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82 Advances in Biochemical Engineering / Biotech nology Series Editor: T. Scheper E d i t o r i a l B o a r d : W. Babel . H. W. Blanch. I. Endo. S.-O. E n f o r s A. F i e c h t e r • M. H o a r e • B. M a t t i a s s o n • H. S a h m K. Sch i ige r l • G. S t e p h a n o p o u l o s • U. v o n S t o c k a r G. T. T s a o . J. V i l l a d s e n • C. W a n d r e y • J.-J. Z h o n g Springer Berlin Heidelberg New York Hong Kong London Milan Paris Tokyo Biomethanat ion II Volume Editor: Birgitte K.Ahring With contributions by B. K. Ahring, I. Angelidaki, J. Dolfing, L. EUegaard, H. N. Gavala, F. Haagensen, A. S. Mogensen, G. Lyberatos, P. E Pind, ]. E. Schmidt, I.V. Skiadas, K. Stamatelatou ~ Springer Advances in Biochemical Engineering/Biotechnology reviews actual trends in modern biotechnology. 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Babel Section of Environmental Microbiology Leipzig-Halle GmbH Permoserstrafle 15 04318 Leipzig, Germany E-mail: babel@umb.ufz.de Prof. Dr. I. Endo Faculty of Agriculture Dept. of Bioproductive Science Laboratory of Applied Microbiology Utsunomiya University Mine-cho 350, Utsunomiya-shi Tochigi 321-8505, Japan E-mail: endo@cel.riken.go.jp Prof. Dr. A. Fiechter Institute of Biotechnology Eidgen6ssische Technische Hochschule ETH-H6nggerberg 8093 Ztirich, Switzerland E-mail: ae.~echter@bluewin.ch Prof. Dr. H.W. Blanch Department of Chemical Engineering University of California Berkely, CA 94720-9989, USA E-mail: blanch@socrates.berkeley.edu Prof. Dr. S.-O. Enfors Department of Biochemistry and Biotechnology Royal Institute of Technology Teknikringen 34, 100 44 Stockholm, Sweden E-mail: enfors@biotech.kth.se Prof. Dr. M. Hoare Department of Biochemical Engineering University College London Torrington Place London, WC1E 7JE, UK E-mail: m.hoare@ucl.ac, uk VI Editorial Board Prof. Dr. B. 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Save 15 % We recommend a standing order for the series to ensure you automatically receive all volumes and all supplements and save 15 % on the list price. Preface In November 1776, Alessandro Volta performed his classic experiment disturb- ing the sediment of a shallow lake, collecting the gas and demonstrating that this gas was flammable. The science of Biomethanation was born and, ever since, sci- entists and engineers have worked at understanding this complex anaerobic bio- logical process and harvesting the valuable methane gas produced duringanaer- obic decomposition. Two lines of exploitation have developed mainly during the last century: the use of anaerobic digestion for stabilization of sewage sludge, and biogas production from animal manure and/or household waste. Lately, the emphasis has been on the hygienic benefit of anaerobic treatment and its effect on pathogens or other infectious elements. The importance of producing a safe effluent suitable for recirculation to agricultural land has become a task just as important as producing the maximum yield of biogas from a given type of waste. Therefore, anaerobic digestion at elevated temperatures has become the main area of interest and has been growing during the last few years Anaerobic digestion demands the concerted action of many groups of microbes each performing their special role in the overall degradation process. Both Bacteria and Archaea are involved in the anaerobic process while the importance, if any, of eukaryotic microorganisms outside the rumen environ- ment is still unknown. The basic understanding of the dynamics of the complex microflora was elucidated during the latter part of the last century where the concept of inter-species hydrogen transfer was introduced and tested. The isola- tion of syntrophic bacteria specialized in oxidation of intermediates such as volatile fatty acids gave strength to the theories. Lately the use of molecular tech- niques has provided tools for studying the microflora during the biomethana- tion process in situ. However, until now the main focus has been on probing the dynamic changes of specific groups of microorganisms in anaerobic bioreactors and less emphasis has been devoted to evaluating the specific activities of the different groups of microbes during biomethanation. In the future we can expect that the molecular techniques will be developed to allow more dynamic studies of the action of specific microbes in the over-all process. From the present studies we know that many unknown microbes are found in anaerobic bio- reactors. Especially within the domain of Archaea, there are whole phyla of microbes such as the Crenarchaeota, which make up significant fractions of microbes in a reactor but without cultured representatives. Improving the techniques for the isolation of presently unculturable microbes is a major task for the future. X Preface Anaerobic digestion of waste has been implemented throughout the wodd for treatment of wastewater, manure and solid waste and most countries have sci- entists, engineers and companies engaged in various aspects of this technology. Even though the implementation of anaerobic digestion has moved out of the experimental phase, there is still plenty of room for improvements. The basic understanding of the granulation process, the basis for the immobilization of anaerobic microbes to each other without support material in UASB reactors, is still lacking. Like any other bioprocess, anaerobic digestion needs further con- trol and regulation for optimization. However, until now suitable sensors for direct evaluation of the biological process have been lacking and anaerobic bioreactors have generally been controlled by indirect measurements of biogas or methane production along with measurements of pH and temperature. The newly development of an on-line monitoring system for volatile fatty acids could be a major step in the right direction and the use of infra-red monitoring sys- tems could bring the price down to a reasonable level. A better performance of large-scale anaerobic bioreactor systems for treatment of complex mixtures of waste can be expected to be based on on-line monitoring of the process in the future along with controlling software for qualified management of these plants. Besides treatment of waste, anaerobic digestion possesses a major potential for adding value to other biomass converting processes such as gasification, bioethanol or hydrogen from ligno-cellulosic materials. Conversion of ligno-cel- lulosic biomass will often leave a large fraction of the raw material untouched which will be a burden for the over-all economy of the process and will demand further treatment. Anaerobic digestion will on the other hand be capable of con- verting the residues from the primary conversion into valuable methane, which will decrease the cost and the environmental burden of the primary production. Biomethanation is an area in which both basic and applied research is involved. Major new developments will demand that both disciplines work together closely and take advantage of each other's field of competence. The two volumes on Biomethanation within the series of Advances in Biochemical Engi- neering and Biotechnology have been constructed with this basic idea in mind and, therefore, both angles have been combined to give a full picture of the area. The first volume is devoted to giving an overview of the more fundamental aspects of anaerobic digestion while the second volume concentrates on some major applications and the potential of using anaerobic processes. The two vol- umes will therefore be of value for both scientists and practitioners within the field of environmental microbiology, anaerobic biotechnology, and environ- mental engineering. The general nature of most of the chapters along with the unique combination of new basic knowledge and practical experiences should, in addition, make the books valuable for teaching purposes. The volume editor is indebted to all the authors for their excellent contribu- tions and their devotion and cooperation in preparing these two volumes on Biomethanation. Lyngby, January 2003 Birgitte K. Ahring Contents Applications of the Anaerobic Digestion Process I. Angelidaki, L. EUegaard, B. K. Ahring . . . . . . . . . . . . . . . . . . . . 1 Anaerobic Granular Sludge and Biofilm Reactors I.V. Skiadas, H. N. Gavala, ]. E. Schmidt, B. K. Ahring . . . . . . . . . . . . . 35 Potential for Anaerobic Conversion of Xenobiotics A. S. Mogensen, L Dolfing, F. Haagensen, B. K. Ahring . . . . . . . . . . . . 69 Monitoring and Control of Anaerobic Reactors P. F. Pind, I. Angelidaki, B. K. Ahring, K. Stamatelatou, G. Lyberatos . . . . . 135 Author Index Volumes 51-82 . . . . . . . . . . . . . . . . . . . . . . . . . 