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3IdllThePhilipPine
Exper;-e?',.::
bJ. * 2; D. Maramba, Sr.
7,
.*, J.,,-2d by:
%erty Flour Mills, Inc.
claya Farms Division
Liberty Building, Pasay Rd.
Legaspi Village, Makati
Metro Manila, The Philippines
Available from:
Liberty Flour Mills, Inc.
Maya Farms Division
Liberty Building, Pasay Rd.
Legaspi Village, Makati
Metro Manila, The Philippines
Reproduced by permission of Liberty Flour
Mills, Inc.
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form is subject to the same restrictions as those
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IQGAS
AND
WMTE RECYCLING
THE PHILIPPINE EXPERIENCE
BIOGAS AND WASTE RECYCLING
THE PHILIPPINE EXPERIENCE
FelixDI Maramba,Sr.
B.S.,M.S.,D.Sc.(honor/s emma)
ContributingAuthors
EnricoD. Obias,B.S.Ch.E.
JulianBanzon,B.S.Chem.,Ph.D.
CalixtoTaganas,B.S.C.E.
RuthD. Alumbro,B.S.,M.S.
AlejandroA. Judan,Jr.,B.S.B.A.,CP.A.
Maya FarmsDivision
Liberty Flour Mills,Inc.
Metro Manila,Philippines
. ..
ill
_-
Copyright 19%
bY
Felix D. Maramba, Sr.
All rights reserved.No part of
this publication may be reproduced
or transmitted in any form or by
any means,electronicor mechanical,
including photocopy, recording or
any information storageand
retrieval system,without the
written permissionof the senior
author.
Printed by &I RRGAt PRINTING COMPA,NY
iv
In memory of two Filipino scientist-technologists
Manuel L. Roxas
and
BienvenidoMa. Gonzales
Who laid the foundation for Philippine agro-industrial development
V
PREFACE
When Liberty Flour Mills, Inc., decided to establishMaya Farms, an h&grated hve-
stock farm, meat processing and canning operation in the Antipolo Hills of Rizal pro-
vince, Philippines, pollution control was an integral part of the planning. After the NW-
ious alternative methods were studied, anaerobic fermentation was chosen and adopted.
The choice was made on the basisof what I had previously seenof the biogas plants in
India and Taiwan. The biogas practitioners in India were enthusiastic about the biogas
fuel for cooking and lighting, and in Taiwan, about the savings in their fertilizer bills.
However, what particularly impressedme was the absenceof foul odor and flies. It was
evident that the 4ution of the problem involved expertise in chemistry, microbiology,
engineering,etc. II. ,Jastherefore decidedthat a group of specialistswould work together
in a crashdevelopmentprogram.
We read whatever literature we could gather on biogas and started our experiments.
Later, I made another trip, this time to Europe, the United States,Australia and India,
to learn more, principally on the various designsand methods of operation. Chapter VII
showsthe most common designs.We tried a number of biogas plants which we thought
would be applicable,properly modified to fit local conditions, becausewe found no single
designthat would meet varied requirements.Chapter VI is devotedto the discussionof
suitabledesignsfor different conditions.
The biogas plants which we established,successfullycontrolled the air pollution from
the tons of manure produced daily by 10,000 pigs. But though *+ biogas plants greatly
reduced the pollutional characteristics of the manure, the voluminous sludge still posed
the problem of water pollution. Becauseit contained traces of toxic substances,it could
not be applied as fertilizer in large doses.Intensive and expensiveefforts of Maya Farms
to solve the problem resulted in the development of the sludge-conditioning plant dis-
cussedin Chapter VIII.
Sludgeconditioning not only eliminated the toxicity to fish and crops but it also im-
proved the fertilizer performance far beyond what the chemical analysis would indicate.
An unexpectedbonus of great significance was our discovery that the solids recovered
from the sludge could be processedinto an excellent animal feed material. We found
later that the dri& sludgewas rich in vitamin B12, a growth-promoting factor in animal
feeds. Results of f-g trials would also indicate the presenceof other unidentified
growth factors (UGF).
Sludge conditioning may well be Maya Farms’ most significant contribution to bio-
gas technology. The value of the recoverable feed materials alone, without considering
the biogas, biofertilizer, and pollution control, makesthe whole system a profitable ven-
ture. The utilization of the sludge as fertilizer and as a source of feed materials is dis-
cussedin Chapters XIII and XIV. Chapter XV covers the function of the biogas works *
for pollution control.
0
vii
Maya Farms has adopted the term “biogas works” to distinguish a biogas opera-
Lionwith sludgeconditioning from a biogasplant operation.The biogasworks, or opera-
ting combiiation of the biogasplant and sludge-conditioningplant, is discussedin Chap-
ter IX.
After the oil embargoin 1973,we startedexperimentingon the industrial usesof bio-
gas. First it was used as a substitutefor LPG (liquefied petroleum gas). We found that
the biogasmay be used in any appliancesintended for LPG, with minor adjustments,
The EngineeringDivision of Liberty Flour Mills, Inc. started manufacturing appliances
specifically intended to use biogas: gas stoves,refrigerators, lechon oven, etc. It made
adjustmentson mantle lamps and water heatersto usebiogas.It convertedcharcoal flat
irons to use biogas. Biogas was used successfullyto run internal combustion engines
to pump water from deepwells, to operatethe feed-mixingplant, and to operatean elec-
tric generatorthat runs the freezersat night. We also usedthe biogasto fire a boiler, but
wedid not haveenoughgasto do all theseatthe sametime.
After finding so many usesof biogas,our next aim was to find ways to increasethe
daily production and to reduce the costs of construction and operation. The hundreds
of trials on laboratory scaleand pilot scalebiogasplants paid off handsomely.We were
able to increasethe production capacity of the biogas plant by 70-80% with more effl-
cient stirrers, and by reducing the retention time of the waste slurry inside the digester
from SO-60days to 23-30 days. By improving the quality of our starter, we were also
able to produceflammablebiogas the day after charging the digesters,where it used to
take4 to 6 daysbeforegoodgaswasobtained.
Reductionof the retentiontime to one-halfincreasedthe biogasproduction and at the
sametime doubledthe manure-processingcapacity of the biogas plants. In other words,
the capital outlay requiredto construct biogasplants to disposeof the sameamount of
manurewas reducedto one-half.To find other ways of cost reduction, we tried various
designsof the biogasplant. We built modified versionsof the India single-walledvertical
digesterwith floating gasholder,the Taiwan double-walledhorizontal digesterwith float-
ing gasholder,the China cylindrical digesterwith fured-domegasholder.We built conti-
nuous-fedand batch-fed,integratedtype and split type biogasplants. We built digesters
with singlechamber and double chamber,in double rows, in triple rows and in clusters.
We built them above ground and underground.We endedup with our own designsof
both batch-fedandcontinuous-feddigesters.
Becauseof the great potential of biogas operations in waste recycling, our research
and developmentwork spilled over into a recycling system.We not only recycled the
manure, but also converted the bones, blood and meat scrap in the meat processing
plant into feed materials.Then we tried mixir g the corn stover and rice straw with the
manureslurry. Gas production was improved but the stover and straw required drying,
crushing and chopping which consumedtoo much energy. Instead of giving them up
entirely, we looked for a better way of usingthem. We fed them to ruminants and got the
manureof the ruminants for the biogasplant. Thus the stoversand strawstogether with
the weedsstill helpedproduce meat before reaching the biogas plant. The inedible por-
tion of thecrop residueswerecompostedto serveassoil conditioner.
To fmd other ways of recycling our excessliquid sludge,we also experimentedon
producingchlorella asa protein sourcefor the hog feeds,but the high costsof harvesting
...
vu1
and drying chlorella made its production cost much higher than the cost of other avail-
ableprotein sourceslike soybeanoil meal and fishmeal.Instead,we decidedto grow the
algaein fishpondssothat the fishcanfeedon themdirectly.
Seeingall the benefitswe weregetting out of the recycling operations,it did nclt t+e
long to realize the socio-economicimpact if such recycling systemscould be praet.icG
throughout the country. Part IV discussesthis matter and presentspossibleapplications
of a recycling systemof farming, introducesthe variedroles that biogascan play in rural
developmentandshowsthebeginningof biogaspracticein the Philippines.
This book is a summary of our experiences- of our attemptsto solve one problem,
that of pollution, and of how the solution evolvedinto a sort of wonder pill for the mo-
dem world’s major headaches:pollution, the energy crisis, food shortage and under-
employmentof the farmers.Aside from solvingour pollution problem,the biogasworks
turnedout to be a rich sourceof a fuel gas,organicfertilizer and feedmaterials.The so-
lution did not comeeasily.Therewere failures and near misses,financial gamblestaken
and sometimeslost, but in the process,we havelearneda lot, and are still learning.We
feelweshouldsharethis stockof knowledgewith others.
Late in 1976, President Ferdinand E. Marcos directed the Energy Development
Board (now Ministry of Energy) to embark on a crash program to use biogas as a
substitutefuel. In this connection,he instructed the Director of Animal Industry to es-
tablish model biogasworks in their stock farms: at least one in every region within six
months,one in eachprovince within one year, then in every town whereit has a breed-
ing station. The Maya Farms was chargedwith the task of training governmenttechni-
cianswho would take care of constructingand operatingbiogasworks and propagating
theiruse.We arehappyfor havingbeengiventhis opportunity.
Felix D. Maramba,Sr.
