Hence, it can be used as fuel indirectly by making fuel cells for producing electricity • Even under a scenario of technical success and strong policy, it may still be probably 10–15 years before hydrogen energy technologies start to enter the market Therefore, they may have no immediate effect on the current oil usage and or carbon dioxide emissions 11.6 Status of Hydrogen in the Developed and the Developing Countries Biofuels are attracting growing interest throughout the world, with some governments announcing commitments to the biofuel programs as a way to reduce Biohydrogen Production Process 365 greenhouse gas emissions and dependence on petroleum-based fuels Among all the bio-based fuel, hydrogen gains popularity Over the next 10–20 years, vigorous government-supported RD&D programs on hydrogen and fuel cell technology will be pursued However, the extent to which hydrogen is considered to play a role in the global energy system in the future ranges widely across the world depending on the policy adopted, the cost analysis, and the technology breakthroughs Under the most favorable conditions, hydrogen vehicles are projected to reach shares of 30–70% of the global vehicle stock by 2050, resulting in a hydrogen demand of EJ to 16 EJ As per the current situation, it is predicted that most of this demand will be from central Europe, North America, and China The resulting reduction of oil consumption would be in the range of 7–16 million barrels per day (Ball and Wietschel, 2009) Although most hydrogen research is taking place in the industrialized countries, developing economies must also decide to invest in this venture, since their economies are more liable to suffer due to the political instability of the oil-producing countries However, due to the lack of necessary funds, the developing countries may not be able to afford the cost of participating in R&D However, engaging the developing countries early in the process may help to speed up the transition to hydrogen Statistics indicate that in the near future the developing countries are expected to account for the bulk of the increase in global energy consumed in the coming decade This would mean more utilization of fossil fuels, if breakthrough in energy policy is not endorsed Therefore, the earlier these countries begin the transition to hydrogen, the quicker the world could achieve energy stability By far the largest ongoing projects related with hydrogen are being carried by the United States, Japan, and the EU The challenge is to link the international and regional activities using common methodologies and tools, augmenting analysis for all countries and supporting development efforts Some countries have integrated R&D programs that cover all elements of hydrogen supply and end uses Primarily, the approach the governments adopt to implement the hydrogen program will reflect their own needs and resources For example, Australia focuses on hydrogen production from coal, because it has large coal reserves However, Germany focuses on fuel cell for vehicles as they are leaders in vehicle manufacturing Accordingly, the amount of budget distributed and the resources used by different countries varies within their framework 11.6.1 United States Hydrogen received a great boost in the United States during the second term of the Bush administration The then government showed much interest in developing hydrogen fuel cell technologies within the transportation sector This interest was mainly driven by the desire to decrease the dependence of the United States on foreign oil and reduce the environmental impact caused due to the burning of fossil fuels The initiative to promote fuel cell 366 Biohydrogen Production technology was announced by former President Bush in his State of the Union Address in 2003 In accordance to this, a new national commitment, a Hydrogen Posture Plan, was created in order to begin to map the future of hydrogen technology research, development, and demonstration In order to accelerate research, development, and demonstration, former President Bush announced plans to appropriate $1.2 billion to hydrogen research Most of the hydrogen and fuel cell research in the United States is funded by the Department of Energy (DOE) The government’s strategy is to concentrate funding on high-risk applied research on technologies in the early stages of development and leverage private sector fundings through partnerships The United States Federal Government has created several programs to promote alternative fuels including hydrogen These include programs such as “clean cities