183 Subject Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 197 Contents of Volume 81 Biomethanantion I Volume Editor: Birgitte K. Ahring Perspectives for Anaerobic Digestion B. K. Ahring Metabolic Interactions Between Methanogenic Consortia and Anaerobic Respiring Bacteria A. J. M. Stams, S. J. W. H. Oude Elferink, P. Westermann Kinetics and Modeling of Anaerobic Digestion Process H. N. Gavala, I. Angelidaki, B. K. Ahring Molecular Biology of Stress Genes in Methanogens: Potential for Bioreactor Technology E. Conway de Macario, A. J. L. Macario Molecular Ecology of Anaerobic Reactor Systems J. Hofman-Bang, D. Zheng, E Westermann, B. K. Ahring, L. Raskin Applications of the Anaerobic Digestion Process Irini Angelidaki 1 · Lars Ellegaard 2 · Birgitte Kiœr Ahring 3 1 Environment & Resources, The Technical University of Denmark, Block 115, 2800 Lyngby, Denmark. E-mail: ria@er.dtu.dk 2 BWSC, Gydevang 11, 3450 Allerød, Denmark 3 Environmental Microbiology & Biotechnology, Biocentrum, The Technical University of Denmark, Block 227, 2800 Lyngby, Denmark At the start of the new millennium waste management has become a political priority in many countries. One of the main problems today is to cope with an increasing amount of primary waste in an environmentally acceptable way. Biowastes, i.e., municipal, agricultural or indus- trial organic waste, as well as contaminated soils etc., have traditionally been deposited in land- fills or even dumped into the sea or lakes without much environmental concern. In recent times, environmental standards of waste incineration and controlled land fillinghave gradu- ally improved, and new methods of waste sorting and resource/energy recovery have been de- veloped. Treatment of biowastes by anaerobic digestion processes is in many cases the optimal way to convert organic waste into useful products such as energy (in the form of biogas) and a fertilizer product. Other waste management options, such as land filling and incineration of organic waste has become less desirable, and legislation, both in Europe and elsewhere, tends to favor biological treatment as a way of recycling minerals and nutrients of organic wastes from society back to the food production and supply chain. Removing the relatively wet organic waste from the general waste streams also results in a better calorific value of the remainder for incineration, and a more stable fraction for land filling. Keywords. Anaerobic digestion, Reactors, Codigestion, Biowastes, Solid waste, Slurries, Manure, Industrial waste 1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 2 Factors Influencing the Biogas Process . . . . . . . . . . . . . . . 4 2.1 Temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 2.2 pH . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 2.3 Toxicity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 3 Digestion of Slurries . . . . . . . . . . . . . . . . . . . . . . . . . 7 3.1 General . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7 3.2 Process and Plant Configuration . . . . . . . . . . . . . . . . . . 8 3.3 Veterinarian Aspects . . . . . . . . . . . . . . . . . . . . . . . . . 9 3.4 Combined Digestion of Livestock Waste and Industrial Waste . . 11 3.5 Process Tank Configuration . . . . . . . . . . . . . . . . . . . . . 13 3.6 Equipment Characteristics . . . . . . . . . . . . . . . . . . . . . 14 CHAPTER 1 Advances in Biochemical Engineering/ Biotechnology, Vol. 82 Series Editor: T. Scheper © Springer-Verlag Berlin Heidelberg 2003 3.6.1 Mixing Technique . . . . . . . . . . . . . . . . . . . . . . . . . . 14 3.6.2 Pumping . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15 3.6.3 Heat Exchanging . . . . . . . . . . . . . . . . . . . . . . . . . . . 16 3.6.4 Biogas Cleaning . . . . . . . . . . . . . . . . . . . . . . . . . . . 17 3.6.5 Biogas Transmission . . . . . . . . . . . . . . . . . . . . . . . . . 20 3.6.6 Fiber Separation . . . . . . . . . . . . . . . . . . . . . . . . . . . 21 3.6.7 Odor Control Systems . . . . . . . . . . . . . . . . . . . . . . . . 22 3.7 Operational Experience and Results . . . . . . . . . . . . . . . . 22 3.7.1 Production Results . . . . . . . . . . . . . . . . . . . . . . . . . . 22 4 Digestion of High-Solid Wastes . . . . . . . . . . . . . . . . . . . 23 4.1 Pretreatment of Municipal Solid Waste . . . . . . . . . . . . . . . 24 4.2 Post Treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25 4.3 Biological Treatment . . . . . . . . . . . . . . . . . . . . . . . . . 25 4.3.1 Wet Digestion Systems . . . . . . . . . . . . . . . . . . . . . . . . 26 4.3.2 Dry digestion Systems . . . . . . . . . . . . . . . . . . . . . . . . 27 4.3.3 Multi-stage Anaerobic Digestion Systems . . . . . . . . . . . . . . 29 4.4 Summary of Processes Used for Anaerobic Treatment of Solid Wastes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31 5 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32 1 Introduction Anaerobic degradation or digestion is a biological process where organic carbon is converted by subsequent oxidations and reductions to its most oxidized state (CO2), and its most reduced state (CH4).A wide range of microorganisms catalyze the process in the absence of oxygen. The main products of the process are car- bon dioxide and methane, but minor quantities of nitrogen, hydrogen, ammonia and hydrogen sulfide (usually less than 1% of the total gas volume) are also gen- erated. The mixture of gaseous products is termed biogas and the anaerobic degradation process is often also termed the biogas process. As the result of the removal of carbon, organic bound minerals and salts are released to their solu- ble inorganic form. The biogas process is a natural process and occurs in a variety of anaerobic en- vironments. Such environments are, marine and fresh water sediment, sewage sludge, mud, etc. The interest in the process is mainly due to the following two reasons: – A high degree of reduction of organic matter is achieved with a small increase – in comparison to the aerobic process – in the bacterial biomass. – The production of biogas, which can be utilized to generate different forms of energy (heat and electricity) or be processed for automotive fuel. Biogas has a lower calorific value than natural gas, and in specific applications, such as automotive fuel, treatment of the biogas to improve its quality is required. 2 I. Angelidaki et al. In Table 1, the upper and lower calorific value of biogas in comparison to natural gas is shown. The biogas process has been known and utilized for many years, but especially after the rise of energy prices in the 1970s, the process received renewed atten- tion due to the need to find alternative energy sources to reduce the dependency on fossil fuels.Although the price of fossil fuels decreased in 1985, the interest in the biogas process still remains due to the environmental benefits of anaerobic waste degradation. Additionally, the biomass used for biogas production was originally produced by photosynthetic fixation of carbon dioxide from the at- mosphere, and combustion of biogas thus does not add extra carbon dioxide to the atmosphere as it does when combusting fossil fuels formed millions of years ago. The anaerobic degradation process has been used for years for energy pro- duction and waste treatment. It is used in closed systems where optimal and con- trolled conditions can be maintained for the microorganisms. The process can be utilized for the fast and efficient degradation of different waste materials. The anaerobic process is today mainly utilized in four sectors of waste treatment. 1. Treatment of primary and secondary sludge produced during aerobic treat- ment of municipal sewage. The process is utilized to stabilize and reduce the final amount of sludge and at the same time biogas is produced, which can be used to partly cover the need for energy in the sewage treatment plant. This application is widespread in the industrialized world in connection with the establishment of advanced treatment systems for domestic wastewater. 2. Treatment of industrial wastewater produced from biomass-, food-processing or fermentation industries. These wastewater types are often highly loaded and can successfully be treated anaerobically before disposal directly to the en- vironment or sewage system. The produced biogas can often be utilized to cover the need for process energy. With the environmental concerns and cost of alternative disposal this application of the anaerobic process is increasing. 3. Treatment of livestock waste in order to produce energy and improve the fer- tilizing qualities of manure. Due to more strict rules concerning the usage, dis- tribution, and storage of manure this application is growing especially in countries with a high animal production density. 4. A relatively new sector for use of the anaerobic processes on an industrial scale is treatment of the organic fraction of municipal solid waste (OFMSW). The aim of this process is first of all to reduce the amount of waste in other treat- ment systems, i.e. landfills and incineration plants, and secondly to recycle the nutrients from this type of waste to the agricultural sector. Applications of the Anaerobic Digestion Process 3 Table 1. Calorific value of biogas and natural gas Gas composition Biogas 65% CH4 Biogas 55% CH4 Natural gas Upper calorific value KWh/m3STP a 7.1 6.0 12.0 Lower calorific value KWh/m3STP a 6.55.5 10.8 a STP (standard temperature and pressure), i.e. the volume at 0 °C and 1 bar pressure. 