ACKNOWLEDGMENT
The help of the following technical men, who are all involved in the researchand de-
velopmentwork on biogasat Maya Farms,is gratefully acknowledged:
Domingo Bautista,B.S.M.E. RegisteredMechanical Engineer
Dr. Patrocinio Santos,Ph.D. Formerly Microbiologist of the National
Institute of Science& Technology
Dr. Leopold0Castillo, Ph.D. Animal Nutritionist of theUP. College
of Agriculture
Dr. Mario Tongson,D.V.M. Chief Parasitologistof theU. P. College
of Veterinary Medicine
FidelJunatas,B.S.&E. RegisteredSanitary Engineer
PacificoPangilinan,B.S.E.E. RegisteredElectrical Engineer
Hector Gatchalian, B.S.Chem. RegisteredChemist
RomeoA. Icasas,B.S.A. Animal Husbandman
Dr. Leopold0Capistrano,D.V.M. Veterinarian
Alfred0 Hemaez,B.S.A. Formerly Agronomist of theBureauof
Plant Industry
FelipeAgdeppa,B.S.H. Soil Technologistof theBureauof Soils
Agustin Mangila, B.S.A.,LLB. Agricultural Economist
RamonDizon, B.S.M.E. RegisteredMechanical Engineer
Home AppliancesManufacturer
EstrellitaS.Tala, B.S.Ch. E. ChemicalEngineer
Meynardo Maghirang, B.S.Ch. E. ChemicalEngineer
RositaImmaculata, B.S.Chem. Chemist
ZenaidaS.Hemandez,B.S.Med. Tech. Laboratory Technician
More thanksare due : to the difYerent embassiesin the Philippines for their help in
gathering information on the researchand application of biogas
in thair respectivecountries;
: to the Philippine embassiesabroad for furnishing us with biogas
literature;
: to the Ministry of Energy and the National ScienceDevelop-
mentBoard for their encouragement;
: to the National Pollution Control Commission for their valuable
suggestions;
: to the National ResearchCouncil of the Philippines for making
possibletlle publication of this book.
X
CONTENTS
Preface
Acknowledgment
Part1 - ScientificAspects
Chapter I
II
III
IV
V
Part II - BiogasTechnology
Chapter VI
VII
VIII
IX
X
XI
Nature andHistory of Biogas
BiochemistryandMicrobiology
Laboratory andPilot Plant Experiments
RawMaterials for BiogasProduction
TheSludge
Fundamentalsof BiogasPlant Design
BiogasPlant DesignsAround theWorld
Sludge-ConditioningPlant Designs
BiogasWorks Designs
Planningand Establishingthe BiogasWorks
OperatingBiogasWorks
PartIII - Utilization andEconomics
Chapter XII BiogasasFuel
XIII SludgeasFertilizer
XIV Sludgefor FeedandOther Uses
xv BiogasWorks for pollution Control
XVI TheEconomicsof BiogasWorks
PartW - WasteRecycling‘I’hroqh the BiogasWorks
Chapter XVII RecyclingSystemof Farming
XVIII Rural Developmentthrough WasteRecycling
XIX BiogasWorks in Practice
Socio-EconomicImpact of BiogasWorks
143
145
153
159
165
171
181
185
193
201
213
Glossaryof Terms 218
Bibliography 223
Ill&X 221
Vii
X
3
5
11
21
39
47
61
63
73
87
101
l 115
131
xi
LIST OP TABLES
3-1 Relativevolumeof digesterspaceto containonekilogramof hog manurein
variousmanure-waterratios s
3-2 Weight of componentsin experimentalslurries of various manure-water
ratiosandstarterpercentages
3-3 Rateof biogasproduction
4-1 Elementalcompositionof someproteins
4-2 C/N ratio, total solidsand volatile solidsof somebiogas-producingmate-
ri3lS
4-3 Carboncontentof selectedmaterialsrelatedto biogasproduction
4-4 Relativeweightsof componentsof hogmanure
4-5 Characteristicsof hogmanure
5-1 Compositionof sludgein relationto daysof fermentation
5-2 Mineralcompositionof a sampleof total sludge
5-3 Mineral compositionof the solid and the liquid portions of a sampleof
sludge
5-4 Percentagesof constituentsremainingin sludgeand percentageconverted
to biogas
5-5 Theoreticalmaximumvolume of biogasproduciblefrom one kilogram of
material
5-6 Conversionpercentageof hogmanureto biogas
10-l Approximatedaily manureavailablefrom di&rent animals and the daily
biogasproduction
10-2 Biogasconsumption
10-3 Kind of manurerequirement,gasproductionandcostof biogasplant
f2-I Compositionof biogasandthecommonfuelgases
Page
31
35
36
39
43
44
44
45
48
48
48
54
55,
57
116
117
118
146
se j
~$3,.
s
12-2 Heatingvalueof biogasandthecommonfuelgases
12-3 Heatingvalueof otherenergysources
13-1 Plot fertilize!experimentonrice
15-l Quality standardsfor differentclassificationsof water
15-2 Characteristicsof wastewaterfrom different sampling stations at Maya
Farms
15-3 Qualitativedescriptionof odors
15-4 Threshold odor numbersof wastewaterat different sampling stations at
Maya Farms
16-1 Comparativecostsof constructionof smallbiogasplants
146
147
155
169
169
170
170
173
...
Xl11
4
:
3-l
3-2
3-3
3-4
3-5
3-6
3-7
3-8 Effect of ageof starter on gasproduction
3-9 Ratio of volume of gasper day to volumeof digesterslurry
LIST OF FIGURES
Page
Laboratoryset-upfor study of biological production of methane 22
Typicalbiogasproduction curve 24
Gas production curvesfor various manure-waterratios 26
Gas production curves on equal slurry volume and equal manure weight
basis 27
Gasproduction curvesfor storedpig manure 29
Gasproduction curvesfor varying starterpercentage 29
Relation of percentageof starter and number of days to produce 50 liters of
biogas 29
29
32
3-10 Rates of biogas production during active growth and senescencein relation
to dungconcentration
3-11 Gas production curvesfrom chicken manureslurries
3-12 Gas production curvesfor corn stalk andrice straw
5-l Changesin percentagecomposition of sludge during methane fermentation
of hogdung
5-2 Changes in weight of components of siudge during methane fermentation
of hogdung
5-3 Percent reduction in weight of protein, fat, total carbohydrates, volatile
solidsandtotal weighi
5-4 Percentdistribution of total weight loss
6-l Integratedbiogasplantflowsheet
32
32
32
53
53
56
56
70
706-2 Splitcontinuous-fti biogasplant
xiv
7-I
7-2
7-3
7-4
7-5
7-6
7-7
7-a
7-9
7-10
7-11
7-12
7-13
7-14
7-15
7-16
7-17
7-18
7-19
7-20
7-21
7-22
biogas1plant
6-4 Night soilbiogasplant
Gobar gasplant, with overflowoutlet (Patel)
Gobar gasplant, with pipeoutlet
Manuregasplant with latrine (Gotaas)
BelurMath gobargasplant
Taiwansinglestagebiogasplant
Taiwan 2-stagemethanegenerator
Chinabiogasplant
Anaerobicdigestionof pig waste
Darmstadtsystem
Schmidt-Eggersglusssystem
Webersystem,cow dungtype
Bihugas-Anlage(Poetsch)
Ducellier-Ismansystem
Gartner-Ikonoff system
Drum digesterfor fibrousmaterials(Buswell-Boruff)
Gasgeneratingplant for vegetablewastes(Burke-Jacobs)
Organicdigester(Fry)
Methanerecoverydigester(Chan)
Sanamatictank (Co&hard)
Kenyabatchdigester
Continuousorganicwastedigester(Araneta)
Garbagefermentationtank (Valderia)
1
’ :
xv
71
71
78
I&
33
78
79
79
79
79
80
80
80
80
81
81
81
81
82
82
82
82
83
83
7-25
‘7-26
7-27
7-28
7-29
7-30
7-31
l-32
8-l
8-2
8-3
9-l
9-2
9-3
9-4
9-5
9-6
9-l
9-8
9-9
Methanegasproducingdevice(C&-Velasquez)
Night soil digester(Maya Farms- Bautista)
Horizontal continuous-fedbiogasplant(Maya Farms-Obias)
Continuous-feddigesterfor livestockfarms(Maya Farms-Taganas)
Batch-feddigestersfor agro-industrialoperations(Maya Farms-Maramba)
Floatingdomegasholderfor split typebiogasplants
Continuous-feddigesterfor slaughterhouses(Maramba-Taganas)
Vertical continuous-fedbiogasplant(Maya Farms-India)
Fixeddomecontinuous-fedbiogasplant(Maya Farms-China)
Double-walledcontinuous-fedbiogasplant (Maya Farms-Taiwan)
Singlepondsludge-conditioningplant
Doublelagoonsludge-conditioningplant
Multi-lagoon sludge-conditioningplant
Family farm biogasworks flowsheet
Crop-livestockbiogasworks flowsheet
Agro-pulp biogasworks flowsheet
Livestockbiogasworks flowsheet
Feedlotbiogasworks flowsheet
Integratedmeat-processingbiogasworks flowsheet
Agro-industrial biogasworks flowsheet
Slaughterhousebiogasworks flowsheet
Cooperativebiogasworks flowsheet
9-10 Night soil biogasworks flowsheet
1l- 1 Floor plan for compostbunk
xvi
83
83
84
84
84
84
85
85
85
85
98
99
100
106
107
108
109
110
111
112
113
114
114
139
17-1Recyclingchart, Maya Farms
19-i Sta Barbarabiogaspiant
19-2 BAI biogasplant
19-3 PAC biogasplant
19-4 UPCA biogasplant
183
206
206
206
206
xvii
l-l
l-2
l-3
l-4
l-5
l-6
l-7
l-8
1-9
2-l
2-2
2-3
2-4
2-5
2-6
2-7
2-8
2-9
2-10
2-11
2-12
2-13
LIST OF ILLUSTRATIONS
Microbiology laboratory at Maya Farms
Microbiological assayof vitamin B12
Pollutioncontrol laboratory
Experimental laboratory digesters at Maya Farms
Pilot piaint batch-fed digesters
Pilot plant continuous-fed digesters
First experimental biogas plant
Laboratories and one of the pilot plants for biogas research at Maya Farms
Animal manure and crop residues are the biggest potential sources of biogas
Eiogas works at Maya Farms
Industrial scale biogas plant
Gasholders for the fourth biogas plant unit under construction at Maya
Farms
Settling basins
Sludge-conditioning canals with overflow dams
Waterwheelaerator
Solid sludgedrier .
