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1、厌氧消化技术厌氧消化技术Technology of Anaerobic Digestion2009.11.16E-mail: Part 21主要内容主要内容1、History2、Three-stage of Anaerobic Digestion3、Rural Biogas4、Biogas Engineering21、HistoryIn 1630, van Helment, the first man noted biogasIn 1776, A. Volta discovered “flammable air”In 1806, W. Henry pointed out “flammable
2、air” is CH4In 1808, H. Davy produced manure gas with cow dungIn 1866, Bechamp think methane production is a microbial processIn 1875, Popoff researched methane fermentationIn 1883, Gayon researched anaerobic digestion3In the last of 19th, Louis Mouras built the first digester treating waste water in
3、 France.In 1896, Exeter of Britain built digester treating sewage, sludge gas used for lighting street.In 1900, Matunga of India built biogas digester with human excrement as feedstock. 4In 1901, Shngen brought forward the concept of methane bacteria.In 1916, Omeliansky first isolated a strain of me
4、thane bacteria Methanobacterium omelianskii.In 1930 & 1934, van Niel brought forward a theory of carbon dioxide reduction methane.4H2A4A8HCO28HCH42H2OTotal reaction：4H2ACO24ACH42H2OIn 1936, using chemically synthesized media to culture river sludge, Barker obtained a kind of microorganism being bett
5、er suitable for fermentation of alcohol, propanol and butanol.At the same time, Heukelekian & Heinmann reported a technique for calculating the number of methane bacteria.5In 1948, Buswell & Sollo founded out theory of direct conversion from methyl group to methane： 14CH3COOH14CH4CO2 CD3COOHH2OCD3HC
6、O2H2O 4CH3OHD2O3CH3DCO2In 1956, Barkers hypothesis, it is thought that methane is formed through two pathways. During the process, methyl group of acetic acid is directly reduced to methane and that carboxyl group of acetic acid is converted to carbon dioxide, and then the latter is again reduced to
7、 form methane.6In 1940, H. A. Barker first isolated and cultivated methanogens with barker tube.In 1950, R. E. Hungate established anaerobic technique which greatly contributed to the research of methanogens.In 1965, Hungate technique was developed by Bryant.In 1967, Bryant purified Methanobacterium
8、 omelianskii and identified it, being a union of Methanobacterium MOH and “S” organic strain, the union is interspecies H2-transfer.7A. p-pH-OH+K2CO3 Tube (Barker 1940) B. Hungate Roll Tube (1950) C. Hungate Beef Soup Tube (1960) D. Balch Tube (1976) ABCD8In 1956, Methanobacteriaceae was first summe
9、d up in one family, including 4 genera and 9 species by BarkerIn 1974, in the Bergys Manual of Determinative Bacteriology(8th edition), methanogen was summed up in one family, including 3 genera and 9 speciesIn 1979, W. E. Balch: 3 orders, 4 families, 7 genera and 13 species In 1988, International S