2 Factors Influencing the Biogas Process The biogas process as a complex biological process is influenced by several en- vironmental factors. The interdependence of the bacteria is a key factor of the biogas process. Un- der conditions of unstable operation, intermediates such as volatile fatty acids and alcohols accumulate at different rates depending on the substrate and the type of perturbation causing instability. Thus, changes in the concentration of in- termediates indicate disturbance of the biogas process. The most important environmental factors that can influence the balance of the system are temperature, pH, substrate composition and toxins. 2.1 Temperature Temperature is one of the main environmental factors affecting bacterial growth. Anaerobic bacteria are affected in the same way as the aerobic ones. Growth rates often increase with increasing temperature up to a certain limit, while there is a rapid decrease in growth as the temperature approaches the upper limit for sur- vival of the bacterium. Besides the influence on growth rates of bacteria, tem- perature also influences physical parameters such as viscosity, surface tension and mass transfer properties.Apart from the general steady state dependency on temperature, also temperature stability is important, since even relatively small changes in the temperature result in an efficiency drop until adaptation has occurred. Treatment of waste in anaerobic reactors is normally carried out within two temperature ranges: around 25–40 °C, known as the mesophilic range, and higher than 45 °C, known as the thermophilic range. Several advantages of anaerobic waste digestion at thermophilic temperatures have been reported previously. At higher temperatures: – the rate of digestion is faster, and thus shorter retention times are required, – smaller reactor volumes are required for treating the same amount of waste, – higher rate and efficiency of particulate matter hydrolysis, – more efficient destruction of pathogens. Poor stability was previously believed to be associated with thermophilic tem- peratures. However, many years of experience with full-scale biogas plants op- erating at thermophilic temperature, have demonstrated that this is not the case. Temperature has a positive effect on the digestion rate, resulting in higher volumetric methane production rates. Casali and Senior found that the methanogenic rate in refuse increased 2.6 times when the temperature was in- creased from ambient temperature to 30 °C and further 3 times when the tem- perature was increased from 30 to 40 °C. However, the ultimate methane yield from organic matter is not influenced by temperature in the range 30 to 60 °C. Consequently the effect of temperature on 4 I. Angelidaki et al. growth rates can only be seen when the loading rates are high or retention times short. Varel et al. found with waste of beef-cattle in semi continuous reactor ex- periments that the effect of temperature on the rate of methane production was more noticeable at short retention times.As the retention time was decreased, ac- tive fermentation could only be achieved at thermophilic temperatures.At 3 days RT, active fermentation could only be achieved at temperatures between 45 and 60 °C and at 2.5 days RT only at 60 °C. Methanogenesis is also possible under psychrophilic conditions (below 25 °C) but at lower process rates. Anaerobic bacteria can adapt quite easily to low tem- peratures, and high rate anaerobic treatment has been achieved at psychrophilic conditions, when bacteria have been immobilized or otherwise retained in the process. It has been found that when shifting from mesophilic to psychrophilic tem- peratures the microbial populations still have the same composition as under mesophilic temperatures. This could indicate that at these temperatures psy- chrotolerant rather than true psychrophilic organisms are active. 2.2 pH The anaerobic digestion process is limited to a relatively narrow pH interval from approx. 6.0 to 8.5; a pH value outside this range can lead to imbalance. Each of the microbial groups involved in anaerobic degradation has a specific pH optimum and can grow in a specific pH range. The methanogens and aceto- gens have pH optimum at approx. 7, while acidogens have lower pH optimum around 6. Methanogens at pH lower than 6.6 grow very slowly. In an anaerobic reactor, instability will as a rule lead to accumulation of VFA, which can lead to a drop in pH (acidification). However, accumulation of VFA will not always be expressed as a pH drop due to the buffer capacity of some waste types. In manure there is a surplus of alkalinity, which means that the VFA ac- cumulation shall exceed a certain point before this can be detected as a signifi- cant change in pH. This means that when a drop in pH in the reactor is eventu- ally observed, the concentration of volatile fatty acids is most probably very high and the process may already have been affected. There are many factors which influence pH. It is especially organic acids and carbon dioxide which lower pH, while ammonia will contribute to an increase of pH. Other compounds contributing to the buffering capacity are hydrogen sul- fide and phosphate. 2.3 Toxicity A number of compounds are toxic to the anaerobic microorganisms. Methan- ogens are commonly considered to be the most sensitive to toxicity of the micro- organisms in anaerobic digestion. However, the process can acclimatize, and higher concentrations of the toxicant can be tolerated after a period of adapta- tion. The most common inhibitor for the anaerobic process is ammonia. In anaer- Applications of the Anaerobic Digestion Process 5 obic digestion ammonia originates from soluble ammonia in the influent, from protein degradation and other compounds such as urea. Many substrates used for anaerobic treatment often contain ammonia in toxic concentrations. Such sub- strates include pig and poultry manure, slaughterhouse waste, potato, juice, highly proteinaceous sludge, wastewater from shale oil and coal liquefaction processes. The results concerning ammonia-N inhibitory level are conflicting, as they depend on parameters such as pH, temperature and adaptation of the in- ocula. It is generally accepted that it is the non-ionized form of ammonia that is responsible for inhibition, pH has a significant effect on the level of ammonia in- hibition, as the pH value determine the degree of ionization. The free ammonia ratio to total ammonia/ammonium ratio can be calculated from the equilibrium relation as follows: [NH3]/[T – NH3] = 1/(1+[H+]/Ka) where, [NH3] and [T – NH3] are the free ammonia and the total ammonia/am- monium concentrations respectively, and Ka is the dissociation constant, which is temperature dependent. In Fig. 1 this dependency is shown graphically. As pH and temperature in- crease the free ammonia fraction also increases. Especially pH has a strong in- fluence on the degree of ionization of ammonia. Bhattacharya and Parkin found the maximum tolerable free-ammonia concentration to be only 55 mg-N/l. Most reported inhibitory levels are, however, higher.Angelidaki and Ahring found that the biogas process could be adapted to tolerate free ammonia concentration of 800 mg-N/l. The inhibitory level of free ammonia depends strongly on the degree of acclimatization of inoculum to ammonia. As the free ammonia concentration decreases with decreasing pH it could be expected that even a slight reduction of pH would have a positive effect on ammo- 6 I. Angelidaki et al. Fig. 1. pH and temperature influence on NH3 dissociation nia inhibition. It was indeed found by several investigators that a pH decrease reduced ammonia inhibition. Free ammonia inhibition result in VFA accumula- tion, which in turn lower pH and decrease the ratio of free ammonia, with the result that free ammonia inhibition is relieved. Due tothis self-stabilizing mech- anism, processes can be maintained in a stable ammonia inhibited state, where a balance between VFA concentration and ammonia loading exist. The carbon/nitrogen (C/N) ratio is also important for process stability.A C/N ratio of 25 to 32 has been reported to have a positive effect on the methane yield. At lower C/N ratios the risk of excess nitrogen not needed for biomass synthesis and therefore becoming inhibitory increases. Opposite, a very high C/N ratio would lead to N deficiency for biomass synthesis.Waste with very high COD con- centration and low content of nitrogen such as olive mill effluents has been shown not to be able to be degraded alone. Addition of either nitrogen or codi- gestion with wastes with a lower C/N ratio was needed in order to digest olive mill effluents successfully. Anaerobic treatment of wastewater containing high sulfate