Detoxifier
Incinerator
Compostbunk
Biogasplant
Sludge-conditioningplant
Biogasworks with a windmill
...
XVlll
2
19
19
22
37
31
38
38
46
60
72
86
95
95
95
96
96
97
97
105
105
140
@ST, -
2>::
(.,‘
b ” ” 3-l
‘_
3-2
3-3
3-4
3-5
3-6
3-7
3-8
3-9
4-l
4-2
4-3
4-4
4-5
4-6
4-7
4-8
4-9
4-10
4-11
4-12
4-13
4-14
4-15
Biogas-powereddeepwellpump
Biogas-poweredfeedmill
Biogas-heateddrying room
Pigbrooderandpoultry brooderconverted to use biogas
Cookingwith biogasat Maya Farms canteen
Lechon roasters
Crop drier
Fertilizer test plots
Crop field and fishponds
Waste recycling at Maya Farms
Biofertilized vegetableson trellis
Harvesting tilapia at Maya Farms
Fishponds and crop fields
Biogas-powered 60 kva electric generator at Maya Farms
IPOPI charcoal-fed trucks
Windmill
Solar heater
Rice hull firing chamber
Biogasplant in Calasiao,Pangasinan
Sta.Barbarabiogasworks
Biogasplant at BAI breedingstation
Night soilbiogasplantat Liberty FoundationDormitory
India model
Chinamodel
142
150
151
151
152
153
154
158
158
180
191
191
192
198
199
199
199
200
209
210
210
211
211
212
xix
4-17 Maya Farmhousemodel
4-18 Biogasfor householdappliances
4-19 Ducksfeting on scum
212
2i2
217
217
xx
P4RT I
SCIENTIF‘IC ASPECTS
Chapter I Nature and History of Biogas
II Biochemistry and Microbiology
III Laboratory and Pilot Plant Experimerits
IV Raw Materials
V Sludge
Illustration I- 1: Microbiology laboratory.
PART I
SCIENTIFIC ASPECTS
The initial difliculty to becontendedwith whena piggerywassetup at Maya Farms in
1972 was ecologicalin nature. The hog farm polluted the drainagecreek and diffused
odors. A good number of possiblesolutions were considered.One was to dry the pig
manureand sellit as fertilizer. However,therewould be high energyrequirementsduring
the long rainy months,to say nothing of the unpleasantsteamingodors arisingfrom the
forceddrying. Another methodproposedwasstandardsewagetreatment,but calculations
showedthat the cost would be high. Still another method consideredwas anaerobic
fermentation,but there was no availablerecordedexperienceto go by. The potential to
produce methanegas was presentand this at a time when the supply of energy was
becomingevenmorecritical thanthat of food.
Literatureon methanewasamplebut not on methanefermentation.Hugequantititesof
methanehad by now beenalreadymined in many regionsof the world. This natural gas
occurs in nature, and is often associatedwith petroleum oil. In contrast to thesehuge
natural deposits,decaying straw, leaves and other organic matter buried in muddy
stagnantwaters,producethe samemethanegasby action of microorganisms;hencethe
namesswampgas,marshgas,muck gas.In someswamps,the gasignites,very likely due
to another naturally produced gas, phosphine,which is self-igniting when it comes in
contactwith air. (Suchpergolicsubstanceskeepmodernjet enginesalwaysaflame.)These
eeriebluishdancingflamesshimmeringin swampswerecalledignisfatuus by theRomans,
thedeceivinglight, for a personwho is fascinatedby the flameis lured farther andgetslost
in the tracklessswamps.Eventoday, in Englishdictionariesand encyclopedias,the word
or term “will-o-wisp” remains.In still anotherform, methaneappearsasthe eternalflame
burningin shrinesof diversecults and beliefs.Methanegasis not the only legacyhanded
down to usby naturethrough eonsof time duringwhich organicmatter wasconvertedto
productswearenow dependenton for energy.The presentreservesof coal, petroleumoil
andnaturalgasmay betracedbackto the plantsandanimalsthat existedin agespast.The
remainsof theseprehistoric living organismswere convertedby high temperature,high
pressureand microorganismsoverthe long geologicalperiodsto our present-daysources
of energy.
It is now almost certain that the methanein natural gas was formed throu.ghthe
bacterialdecompositionof organicmatter, vegetationand otherorganismsthat lived eons
ago. At the presenttime this decomposingprocessis still going on. A few years ago,
a garbagedump near the Rizal Coliseumin the City of Manila emitted an inflammable
gasduring attemptsto sink awellfor water.
In the Philippines,there hasbeenas in many countries,sporadicinterestin biogas.In
1965 M. Felizardo went to Europe on an official mission for the Philippine Coconut
Administration; he returned with an unusually enthusiasticreport on the experienceof
Germanyon biogas.Work on biogasstartedsoonafter: Eusebio,Alicbusan,the groupsat
3
Pampanga Agricultural School, the Bureau of Animal Industry, the Economic
DevelopmentFoundation, and Maya Farms. Patentsbeganto appear: Valdeda, Cadiz,
Velasquez,Araneta,etc.
It is to be noted that during the oil embargo in 1973, interest shifted to energy
production, and the pollution control aspectwas kept in the background.But eventually
the animal raisers,especiallyof hogs and poultry, found themselvesstaring into the real-
ities of the pollution evil, and anaerobicfermentationagainregainedattention asa means
of control.
Chapter I
Nature and History of Biop
MethmiE:is the simplest member of a large family of chemical compounds called
hydrocarbons. They contain only the elementscarbon and hydrogen. The first six
membersof thisfamily are:
Methane CH4 Butane C4H10
Ethane C2H6 Pentane C5H12
Propane C,H, Hexane CeH 14
Methaneis a gasat our ambienttemperatureand pressure.It is a colorless,odorlessgas
about half asheavyas air. It is characterizedby a critical temperatureof - 82OCand a
critical pressureof 45.8 atmospheres.In other words, methane liquefies only if the
temperatureis at or lower than - 82OCandrequiresat leasta compressionpressureof 45.8
atmospheres.By contrast, butane(lighter fluid) can be obtained as a liquid at ambient
temperaturesandat pressuresslightly higherthan atmospheric.Liquefiedpetroleumgasor
LPG is butane or propane or a mixture of both. Butane and propane have critical
temperatureshigh enoughso they can exist as liquid at ambienttemperatures.The next
higherhydrocarbonis pentane;it is a liquid anda componentof gasoline- from methane
to ethaneto propaneto butaneand to pentane,the critical temperaturesincreaseand the
gasesbecomeeasierto liquefy.
It canbeseennow why compressionalonewill not liquefy methane.However,methane
can becompressedto a gssvolumeso smallasto be comparableto a liquefiedgasas far
asvolumereductionis concerned,but certainproblemsarise: 1)the tank containermust
be extra strong, thick, heavy and of specialconstruction; 2) a costly high compressor
systemis necessary;3) expensivegaspressurereductiondevicesareneededfor everytank
whenthecompressedgasis used.
There8fe many advantagesto be gainedin transporting methaneas a liquid evenwith
the smm requirementof maintaininga temperatureof at most - 82OCand a pressureof
at least 45.8 atmospheresthroughout the time of transport and storage.The volume of
the gqu& however,is approximatelyonly l/600& that of the gas at 25OCand this is an
advantagein storage.The problemsmet in handlinggasesat suchcryogenictemperatures
havebeenquite satisfactorily solvedin the developmentof spacerockets.But would it be
economical to apply this knowledge to methane? Let us quote from a well-known
magaxine:
Thii schemewas the subjectof successfulexperimentsin 1959when the converted
Me&me P&NW ma& seventrips from Louisiana to England.Each cargo of 2000
coldtonswarmedup into 100million cubicfeetfor London’sgassystem.Franceand
Englandarenow buildingmethanetankers.
Methane burns in air with a pale, faintly luminous, very hot flame. The heat of
combustionis 978 BTU per cu. ft. Its auto ignition temperatureis 650°C. The explosive
5
those over 5.53% methaneand those lower than 14%. Methane,
unlike carbon dioxide, is very sparingly solublein water. Hydrogen constitutes 25% of
methanein contrastto 16.7%in pentaneor 11.11%in water; evenammoniacontainsonly
17.6%hydrogen.By making methanereact with steamof high temperatures,the hydrogen
output is doubled:CH4 + 2H20 + CO2 + 4H 2. Carbon black,fluffy material of colloi-
dal finenessand usedto make rubber tough and resistant to wear, is obtained by crack-
ing methane.Other industrially important products synthesizedfrom methaneare methyl
chloride, chloroform, carbon tetrachloride, methyl alcohol, formaldehyde, nitromethane
and others. As mentioned earlier, one large use of methane is to supply hydrogen for
fertilizer (ammonia)manufacture.
Methane is nowadays industrially produced by destructive distillation of bituminous
coal(coal gasproduction) andby coal carbonization.