10、ociety of Methanogenic Classification was foundedIn 1989, Bergys Manual of Determinative Bacteriology(9th edition): 3 orders, 6 families, 13genera and 43 speciesIn 1989, R. D. Boone: 3 orders, 6 families, 16 genera and 55 speciesIn 1990, J. L. Garcia: 3 orders, 7 families, 20 genera and 70 speciesIn
11、 1993, R. D. Boone: 5 orders, 10 families, 25 genera and 59 speciesIn 2001, Bergys Manual of Systematic Bacteriology(2th edition): 5 orders, 10 families, 26 genera and 78 species9In 1955, G. J. Schroepfer developed anaerobic contact (AC) processBiogasFeedingSludge circumfluenceSedimentation pool10In
12、 1961, W. W. Eckenfelder proposed a four-step process: hydrolysis, acidification, acid decaying and methane productionIn 1962, R. E. Mckinney proposed a two-step process: acid-producing and gas-producingIn 1967, O. W. Lawrence & P. L. McCarty proposed a three-step process: hydrolysis, hydrogen and a
13、cid production, and gas or methane production11In 1969, Young & McCarty developed Anaerobic Filter，(AF) with organic waste water, it has been 1972BiogasFeedingFillingEffluence12In 1971, S. Ghosh of American anaerobic digestive expect developed Two-phase Anaerobic Digester ProcessBiogasFeedingAcidize
14、dSeparatingMethane fermentationEffluence13In 1974，Prof. G. Lettinga, Agricultural University of Wageningen, Department of Water Pollution Control, developed Upflow anaerobic sludge bed, UASB，UASB has been application since 197714In 1981, developed Expanded Granular Sledge Bed，EGSB 15In 1985, PAQUES
15、BV Company of Netherlands, developed Internal Circulation, IC 16G1 Reactor: HRT=SRT=MRTAnaerobic Contact; Complete Stirred Tank ReactorG2 Reactor: SRT, MRTHRTAF; UASBG3 Reactor: contact materials and sludgeIC; EGSB17In 1970, the coenzyme M(CoM) was discovered with Methanobacterium MOH strain by McBr
16、ide & R. S. Wolfe.In 1972, the factor 420(F420) was discovered with Methanobacterium MOH strain by P. Cheeseman etc.In 1974, Taylor & R. S. Wolfe have confirmed the CoM structure.18In 1977, A brilliant concept, Archaebacteria has been raised by a team headed by Carl. R. Woese, Illinois, University,
17、America.19In 1978, L. D. Erich etc. have confirmed the F420 structure.In 1978, R. P. Gunsalus & R. S. Wolfe separated to get the factor 430 (F430) from Methanobacterium thermoautotrophicum H strain.20B21 正常脂质与古细菌脂质的比较正常脂质与古细菌脂质的比较22肽聚糖与假肽聚糖初级结构的比较肽聚糖与假肽聚糖初级结构的比较23In 1978, Tornabene etc. have first r
18、esearched lipids of methanogens.ArchaeolCaldarchaeol24Macrocylic archaeolsn-3 hydroxyarchaeol25sn-2 hydroxyarchaeol26In 1983, M. Thomm, A. G. Wood & L. Meile have separated to get three plasmids from methanogens.pMP1 come from Methanococcus strain PL-12/M27pME2001 come from Methanobacterium thermoau
19、totrophicum strain DSM213328pUR500 come from Methano C529Carl R. Woese, Bacterial Evolution, Microbio. Rev., 1987, 51: 221-271This paper is symbol of establishing modern classification of bacteria.In 1992, Carl R. Woese changed Archaebacteria to Archaeon，it means Archaeon is not bacteria, so he thre