concentrations can cause inhibition as a result of the formation of hydrogen sulfide. It has been reported that total hydrogen sulfide concentrations of 100 to 300 mg/l or free hydrogen sulfide concentrations of 50 to 150 mg/l caused severe inhibition re- sulting in complete cessation of biogas production. Long chain fatty acids, such as oleate and stearate, have been found to be toxic to the anaerobic process. No adaptation to the fatty-acid toxicity was observed. However, the presence of particulate material can increase the resistance of the process to long-chain fatty acids as LCFA are absorbed on the particulate mate- rial and thus not active as inhibitor. For other organic compounds such as phe- nols, chloroform and formaldehyde a reversible toxicity has been observed. Heavy metals are toxic for anaerobic microorganisms in concentrations in the range 10–3 to 10–4 M. However, experiments have shown that acclimatization to high heavy metal concentrations can occur and often the level of heavy metals would become an environmental problem before affecting the process. In a re- actor, the actual concentration of soluble metal ions is normally low due to pre- cipitation of insoluble metal salts, e.g., as sulfides. It has been shown that less than 2% of the metals may be in the soluble form. Although anaerobic bacteria are inhibited by several toxicants they can also tolerate a number of toxicants. Complete anaerobic degradation of pen- tachlorophenol has been reported. A number of other toxicants have been re- ported to be detoxified in anaerobic reactors such as nitroaromatic compounds, chlorinated aliphates, N-substituted aromatics and azo dyers. 3 Digestion of Slurries 3.1 General One type of anaerobic waste treatment plants which have emerged since the mid 1980s in Denmark and elsewhere, are large scale manure treatment plants serv- Applications of the Anaerobic Digestion Process 7 ing a number of farmers, treating a slurry of manure, often with a fraction of other waste as supplementary substrate. The main objective is to extract energy and to improve the fertilizing quality of manure, resulting in less nutrient leakage to ground and surface waters from the agricultural sector. The description below gives an impression of the most important elements of such a slurry treating biogas plant, also illustrating some of the practical design considerations not directly related to the reactor system itself, as well as illus- trating the gradual technical development waste treatment plants often undergo. 3.2 Process and Plant Configuration The main elements in a typical large-scale manure biogas plant, are shown in Fig. 2. Raw material is transported by special constructed lorries from/to farm- ers and is kept in pre-storage buffer tanks. It is then pumped through heat ex- changers into the reactor at the desired flow rate. The effluent is pumped to an 8 I. Angelidaki et al. Fig. 2. Concept of manure biogas plants top Farm biogas plant bottom Centralized biogas plant after-storage tank, before it is brought back to the farmers and finally utilized on fields as fertilizer. A biogas plant is in reality much more complex than described above. Many unit operations are or may be utilized in such a plant i.e.: – transport/pumping – stirring/mixing – macerating/grinding – heat exchanging – biogas treatment and cleaning – biogas compression and transportation – biogas storage – filtration/separation Figure 3a shows a picture of a biogas plant (Blaabjerg biogas plant, Denmark), where some of these unit operations are employed, is shown. In Fig. 4 the general lay-out of a full-scale biogas plant (Blaabjerg, Denmark) is shown. Many process and lay-out variations are possible, often dictated by local con- ditions and needs. 3.3 Veterinarian Aspects Mixing and redistribution of manure, from several farms, requires adoption of a sufficient level of sanitation, in order to avoid the risk of spreading pathogens. The veterinarian requirements in Denmark concerning manure are to ensure that the manure is kept at a thermophilic temperature (> 50 °C) for a minimum Applications of the Anaerobic Digestion Process 9 Fig. 3. A centralized biogas plant (Blaabjerg, Denmark) of 4 hours. The required sanitation can be obtained directly in a thermophilic process by observing special pumping routines, whereas a mesophilic process re- quires a passive pre- or after sanitation stage (Fig. 5). It has been documented that the above requirements ensure an effective pathogen reduction, reaching a level equal to or better than 4 log-units when us- ing Faecal streptococcus as an indicator organism. Certain types of supplemen- tary waste suitable for codigestion in manure based biogas plants, such as sewage-sludge, require more strict sanitation, due to the potential content of hu- man pathogens. Originally such types of waste required heating to 70 °C for a minimum of 1 hour.A special Danish veterinarian research effort, utilizing high temperature resistant bacteria and vira as indicators, has resulted in the defini- tion of alternative temperature/time combinations, which in conjunction with a biogas process, are considered equivalent to a 70 °C/1 h heating. For a ther- mophilic biogas process (minimum 52 °C), a guaranteed temperature/retention time of 52 °C/10 hours, 53.5 °C/8 hours or 55 °C/6 hours is considered equivalent to 70 °C/1 hour. The retention can take place in separate sanitation tanks before or after the reactor stage, or directly in the reactor if pumping sequences allow the necessary pauses. For mesophilic biogas plants slightly higher retention times are required and sanitation must take place in a separate tank at a thermophilic temperature level.While inclusion of “problematic” waste in the past required a separate pretreatment step, all the biomass can now be sufficiently sanitized in a single thermophilic process, provided the longer guaranteed retention times is built into the design. 10 I. Angelidaki et al. Fig. 4. Typical lay-out of a centralized biogas plant (Blaabjerg, Denmark). This plant is treat- ing approx. 100,000 ton of manure and industrial waste per year, and producing approx. 3 mil- lion m3 of biogas per year 3.4 Combined Digestion of Livestock Waste and Industrial Waste Construction of Joint Biogas Plants gives the possibility for combined anaerobic treatment and utilization of livestock waste and several types of organic waste from the food processing industry. Organic industrial waste is usually characterized by high pollution loads and often contains high concentrations of rapidly degradable substrates such as sac- charides, starches, lipids and proteins. Manure usually has a rather low solids concentration (typically 3–5% total solids (TS) for pigs and 6–9% for cattle and dairy cows). In addition the manure contain particles and straw/fibers with a content of ligno-cellulose. This fiber fraction is highly recalcitrant to degradation and will often pass through the re- actor mainly undigested. The high content of water together with the high frac- tion of fibers in manure is the reasonfor the low methane yields of manure, typ- ically ranging from 10–20 m3 CH4/ton of manure treated. However, manure is an excellent basic substrate for co-digestion of industrial waste, which could otherwise be difficult to process alone. The reasons for this are: – the high content of water in manure acts as a solvent for the dryer types of wastes, solving problems of pumping and mechanical treatment of solid wastes. Applications of the Anaerobic Digestion Process 11 Fig. 5. Plant configuration examples: 1 Thermophilic plant with two reactors and heat ex- changing; 2 Mesophilic plant with two reactors, heat exchanging and thermophilic post sani- tation – the high buffering capacity of manure protects the process against failure due to pH drop if the VFA concentration increase. – manure is rich in a wide variety of nutrients necessary for optimal bacterial growth. By combining different types of waste, such as manure, municipal solid waste and organic industrial waste, a much higher gas yield can be obtained from biogas reactors since organic industrial wastes in particular are more easily degraded and have a higher gas potential than manure. As most types of indus- trial organic waste result in methane yields varying from 30 to 500 m3/ton, these sources constitute a very attractive supplementary substrate for manure based biogas plants. The gas yields from different types of organic industrial waste is shown in Table 2. Besides increasing the yield, addition of easily degradable material has been shown to stabilize the anaerobic digestion process if added in a controlled fash- ion. This effect could be partly due to a higher active biomass concentration in the reactor, which will be more resistant to inhibitory compounds. Furthermore, the inorganic parts of some organic wastes, such as clays and iron compounds, 12 I. Angelidaki et al. Table 2. Methane yield from different types of industrial waste Type of organic waste Composition of the Organic content Methane yield organic material (%) (m3/ton) Stomach and Carbohydrates, proteins and lipids 15–20 40–60 intestine content Flotation sludge 65–70% proteins, 30–35% lipids 13–18 80–130 (dewatered) Bentonite- 70–75% lipids, 40–45 350–450 bound oil 25–30% other organic matter Fish-oil sludge 30–50% lipids and other 80–85 450–600 organic matter Source sorted organic Carbohydrates, proteins, and lipids 20–30 150–240 household waste Whey 75–80% lactose and 20–25% protein 7–10 40–55 Concentrated whey 75–80% lactose and 20–25% protein 18–22 100–130 Size water 70% proteins and 30% lipids 10–15 70–100 Marmelade 90% sugar, fruit organic acids 50 300 Soya oil/Margarine 90% vegetable oil 90 800–1000 Methylated spirits 40% alcohol 40 240 Sewage sludge Carbohydrates, lipids, proteins 3–4 17–22 Concentrated sewage Carbohydrates, lipids, proteins 15–20 85–110 sludge have been shown to counteract the inhibitory effect of ammonia and sulfide, re- spectively. 