From recordsthat are at presentavailable,it is apparentthat this gasnow calledbiogas
has beenobservedand studied since ancient times. After the time of the Romans, the
Greeks and the Chinese,and much later with the ushering in of the scientific era, there
appearsto havebeena continuing interest on the subject leadingto the presentdegreeof
utilization of thisgas.
History of Biogas
One of the earliestto mention biogas was Van Helmont in 1630,in a communication
aboutan inflammablegasemanatingfrom decayingorganic matter.Van Helmont wasone
of the early observersand interpreters of natural phenomenawho nowadays would be
called“sc&nists”. In 1667a man by the nameof Shirley describedthis gas more precise-
1Y;he is now generally consideredas its discoverer (Sathianathan, 1975). An Italian,
Alessandro Volta, (from whom the electrical unit, volt, was denved) wrote a letter on
Nol,timber 14,1776,about a combustiblegasevolvedwhenthe bottom sediments of ponds
nearthe town of Como, northern Italy, and in Lake Verbano, werestirred. He found that
the gasexplodedwhen mixed with air and ignited; he even determined the proportions of
gasto air that gavethe loudestexplosion.
In I870 JosephPriestley, a namewell-known in the history of chemistry, reported an
“air” (that is, a gas) that was produced by the decay of substanceswhen submerged
in water.
The first allusionto animal manurecomesfrom Humphrey Davy, who reportedearly in
the nineteenth century the presenceof this combustible gas in fermenting farmyard
manure. Davy is known for the invention of the miner’s safety lamp. Even today the
principle involved in that lamp may be usedas the simple methodto avoid explosionsin
circumstanceswherea gas(like biogas)is likely to beignited.
It was in 1804 when John Dalton establishedthe chemical constitution of methane.
Dalton is consideredthe father of modem atomic theory. It is to be noted that this gas
methane attractedthe attention of the famousscientistsof that day. Not only chemistslike
John Dalton, Humphrey Davy, and JosephPriestley,but also thosewhom we now clas-
sify as physicists like Alessandro Volta, and William Henry becameinterested in the
muck gas. It was William Henry who deducedthe probable identity of the then synthe-
tic illuminating gasasmethane.This wasin 1806.
6
It appearsthat by that time, the physical scientists (physicists and chemists) had
advancedknowledgeabout biogas,as far as their disciplinesallowed, and from there the
microbiologists took over. Louis Pasteur himself devoted some time to look into the
processbut it wasone of his studentsby the nameof Bechampwho in 1868,tried to show
that microorganismswere involved in the production of methanefrom organic matter. It
appearsthat Bechampwas not able to give a very convincing proof for it and credit is
usually givento Tappeinerwho worked during the years 1882to 1884.Another studentof
Pasteur,Gayon, produced so much gasthat Pasteurentertainedthe idea of usingthe gas
for illumination and heating.
With the chemicalconstitution furedby John Dalton, the microbiological nature of the
prxess demonstratedby Bechampand Tappeiner,and the starting sourcematerial shown
to beorganicmatter by a numberof observersit would do well to considerat this point the
more applieddevelopment.
It is reportedin literature that as early as 1896,gas from sewagewas already usedfor
lighting a streetin Exeter, England. That a combustible and potentially useful gas could
be obtainedfrom human feces,must havebeenamply demonstratedin India, for in 1900
a methane(biogas)generatingplant from humanwasteswasconstructedin a leperasylum
in Matunga, India (Sathianathan, 1975). This was the HomelessLepers’ Asylum, now
known as the Acworth Leprosy Hospital in Wadals, India. This is also mentioned by
Boruff and Bushwell in 1930.It is likely that the asylum was pesteredby the obnoxious
odor of their wastes,resultingin the confinementof this pollutant and later the discovery
of a practicalway to usetheevolvedgas.
The production of biogasin quantity from cellulosicmaterialscameevenlater than that
from human wastes.It appearsthat in 1914 the Dutch tried to produce biogasfrom the
wasteof straw board manufacture.This wasin Indonesiawhenit was still the Dutch East
Indies.
After World War I, in 1918,the British becameinterestedin the production of methane
from farm wastes.This seemsnot to haveprosperedfor a numberof reasonsthat will be
discussedIater.
In 1930 Boruff and Bushwell from Illinois in the United States published articles
about the production of methanefrom farm residueslike cornstalk. Up to 1952Bushwell
was still publishing articles on the subject.Jacobs and also Levine (well-known for his
bacteriologicalendoagar medium)both from Iowa State, alsoin the United States,were
much concernedabout the generation of this gaseousfuel in relation to the enormous
amountsof availablefarm cellulosicwastes.
In theyearsaround 1940,many municipal sewagetreatmentplants in the United States
and elsewherewere already employing anaerobic“digestion” as part of the treatment of
municipal waste,and thereby generatingmethanewhich was usedto generateelectricity
for the plant. This indicated that for pollution control, the anaerobicdigestionprocessis
proveneffective,with additionalbenefitsin theform of a supplyof a usefulgas.
The French in North Africa, betweenthe years 1940-S1, are reported to have made
extensiveefforts to developso-calledmethanedigesters.Thereis ample literature on their
work in Frenchjournals. The designsand prototypes were developedby G. Ducellier and
M. Ismanin thethen FrenchNorth Africa asearly as 1937.
7
Work on biogasdevelopmentin Germany is well summarizedby Tietjen (1975) from
about 1951. There were three groups that developedprocedures: a) Strell, Goetz and
Liebmann at Munich, b) Reinhold and Noack at Darmstadt, c) Schmidt and Eggersgluss
at Allerhop. Later,otherprocedureswereworkedout: the Honhenheim,the SystemBerlin
and the Poe&h. There was parallel work in East Germany. In general,the conclusion
was: “the aspect of energy balance was judged as unfavorable because of climatic
conditions...” Gas from sewagewas another matter since proper sewagetreatment and
disposalcould not be evaded.Tietjen reports that in 1951,48 sewagetreatment plants in
West Germany provided more than 16 million cu. m. of sewagegas,3.4% of which was
utilized for powerproduction, 16.7%for digesterheating, 28.5% was deliveredto the city
gassupplysystemand 51.4%wasusedasmotor fuel for vehicles.
At the latter part of World War II; Germany and the Nazi-occupied areas found
themselvesin a deep crisis with respect to fuel for vehicles.Not only the enginesfor
transport of people,food andmerchandisebut alsothe farm machinery,like tractors, were
sorely in need. Methane (actually biogas) was generated from manure using several
hurriedly developeddigesters.The gas, which could not be liquefied under pra&d
conditions, was compressedat 3,000 psi and chargedinto pressuresteel“bottles”. Such
bottleswerefilled with gastheequivalent of 10gallonsof gasolineand thus servedasfuel
during the crisis. This experienceof Germany showsthat it is possibleto run the farms
through the energy coming from farm waste. It may be cheaperto use petroleum fuel
nowadays but not for long becauseof the present worsening of the energy crisis. A
handicapof thecolder climatesis the requirementof relatively high temperature,certainly
higherthan 26OCandpreferably30°C to 35°Cfor thebiogasproduction.
After World War II, there was extensivedevelopmenton biogas generationin many
countries: South Africa, Rhodesia, Kenya, Uganda, Russia, Australia, Italy, Korea,
Taiwan, Japan,Israel, United States,India, andthePhilippines.
In 1965 Chung PO of Taiwan published a pamphlet on two designs of family-size
digestersandtheusenf the sludgefor fertilizer andchlorella culture.(The so-calledTaiwan
designappearsin anotherchapter.)
A greatdealof significant work on biogashasbeendonein India, but this work reached
the outsideworld only in morerecenttimeswhenalmost every country becameinterested
in the subject.An authoritative reviewof developmentsin India is given by BashbaiPate1
in a paperpresentedin the ESCAP-NIST BiogasUtilization Workshop in 1975.Research
on Biogas(Gobar gas)was undertakenin India since 1939but it was not until 1951 that
therewas a real start in its use.Developmentshoweverwere slow and disappointinguntil-
1961 whenthe Indian Khadi and Village IndustriesCommissiontook over. By 1973-74,
some7000biogasplants had alreadybeeninstalled,and the numbermore than doubledby
1974-75.One reason for this expansion of biogas plants was the improvement in the
design, construction and operation of practical digesters. Furthermore, sufficient
knowledgewas obtained for the utilization of the gas not only for cooking but also for
lighting and running engines.Successmay also be attributed to the very competent
scientistsinvolved,suchasJ. Pate1and Ram Bux Singh,amongothers.The extensivework
on biogas in India may be divided into three phases:experimentation, 1937-1950; pilot
studies,1950-1963;andfull operationalstage,from 1964.
8
In the raising of animals in confinement,made necessaryby an ever-increasingmeat-
eating population, the disposalof animal wastespresentsa pressing pollution problem.
Hence large numbers of studieson the subjectwere reported each year in the countries
af%ected,mostly in the United States.The solution to problemsof animal wastetreatment
or disposalor utilization becamethe object of studiesin academicand researchinstitu-
tions. It becamethe subjectof thesesresearchfor the master’sand evenfor the doctoral
degree.Seminars,regional and international conferences,and symposia have been or-
ganizedon a subject which has,within a brief period, beenfound to be of double value:
a solution to this particular kind of pollution and at the sametime a good energysource
with the extra benefitsof organic fertilizer as a by-product. Nor is this the end of the be-
nefits,aswill beshownin a separatechapter.
9
Chapter II
BiochemistryandMicrobiology
t thereis no longerany doubt about the microbiological origin of biogas.The
m decayingleaves,straw, grass,etc. that are submergedin stagnant
of animal manure,either alone or with straw (farmyard manure).
amity in the rumen or stomach of so-calledruminant animals. In
eachcasebacteriaha&been shownto beassociatedwith biogasformation.