20、w off postfix of “bacteria” in “Archaebacteria”.Bult, C. J. et al., Complete Genome Sequence of the Methanogenic Archaeon, Methanococcus jannaschii, Science, 1996, 273: 1058-107330ProteinCarbohydratesLipidsAmino acidsSaccharidesFatty acidsPyruvic acidVolatile fatty acidsH2CO2NH3H2SCH3COOHH2CO2NH3H2S
21、CH4 CO2NH3H2SH2-producing acetogenic bacteriaHydrolasesAcid-producing bacteriaMethanogens2、Three-stage of Anaerobic Digestion31Acetic acid15%Complex20%Propionic acidOthers15%65%Methane72%35%13%17%15%32Propinoic acid free energyCH3CH2COOH2H2OCH3COOHCO23H2 76.1kJButyric acid:CH3CH2CH2COOH2H2O2CH3COOH2
22、H2 48.1kJEthanol:CH3CH2OHH2OCH3COOH2H2 9.6kJLactic acid:CH3CHOHCOOHH2OCH3COOHCO22H2 9.6kJThe 2nd step：Acid & hydrogen production33Interspecies H2-transfer In 1977, Thauer et al: C2H5OHNAD+CH3CHONADHH+ G=+23.8kJ (1) NAD+: niacinamide adenine dinucleotide NADHH+NAD+H2 G=+18kJ (2)CH3CHOH2OCH3COO-H2H+ G
23、=-32.2kJ (3)Total reaction: C2H5OHH2OCH3COO-2H2H+ G=+9.6kJ (4)PH21atm, the reaction did notPH2 10-4 atm( (reaction 2), G-35.9kJ，the reaction occurred 34Methanobacterium bryantiiS strainOInterspecies H2-transfer 35PH2:10-610-8atmSyntrophobacter wolinii: propionateSyntrophomonas wolfei: butyrate36Prot
24、einsAmino acidAcetic acidCH4NH3, S, etc.Polysac-charidesGlucosePyruvic acidFatsGlycerol Fatty acid373、Rural BiogasIn 1888, in Chaozhou of Guangdong, China38G1: In 1929, Luo Guo-Rui Biogas Digester of China39G2: Far, Big, and DeepBeing demonstrated of biogas stove on Wuhan local industry exhibition o
25、n April 11, 1958, Chairman Mao Zedong instructed “This should be well promoted”. 40G3: Round, Small, and ShallowOn July 10, 1980, when Vice Chairman Deng Xiao- ping visiting a farm household of Cuqiao commune, Cheng- du City of Sichuan Province, and watching the demon- stration of biogas stove there
26、, he said emphatic- cally “Biogas is really good, which is an orientation issue and a world issue”. 41G4: The late of 1980s, deveoloping many small efficient biogas digesters in China曲流布料沼气池曲流布料沼气池塞流式料液自动循环农村沼气池塞流式料液自动循环农村沼气池 水压式厌氧滤器沼气池水压式厌氧滤器沼气池 档板式高效沼气池档板式高效沼气池 42G5: In 2000, Commercialized Househ
27、old Biogas Digester Made of Glass Fiber Reinforced Plastic by Yunnan Normal UniversityKunming 650092, P. R. China43Lou Guo Rui DigesterFar-Big-Deep DigesterRound-Small-Shallow DigesterCommercialized DigesterSmall Efficient Digester4419731983年：仓促发展与回落年：仓促发展与回落 18841991年：调整与重视科技年：调整与重视科技19921998年：回升与效
28、益凸现年：回升与效益凸现19992002年：全面提升与快速发展年：全面提升与快速发展2003年以后：综合进步与迅猛发展年以后：综合进步与迅猛发展45截止到截止到2008年底：户用沼气年底：户用沼气3050万户，年产沼万户，年产沼气气122亿亿m3，相当于，相当于1850万吨超标准煤，减少万吨超标准煤，减少二氧化碳排放二氧化碳排放4500万吨，增收节支万吨，增收节支150亿元亿元玻璃钢沼气池已在一些地区推广应用，并且玻璃钢沼气池已在一些地区推广应用，并且在发展中国家如越南、缅甸、阿塞拜疆、突在发展中国家如越南、缅甸、阿塞拜疆、突尼斯、卢旺达等示范推广，前景十分广阔尼斯、卢旺达等示范推广，前景十分