3.5 Process Tank Configuration Continuous feeding/pumping is often preferred in order to optimize heat exchangers. In order to obtain the necessary guaranteed retention time for sanitation purposes, configurations with two or three reactors (or sanitation tanks) operated in parallel are often seen, Fig. 6. At any given time, one reactor is being fed, one emptied and one resting, i.e., ensuring the sanitation retention time. As fewer larger tanks are often preferred for economical reasons, various schemes with discontinuous pumping or combinations with smaller buffer tanks can also be seen. Applications of the Anaerobic Digestion Process 13 Fig. 6. A biogas plant with two reactors and post sanitation 3.6 Equipment Characteristics 3.6.1 Mixing Technique Initially, submerged electrically driven medium speed mixers, mounted on guid- ing rails were utilized for most mixing tasks. These mixers soon proved rather costly to operate, especially where access and routine service inspection is diffi- cult as is the case for digesters or other closed process tanks. Slow moving, top mounted central mixers with a freely suspended shaft with two propellers have become the preferred solution for reactor mixing. The mixers usually work con- tinuously with a mixing power input of 3–4 W/m3. Service requirements are very limited, but a correct reactor level relative to the upper impeller is very critical in order to avoid annoying floating layer formation. In storage tanks several types of mixers are in use, including improved submerged models. The mixing energy input is often discontinuous (high power for a short period) and average mixing power input typically varies from 10 W/m3 in prestorage/mixing tanks to 1 W/m3 in after storage tanks. The position and type of mixers in combination with tank geometry have proven to be very critical. Hydrodynamic favorable solutions, al- lowing the material to flow to the mixers, generally work best in combination with mixing at different depths. Figure 7 schematically shows the most common mixer configurations. 14 I. Angelidaki et al. Fig. 7. Common mixer configurations: A Top mounted reactor mixer; B Side mounted mixer in process tank/storage; C Submerged mixer on guiding rail; D Top mounted mixer; E Top mounted mixer with submerged angle gear In Fig. 8 a picture of the reactor top with a centrally mounted top mixer is shown. 3.6.2 Pumping Eccentric worm pumps have been used for continuous feeding/extraction of biomass (low flow, high pressure) while centrifugal pumps with open impellers and cutters have been used for biomass transfer between storage tanks (high flow, low pressure). Feeding pumps, in particular those handling fresh biomass have proven to be rather costly to operate due to high wear rates, but, despite several efforts, no viable alternative has been found so far. Low pump speed (< 300 rpm) and a pressure drop as low as possible can somewhat alleviate the problems. Applications of the Anaerobic Digestion Process 15 Fig. 8. Reactor top, showing centrally mounted top mixer. Mixer shaft extends to the bottom of the reactor (approx. 17 m) with two propellers (3.2 m) placed at the top (just below liquid sur- face) and at the bottom 3.6.3 Heat Exchanging Most biogas plants in Denmark utilize heat exchanging between in-going fresh biomass and outgoing digested biomass, although a few plants have been built with no or limited heat exchanging. The choice depends on the value of heat, i.e., the possibility of utilizing heat for other purposes. Due to the high viscosity of manure and other biomass, especially when fresh, it is seldom possible to obtain a turbulent flow without generating an excessive pressure drop. Laminar or transition flow is the result with rather poor heat transfer coefficients. The most common types of exchangers utilize curved flow channels to break up the thermal boundary layers by secondary flow or multi pass design to break up the flow at regular intervals. Most designs attain heat transmission values of approx. 300 W/m2/°C with flowing velocities up to approx. 1 m/s, when exchanging fresh biomass against digested biomass, or approx. two times as much if exchanging against water. Dimensioning, especially for pressure drop, relies very much on experience, as prediction of biomass viscosity is very uncertain.A good design margin and spare pump capacity is necessary to avoid problems. In designs with rather narrow flow passages (< approx. 30 mm) it is considered wise to macerate the fresh biomass, which is also likely to improve the biogas yield slightly. Different heat exchanger configurations are shown in Fig. 9. Typical dimensioning practice (in Denmark) leads to heat exchanger instal- lations with a resulting temperature difference of 10–15 °C. The remaining heat- 16 I. Angelidaki et al. Fig. 9. Different heat exchanger configurations ing up to process temperature, and for heat loss compensation, is by hot water coils in the reactors or with a final biomass/water heat exchanger plusfewer coils for heat loss compensation. In this connection, it is important to recognize and include the heat loss due to evaporation of the water contained in the humid bio- gas leaving the reactor. A typical heat exchanger used in full scale biogas plants is shown in Fig. 10. On the input side of heat exchangers (and pumping systems) the risk of clog- ging is manly due to the possible presence of foreign objects. On the digestate side of heat exchangers, one must reckon with the formation of struvite (MgNH4PO4), which forms due to over-saturation when the biomass is cooled. The scaling occurs mainly in the cold sections and will gradually close flow chan- nels. The struvite needs to be dissolved by flushing with a circulating weak acid at regular intervals. Residual scaling also occurs in cold pipes down stream of heat exchangers, although at a much slower rate. 3.6.4 Biogas Cleaning Dry biogas from manure generally consist of approx. 60–70% v/v methane (CH4), 30–40% v/v carbon dioxide (CO2), 1–2% v/v nitrogen (N2), 1000– 3000 ppm hydrogen-sulfide (H2S) and 10–30 ppm NH3 . The concentration of hydrogen-sulfide stated is typical when operating on manure alone. Other Applications of the Anaerobic Digestion Process 17 Fig. 10. Typical exchanger used in full scale biogas plants substrates, even in relatively small amounts, can result in quite different levels, both lower and higher. Raw biogas is a humid gas, which needs to be cooled and carefully drained be- fore utilization. Early attempts to dry biogas using regenerative absorption equipment designed for pressurized air proved difficult due to accelerated ab- sorbent decomposition, and the preferred solution has instead become to sim- ply cool the biogas and to design the gas system with care to avoid undrained low points. In the case where the biogas is to be utilized in a boiler and emission re- quirements for sulfur-dioxide are not too strict, no further cleaning is necessary. In many cases, however, the biogas is utilized in gas engines for Combined Heat and Power (CHP) generation. In this case the hydrogen-sulfide content needs to be kept below approx. 