Organic Matter
‘

Organicmatteris the materialbfwhich living organismsarecomposed.In this category
are, therefore, the materials that constitute plants and animals. The chemical element
which is found in all organic matter is carbon; however, not aii materiais containing
carbonareorganicmatter, asfor examplelimestone(CaC03) andcalcium carbide(CaC,).
The principal componentsof organic matter arecarbohydrates,fats and proteins,and a
rather heterogeneousgroup wewill designatehereasphenolicssincethey arein someway
related to phenol.Among the phenolics are lignin and tannin. Thesetogether with other
minor groupslike chitin andresinsarefound to be more resistantto microbiological action
than the first three groups. The biggestgroup are the carbohydrateswhich comprisethe
celluloses,hemicelluloses,starches,and sugars.It must be remelmberedthat organicmatter
is a very complex material and there are not only difficulties in classification but also
inadequateinformation.
A simplified scheme of the composition and fate of organic matter in methane
fermentationis shownin thefollowing diagram:
r)I-
e I
%L
,- Carbotydm~es --)6iogm
& Vo&e solids
F&s d
I
Proteins - Sludge
Biogas is observedto arise from the bacterial decompositionof organic matter. The
more knowledgegainedabout a process,the more likely the processcan be improved or
manipulatedto the advantageof mankind. For this reasonthere have beenattempts to
gain asmuchinformation aspossibleabouthow organic matter is changedto biogas.Since
the processis microbiological, it is natural that one of the fist studiesmadewasto isolate
andidentify the specifickind of bacteria andtheparticuiar materialor chemicalcompound
11
“acted upOn; this latter is called the substrate. Thus in the fermentation of sugar, the
microorganism is yeast.,the substrate is sugar and the products are ethyl alcohol and
carbon dioxide. This alcoholic fermentation has been studied very well; it is known, for
example,that the sugaris convertedto alcohol not in one biochemicalstep, but through a
successionof changesbrought about by enzymespresentin yeast.The overall processcan
be summarizedthus: Sugar-alcohol + carbon dioxide. This can be written as a
chemicalreaction,andby employingthe methodsof chemistry wemay say that 100grams
sugar(glucose)give 51.1gramsalcohol and 48.9gramscarbon dioxide. The conversionof
glucoseto alcoholis then 51.1%. This is a theoreticalmaximum,hencea valuablepieceof
information to have. Additionally, because of our precise knowledge of alcoholic
fermentation,andof a successionof biochemicalstepsthat finally leadto the production of
alcohol, it is possible(and this hasbeendoneon an industrial scale)to detour the process
suchthat glyceroland not alcoholis the final mainproduct.
Such basicknowledgeis lacking in the biogasconversionprocess.The searchfor such
knowledgeis madevery difficult becauseit turns out that severalmicroorganisms,and not
only one, are involved in methaneproduction. To compound the difficulty, it has been
found that manychemicalcompoundsin the “parent” organic matter (not sugarsaloneas
in alcoholic fermentation)can serveas substratefor biogasproduction. We havetherefore
a rather complex case of many kinds of microorganisms, acting upon many kinds of
chemicalcompoundsin theproduction of methanegas.
The substrateor raw materialsknown to be acted upon by the methane bacteria are
very simple compounds.They fall into three groups: (1) fatty acids containing 1 to 6
carbon atoms;(2) alcohols containing 1 to 5 carbon atoms (both straight and branched-
chain); and (3) the gasescarbon dioxide, hydrogen and carbon monoxide. Additional
compoundswhich arebelievedto be alsoprobably actedupon by the methanebacteriaare
the long chainfatty acids,somedicarboxylic acids,acetone,2, 3-butyleneglycol and even
somearomaticcompoundslike benzoicacid,
Sinceorganic matter is largely composedof cellulose,starches,gums,pectins,etc. and
theseare rather complex compoundsthe questionarisesas to how theseare convertedto
biogas.The inferencethereforeis that the complexcompoundsare changedto the simple
compoundswhich in turn giverise to biogas.According to H. A. Barker (1956), the con-
versionof thesecomplexcompoundsto methaneis a multi-stageprocessin which bacteria
that cannot form methane most likely convert these substratesto simple compounds
which are then transformed by the methanebacteria to biogas. Symbolically, the series
of changes,maybewritten thus:
m-qv() bacteris 3CH 3COOH bacteria 3CH, + 3CO2
carbohydrate
)
organic acid biogas
Sincethe processof biogasproduction involvesat leasttwo distinct kinds of bacteria,it
appears that the use of a single pure culture of a bacterium, as practised in most
fermentativeprocesses,is not calledfor. As far aspresentknowledgegoes,a mixedculture
is necessary.To complicate matters, even the production of methanefrom. an already
simp!ecompoundhas been found to require Mere-+IaCspeciesof methanogenicbacteria,
dependingon the !&d of this simplecompound.Barker found that evenfor the complete
12
~;~,““y., _
*;q+ ~
+$ >
‘5, fermentationof so simple a compound as vale& acid (C4H&OOH), as many as three
~” speciesof methanebacteriamay berequired.
This rather severeselectivityof substrateby eachspeciesof methane-producingbacteria
hasgivenriseto thedescriptiveterm“extreme substratespecificity”.
TheoriesRegardingthe Origin of Methane
A chemical explanation of methane formation may be shown in the formation of
methanefrom aceticacid asa caseof decarboxylation:
CH,COOH-- CH, -t CO,
From formic acid, decarboxylationgivesCO2 + hydrogen which are gasesalsofound
in biogas:
HCOOH-H2 + CO2
If this bioconversion, as methane formation is often called, is always a process of
decarboxylation, then gasesother than methanewill be formed from organic acids as
indicatedin thefollowing chemicalequations:
CH3COOH r,C02 + CH4
methane
C2HSCOOH ~------+C02 + C2H,
ethane
C3H,COOH =,COz + C3H8
propane
C4H,COOH ,co2 + GH,,
butane
Actual observationindicatesthat only methaneis formed, irrespectiveof the kind of
acid. It is thereforelikely that eventhesesimpleacids are further converted,first to one
kind of compound which then becomes the immediate precursor of methane. This
explanation,the Van Niel carbon dioxide reduction theory, postulatesthat CO 2 and H 2
are the immediateprecursors of methaneand that the carbon dioxide is reducedby the
hydrogenin theprocess.In the bioconversionto methane,the first stepthen is production
of CO 2andH 2from the acid;the secondstepis thechemicalreductionof the CO 2by the
Hz to form methaneasillustratedbelow:
Step1 CH3COOH + 2H20 ,-/ 2C02 + 4H,
Step2 CO2 + ‘tH2 P CH4 + 2H20
Overall CH,COOH P CO2 + CH4
13
That this chemicalexplanationmay be true is indicated by studies which have shown
that as much as 70% of biogas comes from the acetic acid present in the substrate.
Bacteriawhichare normally found in the intestinal tract may also be found free-living in
thesoil andtheseform largeamountsof aceticacid.
The stepwiseformation of CH4 from formic acid may beasfollows:
Step1 QHCOOH L, ‘tco2 + 4H2
step2 c02+ 4H2 c-> CH4 + 2H20
Overall 4HCOOH - CH4 + 3CO2 + 2H20
From othersimplecompounds,the formation of CH4 may begiven asfollows:
1. From a primary alcohol: 2C2HsOH + CO 2 - CH, + 2CH,COOH
2. From a secondaryalcohol:
4CH,CHOHCH3 + CO2 w CH4, I- 4CH$OCH, + 2H20
3. From a higherfatty acid:
2C4H,COOH + CO2 + 2H20  CH4 + 2CH3COOH + 2CH3CH2COOH
4. Frommethanol: 4CH3OH ,-> 3CH4 + CO2 + 2H20
It will b2 noted that CO2 is a reactant in the fast three reactionsgiven above,but not
in the !astreaction It hasbeenpostulatedthat the origin of methaneis CO;! and the pro-
cessinvolvesstepsthat arewell known in chemistry.
+2H
co2 - HCOOH +2H
+2H +2H
0-p HCHO 11111+ CH,OH S-W CH4
-H20 -Hz0
The processstarts with the reduction of CO2 by hydrogento produce formic acid, then
to formaldehydeto methanoland finally to methane.Actual experiments,however,have
failed to showthat this sequenceof eventsactually takesplace.Barker thereforesuggests
that the initial reductive stepis not by hydrogen but by a hydrogen carrier probably in
combiied form representedby XH. The reductive steps,comparableto the CO2 reduc-
tion procc=ssearliergiven,arethen:
+2H +2H +2H
CO2 - XCOOH --H 0 XCHo2
-XCH,OH -d XCH,
2
03 CH4 + XH
Thehydrogencarrier is regeneratedandrecycledasillustrated above.
14
The formationof CH4 &n methanoland from aceticacid may also be shownto
involvethe carrierXH andthusmakepossiblea unifiedtheoryasto the mechanismof
formrtion of CH,, but in thesetwo latter casesthe oxidant is not CO2 althoughthe
reductantisthesame,XH. Thecompleteschemeof Barkeris asfollows:
~xH+co~-xcocm
I
+Z:H
-ho
XCHO
-Hz0
-XH+Cl=l~OH
1
- co2
-XH+cM~COOH - 2H
I
+2kl
XCb42OH
+2H
-I420
- XCH~
I
+2H
m&e - Xkl+cHq
The theory then is that complex chemical compounds are biodegradedto simpler
compounds and ultimately to CO2, CH30H or CH&OOH; theselatter compounds,
through theactionof methanogenicbacteria,yield methanethrough aninitial reactionwith
a hypothetical compound XH. Obviously the compound XH must be found or
demonstratedto exist.It appearsthat theburdenof proof was assignedasa thesisfor a Ph.