29、广阔2008年荷兰政府启动了非洲沼气行动计划年荷兰政府启动了非洲沼气行动计划预计筹资预计筹资20亿欧元，十年建亿欧元，十年建200万个家用沼气万个家用沼气池池46Biogas utilization1、Cooking & lighting2、Supply carbon dioxide(gas fertilizer)3、Fruits keeping fresh4、Grain storage5、Incubating & sericiculture6、feeding fish with entrapping pest47Metabolism and bio-active elements of an
30、aerobic digestion Fermentative bacteriaThe obligateH2-producing acetogenic bacteriaMethanogensBiogsa &bio-slurryHydrolases: Protease, Cellulase, Lipase, AmylaseAmino acids: 20 kinds of amino acidsOrganic acidsAlcoholsHumic acidVitamin B group:B1, B2, B5, B6, B11CytokininFatty acidsAuxinVitamin B12An
31、tibioticsMicro-elements48OrganicOrganicProteinCelluloseProteinCelluloseOrganic acidsNH3Organic acidsOrganic acidsNH3SaccharideNH4+CH4CO2CO2Anaerobic DigestionCompost49 Bio-slurry as fertilizer Bio-slurry as soaking seeds Bio-slurry as disease and pest control Bio-slurry as pig feeding Bio-slurry as
32、fish feeding Bio-slurry as edible fungi culture 50Eco-farming system taking biogas as a key-link 51Biogas fermentation system 52“Four-in-One” biogas model Greenhouse, vegetable, pig stall and biogas digesterOverview of the use of bio-slurry in China53“Pig sty Biogas digesterFruit trees”ModelAnimal h
33、usbandry- Biogas digester- Plantation 54“Five inOne” Eco-Orchard SystemDigester, solar heater, animal stall, water stove & fruit garden 552004年沼气综合利用年沼气综合利用沼液浸种沼液浸种126.8万公顷，增产粮食万公顷，增产粮食82.3万吨万吨沼液喂猪沼液喂猪1151.5万头，节省饲料万头，节省饲料36.5万吨万吨沼液养鱼沼液养鱼9.38万公顷，增产鲜鱼万公顷，增产鲜鱼6.95万吨万吨沼渣育菇沼渣育菇1568.95万万m2，产菇，产菇2.4万吨万吨保鲜水
34、果保鲜水果1.24万吨，减少果品损失万吨，减少果品损失1788.5吨吨沼气贮粮沼气贮粮9.55万吨，减少粮食损失万吨，减少粮食损失1989.2吨吨562004年沼气生态工程年沼气生态工程北方四位一体：北方四位一体：48.36万户万户年出栏牲畜年出栏牲畜419.6万头，户均出栏万头，户均出栏8.7头头年产蔬菜年产蔬菜1056.4万吨，户均万吨，户均21.8吨吨南方猪沼果：南方猪沼果：522.93万户万户年出栏牲畜年出栏牲畜345.54万头，户均出栏万头，户均出栏0.7头头年产蔬菜年产蔬菜2838.99万吨，户均万吨，户均5.4吨吨年产水果年产水果1764.89万吨，户均万吨，户均3.4吨吨574
35、、Biogas EngineeringLarge-Medium Scale Biogas Engineering58Definition of large-medium scale biogas digester大中型沼气工程的界定大中型沼气工程的界定Scale规模规模Single capacity 单池容积单池容积(m3)Total capacity 总池容总池容(m3)Biogas yield 沼气产量沼气产量(m3/d)Large大型大型 3001000 300Medium中型中型503001001000 50Small小型小型205050100 2059Process of ENERG
36、Y ECOLOGICAL disposing and using60Process of ENERGY ENVIRONMENT disposing and using616000m3酒精厂酒精厂沼气工程沼气工程2500m3沼气烤烟工程沼气烤烟工程8000m3养猪养猪场沼气综合场沼气综合利用工程利用工程62坦桑尼亚剑麻废水沼气工程坦桑尼亚剑麻废水沼气工程突尼斯沼突尼斯沼气发电气发电卢旺达生活污水卢旺达生活污水沼气净化工程沼气净化工程6364Porcelain enamel splicing reactor656667Biogas EngineeringOrganic wastesResource
37、sControl pollutionImproving environmentCDMSupplied fertilizerGreen agricultureClean energyFertilizer & pesticideBenefitBiogasElectricity实实现现企企业业可可持持续续发发展展带带动动区区域域新新农农村村建建设设和谐进步和谐进步68PlantationAnimal HusbandryBiogas EngineeringFOODFERTILIZEFUELFEED4F循环经济模式循环经济模式69四大效益四大效益实现可持续发展实现可持续发展企业企业发展发展可可持续、持续、区域区域发展可发展可持续持续4F循环循环经济效益、能源效经济效益、能源效益、环境益、环境/生态效益、生态效益、社会效益社会效益饲料、肥料、食品、饲料、肥料、食品、能源能源/燃料燃料70Thank you!71