700 ppm for conventional gas engines in order to avoid ex- cessive corrosion and too rapid (and costly) lubrication oil deterioration. One method of reducing the hydrogen-sulfide content is to add a commercial ferrous solution to the reactor feed. Ferrous compounds bind sulfur as insoluble prod- ucts in the liquid phase, which reduces the evolution of gaseous hydrogen-sulfide. The method has been utilized in a number of plants, but is rather costly if applied continuously, since the consumption of ferrous material on a stoichiometric ba- sis has proven to be 2–3 times the desired reduction in gaseous hydrogen-sulfide. In some cases, however, ferrous containing waste products can be obtained for codigestion most of the year, with commercial ferrous addition acting as a back up possibility only. Often secondary H2S biogas cleaning is necessary, and in this case a biologi- cal oxidation process has become the dominating solution. By injection of a small amount of air (2–8 % v/v) into the raw biogas, the hydrogen-sulfide content can be biologically oxidized either to free (solid) sulfur or (aqueous) sulfurous acid according to following reactions: 2 H2S + O2 Æ H2O + 2 S (1) 2 H2S + 3 O2 Æ 2 H2SO3 (2) The reaction will occur spontaneously and can take place in the reactor headspace on the floating layer (if any) and reactor walls, if air is injected directly in the headspace. Due to the acidic nature of the products with a risk of corrosion and the dependency of a stable floating layer, it is often preferred to isolate the process in a separate reactor as shown schematically in Fig. 11. The reactor is somewhat similar to a scrubber, consisting of a porous filling (randomly packed plastic elements or similar) where microorganisms can grow, and a sump, pump, and nozzle arrangement allowing regular showering of the filling. Showering has the function of washing out acidic products and supplying nutrients to the microorganisms. The sump must therefore contain a liquid with a high alkalinity and contain essential nutrients, for which digested manure, preferably screened, is the ideal and readily available choice.A reactor loading of approx. 10 m3/h of biogas per m3 of reactor filling and a process temperature around 35 °C has been the normal choice, and the process has proven very effi- cient, provided that sufficient air is injected (slightly more than stoichiometri- 18 I. Angelidaki et al. cally needed). Sump pH must be maintained at 6 or higher.A washing procedure, where the filling elements are gurgled through with an air/water mixture, has to be carried out at regular intervals in order to prevent free sulfur deposits from closing the reactor filling. In some cases, where biogas is stored or passing through a digestate after storage, the H2S reactor is omitted and only air injected. Cleaning is then relying on the formation of a floating layer in the after storage, on which the microorganisms can grow and perform the oxidation. A floating layer can usually be maintained with the choice of a low mixing intensity, without too many problems for operating the tank as a buffer storage. This solution is certainly more cost effective, but can also be more unreliable as floating layers can be rather unstable, i.e., sinking overnight perhaps to resurface some days later. At least some periods with reduced cleaning efficiency can be ex- pected. In Fig. 12, a reactor used for biological hydrogen-sulfide reduction is shown. Applications of the Anaerobic Digestion Process 19 Fig. 11. Schematic diagram of system for biological H2S oxidation 3.6.5 Biogas Transmission Biogas Plants are usually situated at some distance from the nearest town, while biogas utilization in an engine CHP installation often takes place inside or in the vicinity of the town in order to connect to a district heating system. As a conse- quence biogas often has to be transported up to several km between the plants. The first plants utilized high pressure (2–4 bar) dry transmission with piston compressors and absorption drying equipment.As mentioned earlier, absorption drying presented problems, and as piston compressors also proved vulnerable and operationally expensive, which has caused the low pressure wet transmission to be gradually taken over. This solution usually involves a transmission pressure in the range 400–700 mbar in order to deliver at 100–200 mbar, utilizing Roots blowers and a carefully planned buried transmission line, laid with a minimum 3–5‰ slope (preferably in the flow direction) with a limited number of con- densate wells. The bulk of condensation occurs in the first few wells within 100–500 m from the plant. Wells are equipped with valves for regular manual emptying, and the wells are usually designed to hold up to a weeks amount of condensate, meaning that the first wells must be quite large (typically 2 m3), while the last only need to be small (typically 100 liters). 20 I. Angelidaki et al. Fig. 12. Hydrogen sulfide reduction reactor, 80 m3 with 50 m3 filling material. H2S is oxidized by a biological process to acidic products or free sulfur, with injection of a small amount of atmospheric air upstream of the reactor At transmission distances up to a few hundred meters, high speed centrifugal blowers and a transmission pressure of approx. 100 mbar can be employed with advantage. 3.6.6 Fiber Separation Manure and other types of biomass contain fibers (from straw) and other organic structures which are difficult for anaerobic organisms to access.A typical degra- dation “efficiency” of 50–60% is often seen in manure based systems, meaning that the digestate still contain 40–50% of the original organic dry matter content primarily as fibers. Some of the early plants included separators to take out a part of the fibers for production of commercial compost. Marketing thiscompost in relatively small scale proved quite difficult, and compost production has ceased in most plants. Some of the newest plants in Denmark again include separation equipment. The intention now is to produce a fiber fraction with a dry matter content in excess of 45%, which can be utilized as a supplementary fuel in wood chip boilers. This way the overall energy efficiency can be raised by approx. 15% through additional heat production. A side benefit, which in the near future might add to the feasibility of this scheme, is the removal of surplus phosphorous which is predominantly attached to the fibers. Screw type separators dominate, sometimes in combination with a pre-sepa- ration in order to increase the capacity (Fig. 13). Applications of the Anaerobic Digestion Process 21 Fig. 13. Fiber collection wagon, with distribution screw 3.6.7 Odor Control Systems One of the benefits from anaerobic digestion of manure is a considerable reduc- tion in odor nuisance when spreading manure on fields. The biogas plant itself can, however, give rise to local odor nuisance if care is not taken to limit odor emissions. As a first preventive measure, it is of course desirable to situate the plant (if possible) without immediate neighbors. In addition all storage tanks should be covered. Due to service openings and as unloading/loading and internal pump- ing generates tank breathing, it is necessary to arrange a weak suction from the storage tanks and other contaminated sections of the plant. This air must be treated in order to avoid odor emission. Air treatment is usually chosen either as a biological cleaning in a compost filter or as a combustion. Compost filters are relatively cheap but operational experience. Careful attention and maintenance are required in order to ensure satisfactory cleaning, as filters sometimes fail due to acidification (oxidation of hydrogen-sulfide), might collapse and become too dense, or might run dry. Com- bustion in a boiler in conjunction with generating process heat for the biogas plant has been tried, but the need for combustion air is limited, enforcing a compromise on venting flow. Combustion in engines (together with the biogas) has so far not been attempted, due to the fear of affecting the engine negatively. In a few plants, a system involving combustion with regenerative heat exchanging has been em- ployed, a technique commonly utilized for the combustion of gaseous solvents in industrial ventilation air.Although a rather expensive solution, results are positive. 3.7 Operational Experience and Results 3.7.1 Production Results Figure 14 shows the average monthly biogas production during the first opera- tional period of two thermophilic Biogas plants, both with a biomass treatment capacity of 100,000 ton biomass per year. The figure shows typical start-up periods of 4–6 months and illustrates the relative stability of the production, once normal operation is obtained. The sudden rise in biogas production of one of the biogas plants after month 13, was due to the introduction of residual fish oil as a co-substrate. Consumption of process energy of relatively new plants typically amount to approx. 4–5 kWh per m3 biomass treated for mixing, pumping, control etc., and a heat consumption of 15–25 kWh per m3 of biomass treated, including con- sumption for hot water, heating of buildings, etc. This should be compared to a biogas yield of approx. 30 m3 per m3 biomass, corresponding to a lower calorific value (LCV) yield of approx. 200 kWh, i.e., 10–15% of the energy produced is consumed in the process. These figures represent the state of the art level for large-scale manure based biogas plants in Denmark, achieved as a result of the technical development described shortly above. 