D. degree.The student, ThressaStadtman, successfullyunearthedsufficient evidenceto
showthat XH is a cobalt-containingcompoundthat exhibits vitamin B12activity. Adding
support to the possibleinvolvementof vitamin B12in methanefermentationis the finding
that sludgesfrom methanefermentersare quite rich in this vitamin, thus opening a new
potentialof usefulnessof thebioconversionprocess.
The presentoverallpicture of theprocessof biogas(or methane)formation from organic
matteristhenasfollows:
1. The agent of change (from organic matter to biogas) consistsof two groups of
bacteria: the methane-formingand the nonmethane-formingbacteria. Theselatter
act on the complex organic compounds in the substrate (raw material), such as
cellulose,starch, proteins, fats, etc., converting them to more soluble compounds
largely by hydrolysis: the carbohydratesto simple sugars,the fats to fatty acids
andglycerol,the proteinsto proteoses,peptones,etc.
2. This initial change is followed by a conversion of these compounds la.rgely to
acids of one to six carbon atoms, to alcoholsof one to five carbons and to other
similarly simplecompounds.Free oxygen is not neededin the processand is even
harmful.
3. The methanogenicbacteria act on these acids, alcohols, etc.; the final metabolic
products are CH4 and CO2 (biogas). These bacteria demand strict anaerobic
conditions;evenmildoxidizing substanceslike nitrates mustbeabsent.
4. The mechanismof formation of biogas from simple coqwunds is not yet very
clearbut there is evidencethat a vitamin B 12 compoundis involved, hencethe ap-
parentenrichmentof this vitamin in thesludge.
5. A decreasein pH as a result of acid formation inhibits the growth of the methane-
forming bacteria, therefore acid formation must proceedslowly and in step with
the methane-forming process. The maintenance of a proper range of pH is of
courseattained through the presenceof buffers which are generatedin the ferment-
ting medium.
6. It is apparent that the rate of acid formation will dependon the rate of the con-
versionto biogas; that is, acid is allowed to form only about as fast as it is con-
vertedtoCH4andC02.
The Bacteriain BiogasProduction
Pig manure, by itself, generatesbiogas spontaneously,although it takes quite some
time for this to happen. Hobson and Shaw (1967), using a M-liter digester initially
filled with water, added pig manure gradually so that the water was replacedin about
4 weeks’time. By then the total solids was 2%. Operating as a continuous-fedsystem,
pig manurewas addeddaily at the rate of 0.03 lb. per cu. ft. per day. At regular time in-
tervalstheydeterminedthekind andnumberof bacteria.Their resultswereasfollows:
First week: Total countwas5 x lo6 to 5 x 10’ /ml.
The number of amylolytic bacteria (starch decomposers)was greater
than 4 x 1oQnl.
Third week: By this time the methanogenic bacteria (methane producers) began
to appear, numbering about lo3 /ml. and they increased in number
with increasingtime.
Fourth to fifth weeks: The cellulolytic bacteria (cellulose decomposing), num-
bered lo4 to 105 /ml. The proteolytic bacteria (protein-decompos-
ing) alsoappearedat aboutthis time at greaterthan 4 x lo4 /ml.
Ninth week: The methanogenicbacteriareached10’ /ml.
In another study of the bacteria in pig dung the following results were obtained by
HobsonandShaw(1967)in a slurry of 4% “settable solids”:
Total count at start:
Anaerobic,6.4 x lo8 /ml.
Aerobic, about 2.4 x lo8 /ml.
The nonmethanogenicbacteria were found to be principally the noncellulolytic and
thecellulolytic bacteria.
I. Noncellulolytic bacteria.
1. Streptococci,facultatively anaerobic,constituting 43 to 47% of all isolates.Non-
proteolytic and nonamylolytic, probably play a role in maintaining the anaero-
bit condition in digesters.
16
:
2. Bact&ds, constituting 20 to 80% of the anaerobic bacteria. Gram-negative
pleomorphicrods, shortto medium length; some are coccobacilli, mostly amy-
lolytic.‘Fcrment mono- and disaccharidesaa well as glycerol producing pro-
pionic, aceticandbutyricacids.
3. Clostridia. The most activeproteolytic bacteria,foundbelongto threegroups:
A. Amylolytic; very similar to Clostridium butyricum; fermentation pro-
ductsareaceticandbutyric acids.
B. Proteolytic; fermentsugarsforming aceticandisovalericacids.
C. Proteolytic but do not fermentsugar.
II. Cellulolytic bacteria, a heterogenousgroup present in lo4 to 10’ /ml. were iso-
lated.One isolatewas a Gram-positiverod, generallycurved, often in short chains.From
cellulose, it produced mainly propionic acid, occasionally acetic as well as traces of
formic and succinic. Other isolateswere Gram-negativecoccobacilli or rods of various
morphologies.They form volatileacidsfrom cellulose.
III. Other bacteria isolated in small quantities were lactobacilli, staphylococci, gly-
cerol-fermentersandlipolytic bacteria.
The methanogenicbacteria beganto appearon the third week and by the 9th week
they reacheda count of lo6 /ml. Of acids testedas substrates,only formic and butyric
acids were converted to methane.The organism was classified as Methanobacterium
formicicum, a Gram-negativerod of variable length. It producesmethanefrom a mixture
of CO and hydrogen gasesor from formate, but not from acetate,propionate, isobuty-
rate, valerate, isovalerate, succinate, pyruvate, glucose, ethanol, propanol, butanol or
isobutanol.
The methanogenic bacteria possess the following general characteristics (Barker,
1956):
1. Strictly anaerobic; not only molecular oxygen but also compounds that easily
give oxygen like the nitrates must be absent. In Barker’s studies (1956), pure
cultures of these bacteria were obtained successfully for the first time only by
usingsodiumsulfideto removethe lasttracesof oxygen.
2. Require a pH range for growth of 6.4 to 7.2 (other authors put the optimum
pH at 7.2 to 8.2). However, one speciesgrows at pH 8-9, and in peat bogswhere
thepH is about4, somemethaneis alsoformed.
3. Utilize ammoniumsaltsasnitrogen source.
4. No known need for nutritional factors (probably amply supplied by commonly
usedsubstrates).This is in contrast to otherorganismslike yeast.
5. Producemethaneasa major metabolite.
6. Exhibit extreme substratespecificity; thesebacteria are able to utilize only a few
very simplecompounds.
In accordance with known microbiological techniques, attempts have been made
to grow in strict isolation, each speciesof bacterium that producesmethane.This has
proven to be very difficult; hencethere are only very few that are definitely confvmed
to bemethaneproducers.
17
p’ ,,,
,,_ I
I
Barker(1956)classifiedthemethanogenicbacteriaasfdlows:
Family: Methanobacteriaceae
A. Rod-shapedcells
i. Nonsporulatiqg Methunobucterfum
1. Mikuxfonnicfcum -------- CO, H, , formate’-/
2. Mkt. propionicum ---- propionate
3. M&act. sohngenii----------------- acetate,butyrate
4. M&t. ruminantiud~ -------- CO2 , H 2
II. Sporulating: Methanobacillus
1. Mbac. omelianskii ----------------- H.2, primary and secondaryalcohols
B. Sphericalcells
I. Cellsnot in sarcinaarrangement:Methunococcus
1 l MC* m& - ~~~~~~~~~~~~~~~~~~~ - ---- ----- acetate, butyrate
2. MC.vannielif--------------------------- forma@,H 2
II. Cellsin sarcinaarrangement: Methanosurcinu
1aMs. bark&i --------------------------- CH3OH, acetate,CO, H2
2. Ms. methanica------------------------ acetate,butyrate
Methane Production in the Rumen - Pertinent to this discussionon methaneproducers
are the results of studies on the microflora of the rumen. Hungate and co-workers
(through Thimann, 1963) have shown that the rumen contains many organisms close-
ly relatedphysiologically, mostly short rod, oval or coccus,which actively ferment cel-
lulose to organic acids like acetic and propionic. Methane results from the secondary
fermentationof theseacidsby methanogenicbacteria which have beenfound present up
to 2 x 10” /ml. in rumen fluid. A cow reportedly gives as much as 700 liters of gas
in a day.
Need for a Massive Amount of Starter
Since both methanogenicand nonmethanogenicpopulations are neededfor biogas
production, it is therefore evident that not only should thesetwo kinds of bacteria be
present,but they should also be in the optimum proportion. This proportion is no doubt
presentin an actively fermenting digester,no more than 20 days old, and constitutes
the bestseedor starter. Additionally such a starter has already developedsufficient buf
fers to maintain the pH at the desiredvalue. An actively fermenting material also gene-
rates hydrogen sulfide (and probably other soluble sulfides) which brings about the
highly anaerobiccondition demandedby the methane-producingbacteria. It is now un-
derstandablewhy a massiveamount of inoculant or starter, no less than 20% of total
starting slurry, is insuranceagainstdigesterfailure.
L/ Knownsubstrates.
-2/ Addedto Barker’slist.
18
Ilbtmtion l-2: Rdicmbiological uuy d vita& B,z
Illustration 1-3: Pollution control laboratory
19
Chapter III
Laboratory and Pilot Plant Experiments
(All the experimentsdescribedin this chapterwereconductedin the laboratory at Maya
Farms.)