and clean construction the United States.” The clean city program mostly focuses on practices to reduce the greenhouse gas emissions by the transport sector Clean cities performs these duties through a network of more than 80 offices that develop public/ private partnerships to promote alternative fuels, advanced vehicles, fuel blends, and hybrid vehicles They also provide information about financial opportunities, coordinate technical assistance projects, update and maintain energy databases, and publish fact sheets, newsletters, and related technical and informational material Clean Ports USA is an incentive-based program designed to help reduce emissions by encouraging port authorities to redesign and replace older diesel engines with new technologies and cleaner fuels The U.S Environmental Protection Agency’s National Clean Diesel Campaign offers funding to port authorities to help them overcome the obstacles that prevent the adoption of cleaner diesel technologies These are just two examples There are numerous such ongoing programs run by the DoE to effectively reduce the greenhouse gas emissions and dependence on fossil fuel in the coming decade 11.6.2 Europe Since 1986, the EU has funded some 200 projects on hydrogen and fuel cell energy technologies with a total contribution of over EUR 550 million These projects focused on advancements in research in all the basic areas of hydrogen research including production, storage, delivery, and use of hydrogen in cost-effective fuel cell, hydrogen-fuelled vehicles, and other related policies aimed at transition of hydrogen Further, these projects foster long-term collaborations among different organizations that are active in the same field By working together in projects, they exchange experience and create links that might continue cooperation even after the project has finished Importantly, research is also channeled toward marketable solutions, as businesses and universities co-operate and partners are found to create supply chains Further, to accelerate development and deployment of hydrogen as a fuel in the most efficient way, the EU has joint forces with European Biohydrogen Production Process 367 industry and research institutes in a ­public–private partnership of the Fuel Cells and Hydrogen (FCH), and Joint Technology Initiative (JTI) Together, the partners will implement a programe of research, technological development, and demonstration to accelerate the commercialization of FCH technologies in a number of application areas Additionally, recently, the Danish Government has announced a new Energy Plan 2020 that includes establishment of a range of initiatives for hydrogen infrastructure and FCEVs with the overall aim to reach 100% fossil independence by 2050 The government initiatives follow the recommendations from a recent Danish industry coalition analysis and roadmap on “Hydrogen for transport in Denmark onwards 2050.” The German government has planned to take the hydrogen research to all new levels The Ministry of Transport, Building and Urban Development has taken initiatives to solve the classic “chicken-and-egg” problem It has announced to develop 50 new public hydrogen fuel stations The ministry is estimated to spend more than $50 million in the endeavor within the next year Germany is home to 15 hydrogen fuel stations, enough to power the 5000 hydrogen-powered vehicles that are currently operating in the country The 50 additional stations will pave the way for the rapid adoption of new hydrogen vehicles being released between the years of 2013 and 2015 11.6.3 Asia–Pacific It has been suggested that the pace of funding for the design and rollout of hydrogen refuelling stations will pick up in 2013, especially in Asia–Pacific and Europe Strong interest in hydrogen refuelling stations was apparent in 2012 Japan, for example, released subsidies in 2013 to kick-start the building program of hydrogen-refuelling stations called “Subsidy for Hydrogen Supply Facility Preparation.” The Japanese government has set aside a war chest of $0.5 billion for 2013 The program will provide for half a station construction cost Japan was among the first countries to invest in hydrogen research in a 10-year project, which was completed in 2002 Soon after the finish of the first project the, Japanese government initiated a second project in 2003 The Japanese government is confident that with continued funding in this area, economical hydrogen-based fuel may soon be a reality 11.7 Future Outlook The role of hydrogen in today’s society is inevitable if we want to realize both the energy