22 I. Angelidaki et al. 4 Digestion of High-Solid Wastes A special problem arises when solid wastes are to be treated.Anaerobic treatment of waste water and other liquid types of wastes have been used for decades. How- ever, treatment of high-solids wastes such as municipal solid waste (MSW) is a relatively new application of anaerobic treatment, and many technical aspects need special consideration when inhomogeneous urban waste is the source ma- terial. “High-solid wastes” might be defined as organic material with a content of solids between 10 to 40%, which is not fluid. The most important type of high solid wastes is Municipal Solid Waste (MSW) or Household Solid Waste (HSW). The most common way to dispose of MSW has until recently been land filling or incineration. However, in the recent years attention has focused on recycling. By recycling the valuable elements of waste are converted to useful products and returned to the supply chain, minimizing the pressure on land filling and incin- eration facilities, while also conserving primary resources. Recycling started as a positive but minor part of waste management, but has become a more and more dominant element in the waste policies and strategies in many countries. MSW is a heterogeneous waste, which can be divided into the following frac- tions: – an organic biodegradable fraction, consisting of food residues and sometimes garden wastes Applications of the Anaerobic Digestion Process 23 Fig. 14. Average monthly biogas production from thermophilic manure based biogas plants: from Thorsoe (1994) and Blaabjerg (1996) – a combustible fraction, consisting of an organic recalcitrant fraction, such as wood, paper and plastic – an inert fraction, consisting of stones, glass, metal and other inorganic parts Waste composition varies enormously, both between countries and between lo- cations in the same country. In urban built-up areas, MSW is less rich in organic biodegradable material compared to rural areas and the composition also varies with the social level of the area. The organic biodegradable fraction of the MSW can be treated by anaerobic digestion to produce energy and fertilizer. By anaerobic degradation, one ton of the organic fraction of MSW can give a net energy yield of 100 to 200 kWh elec- tricity plus heat. Most often the technical aspects involved are: – source separation and collection – separation (removal of plastic bags or other packing and foreign elements) – transfer (transporting the material through the process/plant) – heating the substrate – reactor mixing – sanitation of the biomass Digestion of high solids wastes can take place as a continuous or batch process. Continuous processes are most desirable on a larger scale. There are many waste treatment systems specifically designed for treatment of municipal waste (MSW). The most treatment systems consist of the following steps: – Pretreatment – Biological treatment – Post-treatment 4.1 Pretreatment of Municipal Solid Waste Municipal solid waste typically contains less than 1/3 organic material. In order to treat MSW biologically, a sorting of the waste is needed. The sorting can be achieved by either source-separation, mechanical separation, or by hand sorting techniques. Source-separated municipal waste (SSMSW), i.e., waste sorted into frac- tions where it is generated, is the preferred solution from a quality point of view, since it is difficult to derive a clean organic fraction once the waste has been mixed. Such systems are found only in limited areas. However, in several places in Europe, work is being done, in order to introduce source separation of the MSW. Source-separated collection was originally introduced to derive certain valuable components, due to the increased cost of raw materials and a wish to limit the use of primary resources and energy to process new raw materials. As a consequence, source-sorted collections were introduced mainly for paper, valuable metals (such as aluminum and copper), and glass etc. Lately source- separation has also included separation of an organic degradable fraction. This 24 I. Angelidaki et al. is done by including separate waste bins and collection systems in the house- holds.An alternative scheme, which has been implemented in some areas, is source separation into bags of different colors, but collected with only one truck and later sorted out into seperate fractions by an optical sorting machine. This way the extra cost of separate collection or multi compartment collection trucks can be avoided (by utilizing existing collection trucks), albeit at the expense of a sorting machine. Most of the MSW is, however, still not source-separated. Therefore, pretreat- ment is often needed to sort out the organic fraction of mixed MSW. The main goal in the different pretreatment systems is to separate the organic fraction from the inorganic material. Furthermore, effort is applied in recycling several useful components, such as ferrous metals. The fraction obtained by mechanical separation is usually more contaminated then the fraction obtained by source-separation, and a fraction of the organic material will be lost with the other fractions sorted out. It is especially the con- tent of heavy metals and plastics that is higher in the mechanical separated MSW. Even in case of source separation, some form of pretreatment is often needed to guard the plant and end product against elements included in the organic frac- tion by mistake or carelessness. 4.2 Post Treatment Following the biological treatment, the digested material (known as digestate or effluent) is usually dewatered to 50–55% TS with a screw press, filter press or other types of dewatering systems. The press cakes are refined with sieve and composted aerobically. At this point, the compost can be further cleaned by screening, to remove unwanted material such as small pieces of glass or plastic. The compost is often offered for sale as a soil conditioner or potting soil (nitrate approx. N = 0.25 kg/ton, total N approx. 7–8 kg/ton). Press liquid, which may con- tain high concentrations of volatile fatty acids, is centrifuged, recircled or sent to wastewater treatment. 4.3 Biological Treatment There are various classification principles of the existing anaerobic systems for treatment of high solids wastes. There are batch and continuous systems according to the feeding procedure of the wastes to the reactors. Most systems are continuous systems. However, there also exist batch systems such as the Biocel process. The major difference between the various systems is whether a “wet” or “dry” methanization process is used. Digestion of the MSW can take place either in the mesophilic or the thermophilic temperature range, and the hydraulic retention time is 10 to 30 days, depending on the process temperature, the technology used, and the waste composition. Applications of the Anaerobic Digestion Process 25 4.3.1 Wet Digestion Systems With wet digestion systems the total solids content of the waste has to be re- duced to concentrations below 20% in order to create a pumpable slurry. This can be done either by adding water, such as recycled process water, or by co- digestion where MSW is mixed with more dilute streams such as sewage sludge or manure. Codigestion Process Treating high solid waste requires technically complicated and expensive treat- ment systems. Therefore, it is desirable, if possible, to avoid treating the waste as a solid, but instead mix it with other more dilute waste. A new concept, which has been applied successfully in several biogas plants in Denmark (Vegger, Sinding Ørre, Studsgård and Århus) is mixing MSW with ma- nure. Sweden's largest biogas plant in Kristianstad work with the same co-di- gestion concept: household waste is treated together with agricultural waste and industrial waste. The plant at Kristianstad has a capacity of 73,000 tons of bio- mass per year, of which 15% is OFMSW, 18% is industrial organic waste, and 67% is manure. The biogas yield is around 40 m3 biogas per ton feedstock and the pro- duction covers the heat requirements of 600 to 800 households. In this way some of the difficult technical problems treating high solid wastes are avoided. Also economy of scale can be achieved and the waste enters into an established nu- trient/fertilizer recycling system. The plants generally operate at thermophilic temperatures. Another example of the excellent performance of a large-scale co-digestion process of the organic fraction of municipal solid waste is the sewage treatment plant in Grindsted, Denmark where MSW is mixed with sewage sludge. The Waasa Process Another process using codigestion is the Waasa process. The process has been tested on a number of wastes. In the Waasa plant in the city of Vaasa, Finland the following types of wastes have been treated over the years since it started up in 1989; mechanically or source-separated MSW, sewage sludge, slaughterhouse waste, fish waste, and animal manure. The process operates with a TS content of approx. 