It is highly desirableto get the highestpossibleconversionof hog manureto biogasand
the minimum amount of the sludgeby-product. Sinceeventually the sludgewill have to
bedisposedof, largequantitiesmay presenta problem.The fermentingmixture of manure
and water shouldbe asconcentratedas possible.From the beginning,it was clear that the
specificoperatingconditions would haveto beworked out and this would bebetterdonein
a laboratory whereconditions of operation are smallerand easierto control than in large.
installations.
For useasa “digester”, (as the fermentationtank is called in literature on biogas),the
ordinary gallon bottle proved to be suitable. It is easily available, being of local
manufacture and often used as container for many liquid food commodities. It is
inexpensive,andsincecost is a matter of concernwhen up to a hundredsuch bottlesmay
beneededat onetime, it is thereforeadequatefor the task on hand.A chargeof 2.7 liters
of digesterslurry into the 3.8~liter(onegallon) bottle leavesa safeheadspaceof about 1.0
liter. The heightof the slurry in the bottle in relation to the diametergives a 1:1 ratio, CL
very desirableattribute for anaerobicfermentation. The charge of 2.7 liters of slurry is
large enoughfor good reproduciMity amongthe five replicatesthat are always run. The
usual, although minor, difficulty in inserting severalpiecesof glasstubing into a rubber
stopper is not met since the gallon bottle accepts a large stopper and can easily
accommodate3 to 4 piecesof glasstubing.
Laboratory Set-up for Methane Fermentation
The set-upis shownin Fig. 3-1.There aret!!ee one-gallonbottles.Bottle A servesasthe
digester;bottle B is the gas holder and bottle C is the water-overflow collector, empty at
the start. The digester(A) is chargedwith 2.7 liters of the preparedexperimentaldigester
slurry, a mixture of hog manure,water and starter.Bottle B is filed completelywith water.
The rubber stoppers fitted with the interconnecting glass tubing are inserted into the
bottles, preferably wired in place since gas pressure is developed.In operation, gas
generatedin A pushesout an equalvolume of water from B to C. The volume of gascan
be determinedfrom the volumereading in C which has beenpreviously calibrated. Bottle
C may beomittedif a drain canbe provided for tubed in which caseBottle B will haveto
be’markedin liters.The digesterslurry chargedin Bottle A doesnot usually generatemore
than 3 liters of ga$ in 24 hours; hencethe water in bottles B andC neednot be attendedto
more than once a day. The gas collected is allowed to escapeinto the air after due
measurementof its volume or tier samplesaretakenfor analysis;B is refilled with water
collectedin C becausethis.wateris already saturatedwith the gas.Solubility correction for
gas volume is thus diminished. Bottle A is briefly shaken once a day to loosen up gas
lhstration I-1: Experimental laboratory digesters at Maya Farms
--------
tml
----------=-_---_----_--!-1-z---_-----
=I
-----_--_--------
C
Fig. 3- I : Laboratory set-up for study of biological production of methane
22
::
bubblesin the slurry. Gas bubblesare entrappedin the slurry especiallyin thick slurries.
The fermentation room has shelvesto accommodatea hundred three-bottle set-upsand
adjoinsa heateddrying room; thetemperaturein the fermentationroom is thus kept at 3lo
+ 3OCthroughout the year. The fermentation room is preferably well-enclosedwith a
&ntrolled air exit, a smallventilatingfan fixed on a convenientwall.
To setup a fermentationrun, a digesterslurry is made by dispersingfresh hog m.anure
in water, placingthe mixture into bottle A and addingthe starter.If the desiredratio of hog
manureto water is 1:1 and the starter is 25%, then the weight of the starter is 0.25 x 2.7
kg. or 0.675 kg. sincethe digesterslurry totals 2.7 kg. The weight of the manure and the
water is 2.7 kg.- 0.675 kg. or 2.025kg. andhence,manureweightis 1.0125kg. In general
the relationshipis: digesterslurry = manure + water + starter. The water for making the
slurry is unchlorinated;the startercomesfrom an actively-fermentinghog manureslurry in
its 20th to 25thday of fermentation.The volumeof gasevolvedis measuredeveryday.
The Gas ProductionCurve
The plot of the cumulative gasvolume againsttime (day number)is the gasproduction
curve, Fig. 3-2. Its appearanceis similar to the well-known growth curve of bacteria.
However, theinitial lag phaseis not in evidenceprobably becauseof the massiveamount
of inoculant (starter). Gas is measurablewithin 24 hours and continuesto increase;this
portion of the curve is the logarithmic phase.In due time the increase in gas volume
slackens.The curve makesa bendand continuesto increasebut at a much reducedrate.
This part of the curve is the “senescencephase”;the “biopause” phaseis the sectorwhere
the logarithmic phasechangesover to senescence.In Fig. 3-2 the logarithmic or active
growth phase lasts 22 days, followed by the biopause of about 6 days, after which
senescencetakes over. This is the general shapeof a typical gas production curve for
methanefermentation.
It will benoticedin Fig. 3-2 that the rate of gasproduction in the growth phaseis much
higher than that in the sencticencephase.The change-overtakes place during biopause.
Thereis reasonto operatea fermenter(digester)only up to biopausebecauseof thedecline
in gasproduction thereafter.The retention time is the number of days that the fermenting
slurry is retainedin the digester.Sincein the presentexamplethe biopauselasts six days,
the operator of the fermentermay selecthis retention time within this period. It is to be
noted that retentiontime may also be selectedor adopted.The operator may wish, with
reason,to adopt a retention time earlier than biopausealthough he will be losing gas.He
may also prefer a retention time after biopausein which casehe will be wasting digester
spacebecausehis digesterproducesgas inefficiently after biopause.The time when bio-
pauseoccursisthereforeimportant.
The active growth phaseand also the senescencephaseare very closeto being linear.
Assumingthis to be the case,it is possibleto calculatethe rate of gasproduction in each
phase.For thegrowth phaseof 22 days,therateis:
54.7liters
22 days
= 2.5liters per day
23
70I- -
60
4
3 5o
2
3
0
m
q 40
fz
z t
m
$ 30
L -t
a
20
10
I
f
av=54.7 z
At 22
2.48 I/da
/
I I I I I
I I I I I I
0 10 20 30 40 50 60
DAY NlJMl3ER
FIG. 3-2 TYPICAL BIOGAS PRODUCTlON CURVE
“
,c.i
For the senescencephase,taking thegasvolumebetweenthe 32ndand 60th days,the rate
is: (68.6- 65.0)
(50- 32)
= 0.20liter perday.
Therate of gasproduction duringthe growth phaseis more than tentimesthe rateduring
senescence.
The rate of gasproduction during the growth phaseis a good index for the study of
conditionsfor methanefermentation.It is to benotedhoweverthat besidesthe ratein liters
of gasper day, anotherinformativeratio is the numberof liters of gasper kg. of manure.
Thevariousmethodsthat maybeusedin reportinggasproductionareshownbelow:
Gasvolume,liters
Gasperday,liters
Gasperkg.manure
Gasperkg.perday
TheProportionof Manaveto Water
Time Periodin Days
Q-20 O-30 O-60
48.0 64.5 71.4
2.40 2.15 1.19
47.4 63.7 70.5
3.37 2.12 1.12
The raw material for fermentation in the experimentsis hog manure. Foi biogas
production,the questionsthat ariseat the start are: (1) how muchdilution with water is
neededand (2) how much starter is used. To provide answersto these questions,the
following manure-watermixtures or slurrieswereprepared: 1:1, 1:1.5, 1:2.,1:3 and 1:4
usingfreshmanure,i.e.collectedwithin 24 hours,anduntreateddeep-wellwater. Thetotal
volumeof the slurry was kept at 2.7 liters (approx. 2.7 kg.) in order not to overloadthe
gallon jar digester.Each bottle was seededwith a vigorously fermenting starter, the
&v,Ql&iqt Qf j&7&h WZlf ndillatwl Ctl 8s to fiLm&iS_h_ st,m-ei ql~v&~t &l 205!/nj 25% and 33%..WI--~‘“-v- YY
(l/5, l/4 and l/3) of the 2.7 liters of slurry. The amount of starter is calculatedfirst:
20% x 2.7 kg.; 25% x 2.7, and 33% x 2.7 kg. In a 1:2 manure/waterslurry, the weight
. 2.16of manureis (+ or 0.72 kg. and that of water is 0.72 x 2 or 1.44 kg. The weights,
of starter, manure,and water for the experimentsare calculatedin the samemanner
and aretabulatedin Table3-2.
All the experimental“digesters” gavemeasurablevolumesof gaswithin 24 hours.The
amountof gaswas measuredeveryday. The plot of gasvolumesin liters againsttime in
days are given in Fig. -3-3. In all casesthe characteristic gas production curve was
obtained,eachhaving a well-definedactive growth phase,a biopauseand a senescence
phase.Thelowestpercentageof starter employed,namely 2096,appearedto be adequate.
The ratesof gasproduction of slurriesof equalvolume(blutdserent manure-waterratios)
aredifferentfrom *theratescalculatedat equalmanureweightsfor the samemanure-water
ratios.Whencomputedon equalweightbasis,i, e.per kg. of manure,the curvesappearin
the reverseorder as in the experimentalresultswhich are on equalslurry volumeof 2.7
liters (Fig. 3-4).It can be seenfrom the graphthat the volumeof gasper kg. of manureis
larger, the moredilute the slurry. However,the 1:l slurry givesmoregasper day for the
samedigesterspacethan a moredilute slurry becauseof the largerweight of raw material
(manure)in the*1:1slurry but lessgason equalweightof manurebasis.