security and the control of the pollution In fact, globally the demand for energy is increasing in concurrence with socioeconomic standard of living According to survey of the International Energy Agency, world energy demand will increase by half around the year 2030, with more 368 Biohydrogen Production than two-thirds of this increase will come from developing and emerging countries For socioeconomic development, the alternative energy plays an important role The majority of the experts consider that hydrogen has a great role to play as an important energy carrier in the future energy sector Biological production of hydrogen may play a key role though its contribution in today’s time may occur to be insignificant For the role of biological hydrogen to be realized, yields will have to be improved and further the economics of the process needs to be looked into greater depths by analyzing the reactor sizes and efficiencies of production Presently, the size of the bioreactors required is too large for any practical application of the process Concerted efforts would no doubt bring about a greater contribution of this technology to the existing hydrogen production technologies Although research on hydrogen production has come a long way, still concerted efforts are required for an industrial scale production For realistic applications that are economically feasible, the hydrogen yields and production rates must surpass considerably the present achievements More research on pilot scale productions is warranted Already significant work has been reported by various groups in terms of biohydrogen production and yields There is still much work to be done before this translates into any kind of commercial application Thus, the transition from a fossil-based economy to a hydrogen economy is a daunting task and the following points need immediate attention: A common platform such as an organization or an institute which can globally monitor the hydrogen research Moreover, initiatives should be taken to enable researchers working with H2 production, storage, and application research such as fuel cell to work under a common umbrella Glossary CUTE Clean urban transport for Europe DOE Department of energy EU European Union GJ Gigajoules IC-engine Internal combustion engine PPM Parts per million References Balat, M 2007 Hydrogen in fueled systems and the significance of hydrogen in vehicular transportation Energy Sources Part B, 22, 49 Biohydrogen Production Process 369 Ball, M and Wietschel, M 2009 The future of hydrogen—Opportunities and challenges International Journal of Hydrogen Energy, 34, 615–627 Barbir, F., Plass, H J., and Veziroglu, T N 1995 Hydrogen Energy System Production and Utilization of Hydrogen and Future Aspects, ed Yurum, Y NATO ASI Series New 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Proceedings of the IEEE, 94, 1826–1837 Burnham, A., Burke, A Collier, K., Forrest, M., McCaffrey, Z., and M Miller 2004 Hydrogen bus technology validation program: Analysis and update Proceedings, Annual Meeting of the National Hydrogen Association, Los Angeles, CA Dasgupta, C N., Jose Gilbert, J., Lindblad, P et al 2010 Recent trends on the development of photobiological processes and photobioreactors for the improvement of hydrogen production International Journal of Hydrogen Energy, 35, 10218–10238 Das, D., Khanna, N., and Veziroğlu, T N 2008 Recent developments in biological hydrogen production processes Chemical Industry and Chemical Engineering Quarterly, 14, 57–67 Das, D 2009 Advances in biohydrogen production processes: An approach towards commercialization International Journal of Hydrogen Energy, 34, 7349–7357 Demirbas, A 2008 Biofuels sources, biofuel policy, biofuel economy and global biofuel projections Energy Convers Management, 49, 2106–2116 Habermann, W and Pommer, E H 1991 Biological fuel cells with sulphide storage capacity Applied and Microbial Biotechnology, 35, 128–133 Hallenbeck, P C 2009 Fermentative hydrogen production: Principles, progress & prognosis International Journal of Hydrogen Energy, 34, 7379–7389 Hallenbeck, P C 2012 Hydrogen production by cyanobacteria In Microbial Technologies In Advanced Biofuels Production, ed P C Hallenbeck, pp 15–28 New York: Springer Hughes, A N 2007 Organizations and institutions relating to the development of hydrogen and fuel cell activities in the UK UKSHEC social science working paper no 34 London: Policy Studies Institute Leo, H M S., Dubey, P K., Pukazhselvan, D et al 2009 Hydrogen energy in changing environmental scenario: Indian context International Journal of Hydrogen