10–15% and can operate both at mesophilic and thermophilic temper- atures.At the Waasa plant both mesophilic and thermophilic treatment methods are in operation in two parallel reactors. Today the Waasa Process is also in op- eration in Kil, Sweden and outside Tokyo, Japan. Furthermore, a plant in Gronin- gen, the Netherlands is under construction. One characteristic of the Waasa Process is its main reactor, which is divided into various zones in a simple way. The first zone is made up of a pre-chamber inside the main reactor. The mixing in the reactor is by pneumatic stirring, where biogas is pumped through the base of the reactor. A small part of the digestate is mixed into the newly fed bio waste to speed up the process by inoculation. 26 I. Angelidaki et al. 4.3.2 Dry Digestion Systems In many cases, especially in large urban areas, it is difficult to find other wastes to codigest MSW with. Dry digestion systems can cope with solids as high as 35%. The VALORGA Process The Valorga process was developed in France and is a semi-dry process (Fig. 15). The process is a mesophilic process and takes place in the following way: after pretreatment the waste is mixed with recycled process water. The process water is gained from separation of the reactor effluent by centrifugation, filtration or other types of separation.After mixing with process water, the influent is pumped into the reactor. The reactor is of the fully mixed reactor type. Mixing is taking place by pneumatic stirring, i.e., the produced biogas is compressed and sent through the contents of the reactor. Only a small amount of water is recirculated, and the total solids content of the waste in the reactor is still high. Other processes also use the same principle, i.e., recirculation of small or large amounts of process water. The Valorga process is a relatively widely used process. There are several full-scale plants worldwide, such as in Amiens, France (85,000 ton/year), Grenoble, France (16,000 ton/year), Tilburg, Netherlands (52,000 ton/year) (Fig. 16), Papeete, Tahiti (90,000 tons/year) and Tamara in French Polynesia (92,000 tons/year). The DRANCO Process The Dranco (Dry Anaerobic Composting) process is a true dry-process for treat- ment of the organic fraction of MSW (Fig. 17). Indeed, this process requires a high total solids content in the reactor in order to have optimal performance. Applications of the Anaerobic Digestion Process 27 Fig. 15. Principle diagram of the Valorga process Therefore, it is often recommended to mix non-recyclable paper or garden waste into the MSW in order to achieve a sufficiently high TS content. The Dranco process is a thermophilic process. The process takes place in the following way: after the waste is pretreated and screened it is mixed with recirculating material from the reactor. Three quarters of the reactor content is recycled. Mixing of the waste with this large amount of digested material ensures inoculation of the incoming material. The biomass paste is pumped using piston pumps developed to pump con- crete casting mixtures. The reactor is a downward plug-flow type reactor. In the reactorno significant mixing takes place. If the waste consists of high amounts of easily degradable 28 I. Angelidaki et al. Fig. 16. View of a Valorga biogas plant (Tilburg, Holland). The plant has capacity of 52,000 tonnes per year of source separated VGF (Vegetable-Garden-Fruit) waste Fig. 17. Principle diagram of the Dranco process material, the degradation can cause liquefaction of some of the material in the reactor, preventing the plug flow principle with the risk that some particles will flow through the reactor without achieving the required retention time. There- fore, addition of recalcitrant ligno-cellulose material is usually recommended. The digested biomass is extracted from the bottom of the reactor by a special patented sliding frame, pulling material evenly from the reactor cross section into an extraction screw channel. Today, there are several DRANCO plants in operation, Fig. 18, such as the one in Brecht, Belgium (12,000 ton/year), Salzburg,Austria (20,000 ton/year), Bassum, Germany (13,500 ton/year), and Kaiserslautern, Germany (20,000 ton/year). The Kompogas Process The Kompogas process is a dry process developed in Switzerland. The process operates in the thermophilic range with a hydraulic retention time of approx. 15 days. The reactor is a horizontal cylinder and the flow through the reactor is plug flow. In the reactor a stirrer provides some mixing of the waste. Recircula- tion of a part of the effluent to the incoming substrate ensures inoculation. 4.3.3 Multi-stage Anaerobic Digestion Systems Most of the digestion systems for anaerobic treatment of MSW are single-stage reactor systems. However, multi-stage digestion systems are also used. These are usually two-stage systems, although 3-stage systems have also been proposed. The idea with the multi-stage systems is to separate the different phases of the anaerobic digestion process, in order to be able to apply optimal conditions in Applications of the Anaerobic Digestion Process 29 Fig. 18. View of a Dranco biogas plant each of them. Different operating conditions, such as pH and retention time can be kept in the different stages. The BTA Process The BTA process was developed in Germany (Kubler and Schetler 1994). The process is a multi-stage process (Fig. 19). Pretreatment is centered on a hy- dro-pulper, which receives the source-sorted waste from a screw-mill, which opens bags and disintegrates larger agglomerated particles. In the hydro-pulper, the waste is mixed with recirculated process water and the organic material is dis- solved through intense agitation. Floating light elements (plastic, wood etc.) are skimmed from the surface by a periodically operated rake and heavy items (metal, glass etc.) are removed by sedimentation. The pretreatment pro- duces a pulp of approx. 10% total solids (TS). The pulp is pumped to a buffer tank where acidification occurs. The effluent from the acidification reactor is dewa- tered by centrifugation. The thin liquid fraction is fed into a high flow biofilm reactor; while the thick fraction of undissolved material is mixed with process water and fed to a CSTR reactor where further hydrolysis and acidification takes place. The effluent from the CSTR reactor is once again dewatered, and the liquid fraction fed into the biofilm reactor for methanization at mesophilic con- ditions. A part of the thick fraction is removed from the process to take out inert and undegradable material with a TS content of approx. 35%. This “compost”contains approx. 0.2–0.3 kg N per ton. Excess process water, which contains most of the nitrogen (about 4–8 kg N/ton original solid waste; see below) and other nutri- ents that were in the original waste, is disposed of to the sewer system or recy- cled to the agricultural sector as a fertilizer if possible. The volatile solids (VS) destruction is predicted to approx. 85%. 30 I. Angelidaki et al. Fig. 19. Principle diagram of the BTA process 4.4 Summary of Processes Used for Anaerobic Treatment of Solid Wastes There is a wide variety of configurations for anaerobic treatment of solid wastes. One way to classify these reactor systems is depicted in Fig. 20. The batch sys- tems can be considered as accelerated landfill systems. These systems are simple and comparatively cheap. MSW is loaded batch wise in a closed vessel contain- ing inoculum from a previous batch digestion. During the digestion period, leachate is recirculated for mixing purposes of substrate, microorganisms and moisture.When the digestion is complete, the digested material is unloaded and a new batch digestion is initiated. An alternative to batch digestion is the leach bed process, where the leachate from the base of the reactor is exchanged between established and new batches to facilitate start up, inoculation and removal of volatile acids in the active reac- tor.When the methanogenesis is established, the reactor is connected to another reactor containing new MSW. This concept has also been described as sequential batch anaerobic composting (SEBAC). The continuously operating systems can be divided into completely mixed and plug-flow systems. The completely mixed systems can again be classified as sys- tems based on recirculation of process water for dilution of the incoming MSW and in systems based on the codigestion concept. Codigestion is especially well established in Denmark. Several systems are operating on the multi-stage diges- tion concept. However, one-stage systems are much simpler and cheaper and therefore, considerably more widespread. Applications of the Anaerobic Digestion Process 31 Fig. 20. Classification of anaerobic solid waste digestion systems 5 References 1. McInerney MJ, Bryant MP, Stafford DA (1980) Metabolic stages and energetics of micro- bial anaerobic digestion. In: Stafford DA, Wheatley BI, Hudges DE (ed) Anaerobic diges- tion. Applied Science, London 2. Gujer W, Zehnder AJB (1983) Water Sci Technol 15:127 3. Allison MJ (1978) Appl Environ Microbiol 35:872 4. Switzenbaum MS, Giraldo-Gomez E, Hickey RF (1990) Enzyme Microb Technol 12:722 5. 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