Energy, 34, 7358–7367 Momirlan, M and Veziroglu, T N 2002 Current status of hydrogen energy Renewable and Sustainable Energy Reviews, 6, 141–179 Morrison, G M., Kumar, R., Chugh, S., Puri, S K., Tuli, D K., and Malhotra, R K 2012 Hydrogen transportation in Delhi? Investigating the hydrogen-compressed natural gas (H-CNG) option International Journal of Hydrogen Energy, 37, 644–654 Mudler, R A 2006 A pollution-free hydrogen economy? Not so soon Technology Review Online http://muller.lbl.gov/tressays/18_hydrogen.html Ogden, J M., Steinbugler, M M and Kreutz, T G 1999 A comparison of hydrogen, methanol and gasoline as fuels for fuel cell vehicles Journal of Power Sources, 79, 143–168 Ogden, J and Kaijuka, E 2003 New methods for modeling regional hydrogen infrastructure development Presented at the 14th National Hydrogen Association Meeting, Washington, DC 370 Biohydrogen Production Sinha, P and Pandey, A 2011 An evaluative report and challenges for fermentative biohydrogen production International Journal of Hydrogen Energy, 36, 7460–7478 Suzuki, S 1976 Fuel cells with hydrogen-forming bacteria Hospital hygiene Gesundheitswesen und desinfektion, 1, 159 Tredici, M R., Zittelli, G C., and Benemann J R 1998 A tubular internal gas exchange hydrogen production: Preliminary cost analysis In BioHydrogen, ed O Zaborsky, pp 391–402 New York: Plenum Press US DoE Energy Efficiency and Renewable Energy 2003 Hydrogen, fuel cells and infrastructure technologies programme, production and delivery U.S Department of Energy (USDoE), National Energy Technology Laboratory 2004 Hydrogen Infrastructure Delivery Reliability R&D Needs Pittsburgh, Pennsylvania de Vrije, T and Claasen P A M 2003 Dark hydrogen fermentation In Biomethane and biohydrogen, eds J H Reith, R H Wijffels, and H Barten, pp 103–123 The Hague, The Netherlands: Dutch Biological Hydrogen Foundation Wurster, R., Altmann, M., Sillat, D et  al 1998 Hydrogen energy progress XII Proceedings of the 12th World Hydrogen Energy Conference, Buenos Aires, Argentina: Zweig, R M 1995 The hydrogen economy—Phase Proceedings of the Ninth World Hydrogen Energy Conference, PARIS, France, 1995 Chemical Engineering “…covers the biological hydrogen production authoritatively from A to Z … I strongly recommend this excellent book to energy scientists, engineers, and students who are interested in hydrogen production in general and biological hydrogen production in particular, as well as to industrial concerns that are looking for inexpensive hydrogen production technologies.” —T Nejat Veziroğlu, President, International Association for Hydrogen Energy “ an excellent contemporary review of the biohydrogen production research field.” —Nils-Kåre Birkeland, University of Bergen, Norway Biohydrogen Production: Fundamentals and Technology Advances covers the fundamentals of biohydrogen production technology, including microbiology, biochemistry, feedstock requirements, and molecular biology of the biological hydrogen production processes It also gives insight into scale-up problems and limitations In addition, the book discusses mathematical modeling of the various processes involved in biohydrogen production and the software required to model the processes The book summarizes research advances that have been made in this field and discusses bottlenecks of the various processes, which presently limit the commercialization of this technology The authors also focus on the process economy, policy, and environmental impact of this technology, since the future of biohydrogen production depends not only on research advances, but also on economic considerations (the cost of fossil fuels), social espousal, and the development of H2 energy systems The book describes the fundamentals of this technology interwoven with more advanced research findings Further reading is suggested at the end of each chapter Since the beauty of any innovation is its applicability, socioeconomic impact, and cost energy analysis, the book examines each of these points to give you a holistic picture of this technology Illustrative diagrams, flow charts, and comprehensive tables detailing the scientific advancements provide an opportunity to understand the process comprehensively and meticulously Written in a lucid style, the book supplies a complete knowledge bank about biohydrogen production processes K15140 an informa business www.crcpress.com 6000 Broken Sound Parkway, NW Suite 300, Boca Raton, FL 33487 711 Third Avenue New York, NY 10017 Park Square, Milton Park Abingdon, Oxon OX14 4RN, UK ISBN: 978-1-4665-1799-8 90000 781466 517998 w w w.crcpress.com