25
UJ > K-J
LITERS BIOGAS CUMULATIVE
0
WI > N
LITERS BIOGAS CUMULATIVE
LITERS BIOGAS CUMULATIVE
80
60
>”
i=
5
3 50
z
2
2
CD 4o
0
G
iii
w
I==
30
2
20,
10’
0
1:2
1:3
1:4
FIG. 34 GAS PRODUCTION CURVES ON!
EQUAL SLURRY VOLUME AND
EQUAL MANURE WEIGHT BASIS.
- EQUAL WEIGHT BASIS
EQUAL VOLUME BASIS
I I I I
I
I
I I I I 1
10 20 30 40 50 60
DAY NUMBER
27
Thereis a beliefthat storageof pig manurefor a few dayswould enchanceits biogas-
producingcapability. The experimentaltrials of manurestoredat 0, 1 day and 3 days are
shown in Fig. 3-5 and indicate that fresh or one day old manure is best for biogas
production.
Amount of Starter
Sincetheproduction of methaneis a fermentationprocess,the amount of the inoculant
or starteris of prime importance.Literature on the subjectis meager.It is practicalto use
as starter, a portion of a successfulmethanefermentationfrom the activatedsludgein
sewagetreatmentworks. In someprocedures,the manure slurry is allowed to ferment
without benefitof an addedstarter. To determinethe amount of starter, the apparatus
consistedof thepreviously-described3-bottleset-up;thedigesterslurry wasfutedat 2.7 kg.
manure-waterratio at 1:l andthe starteramountvariedto correspondto 0, 5, 10, 15,20,
25 and33%of 2.7kg.Theweightsinvolvedin kg.wereasfollows:
digesterslurry = manure + water + starter
for 0% starter: 2.7 = 1.35 + 1.35 + zero
for 5% starter: 2.7 = 1.28 + 1.28 + 0.135
for 10%starter: 2.7 = 1.21 + 1.21 + 0.270
for 15%starter: 2.7 = 1.15 + 1.15 + 0.405
for 20%starter: 2.7 = 1.08 + 1.08 + 0.540
for 25%starter: 2.7 = 1.01 + 1.01 + 0.675
for 33%starter: 2.7 = 0.90 + 0.90 + 0.90
The figureswere arrived at by calculating as follows: Weight of starter: 5% of 2.7 kg.
= 0.135 kg. Weight of manureand water: 2.7 kg. - 0.135 kg. = 2.565 kg. Weight of
manureor weightof waterfor a 1:1(w/w) ratio isonehalf of 2.565kg. or 1.28kg.
Theresultsof this experimentaregivenin theform of gasproductioncurvesin Fig. 3-6.
It is easilyseenthat a slurry without addedstarteris a very poor performer.An inoculant
is essentialto good gas production. Increasingthe amount of addedinoculant improves
performanceup to 20% after which the gasproduction curvesappearnormal with well-
defmedgrowthphase,biopause,and senescencephase.From this experiment,it seemsthat
the startermustbe at least20% of the weightof the digesterslurry. A digestercontaining
1000 liters of slurry inocultitedwith 1.0 liter of starter is not likely to perform well. It
should be noted that the substratematerial, hog manure, is not given a pre-sterilizing
treatment;henceit is teemingwith many kindsof organismsthat caneasilyoverwhelmthe
bacteriain thestarterif thesebacteriaconsituteonly averysmallproportion.
The betterperformanceof fermentationemployinglarger amountsof starter is further
shownin thefollowing tabulation.
Starter,% (A) 5 10 15 20 25 33
Liters gasproduced,20
~YS 09 15 18 28 38 47 54
Days to produce50 liters
lw (C) 60 45 31 25 21 19
28
90
60
70
560
F
5
g50
0
2
8
zw
cn
E
= 30
20
10’
FIQ. 3-6 GAS PRODUCTION CURVES
FOR STORED PIG MANURE
PRODUCTION CURVES
STORED PIG MANURE
v DAY NUMBERDAY NUMBER
I 1 I I I i
0
7c
6C
5(
4t
3c
ZC
10
0
90
60
70
60
E
am
z
s 40,
%
In
3 30.
P
B
5 20,
10.
10 20 30 40 50 60 70
P
lb
r40
PERCENTAGE OF STARTER
FIG. 3-7 RELATION OF PERCENTAGE OF STARTER
AND NUMbER .OF DAYS TO PRODUCE 60
LITERS BIOGAS.
0 10 20 30 40 50 60 70
DAY NUMBER
FID. 3-6 DAS PRODUCTION CURVES FOR VARYING
1DDT
/
(c) 23 DAY STARTER
go- -
/
BO- -
/
70--
/
BO--
60- -
/T
(8) 30 DAY STARTER
IAI 60 DAY STARTER
40--
30--
20--
FIG. 3-S EFFECT OF AGE OF
fi / STARTER ON GAS
PRODUCTION
DAY NUMBER
I 1 I I i
SYARTER PERCENTAQE
0 10 20 30 40 50 60
With 20 days fermentation time, the 20% starter gave twice as much gas as the 10%
starter.This 2:l relation is also apparent in the 33% and 15% starter, The value B/A is
fairly constant; so is the value of A x C. The plot of starter percent (A) against the 20-day
gas (B) is shown in Fig. 3-7. It is seenthat the higher the percentageof starter, the better is
gas production. The extreme case will be the situation where all fermenting slurry is used
as starter. It is hardly conceivable that this arrangement can be made practical, but it is
what actually happensin a continuous-fed digesterwhich will bediscussedlater.
Ageof Starter
The starter or inoculum should come from a vigorously fermenting slurry; the slurry
should be at the active growth phase. In one set of the laboratory experiments, starters
coming from slurries that had pndergone fermentation for 23 days, 30 days and 60 days
were used as starters (five replicates each). The results, as shown in Fig. 3-8, indicate the
greater gas production rate as well as relatively larger volume of biogas (30-day period)
produced by the 23-day old starter.
Gas Productionat a ConstantVolume of DigesterSlurry and at a ConstantWeight of
Manure
In the laboratory experimentson the effect of dilution of the manure on gasproduction,
the weights of hog manure had to be varied, since the volume of the digester spaceis ne-
cessarily constant at 2.7 liters. Gas production for this kind of situation is given in the set
of curvesin Fig. 3-4. The impression is that the more dilute slurries, like 1:4 manure-water
mixtures, give a poor performance. When gasproduction figures are calculated on the per
kilogram of manure basis,there is a very striking change in the order of performance. The
starred lines of Fig. 3-4 show this. On a constant weight basis,that is, on the p;‘erkg. basis,
the most dilute slurry gives the larger volume of gas. For comparing efficiencies of gas
production from a given material, a comparison based on the yield of one kg. of the
material under varying conditions appears logical. For comparison of actual digester
performance we cannot neglect the imposed condition of a constant volume of digester
slurry.
This discussion brings relative advantages and disadvantages in employing dilute
slurries. With the option of operating a digesteron thin slurry such as 1:4, one can expect
to get a high conversion of manure to gas on the per kg. basis.The retention time is short;
experimentsindicate a period as short as 15 days or even less,and thus the slurry will go
through the digester rather quickly in continuous-fed digesters. Pumps may be used to
move the slurry, which is a great convenience. However, there will be a voluminous
amount of sludgeto disposeof. Since this sludgeis quite well “digested”, it will beexpected
to require lessconditioning to get it ready for further utilization.
The other option is to useasthick a slurry aspossible, 1:1or even thicker. The material
will be difficult to move with pumps. The volume of gas produced per day will be high
although the conversion efficiency per kg. manure will be rather low and the post-digestion
time will be longer. The digester space per unit weight of manure will be small and
retention times wiIl be longer, about 30-40 days, The relative volumes of digester needed
when employing various dilutions are shown in Table 3-l. A 1:4 slurry occupies 2.5 times
the volume of a 1:1 slurry, although both slurries contain the sameinitial weight of manure.
30
RelativeVolumeof DigesterSpaceto Contain
OneKilogramof Hog Manurein Varying Manure-
WaterRatios.(Starter2096,Digester Slurry 2.7
Liters)
Manure-waterratio (dilution) 1:l 1:2 1:3 1:4
Weightof manure,kg. 1.08 0.72 0.54 0.432
Digesterspace(slurry)liters 2.7 2.7 2.7 2.7
Relative digesterspace 1.0 1.5 2.0 2.5
Ratio of Volume of Gas/Day to Volume of Digester Slurry
A useful and simplerule of thumb usedto check on performance of working digestersis
that the value of the ratio of gas volume per day to digester slurry volume, is about 1. Fig.
3-9 givesplots of theseratios in relation to day number of digesteroperation. From the 5th
to the 15th day of operation, the ratio gas volume per day to slurry volume is about 1.5.
After 20 daysthe ratio decreasesto lessthen 1.This is to be ascribedto senescence.Of the
three dilutions studied, 1:1,l: 1.5and 1:2, the last gavethe smallestvalues.A gwd working
digester therefore has a volume ratio of gas to slurry of at least 1:2 (for slurries of 1:l to
1:2).
Rates of BiogasProduction
While the total volume of biogas evolved during the active growth phase is useful
information, the rate at which the gas is produced is equally of value. The rate may be
calculated in liters of gas per day per kg. of starting material. The weight of volatile solids
(W&j or the non-ash dry matter, is often used by scientific workers instead of the dry
matter content. Table 3-3 givestheserates averagedfor each of the following time periods:
O-20,0-30,0-60 days, and for three starter percentages.The 20-day period comesnearest
to the period of active growth, that is, from the start to biopause. The rates are highest in
the O-20 day period and progressively decreasein the longer periods. The decreaseis due
to the onset of the senescencephase (low rate period). The general average rate of bio-
gas formation for the O-20day period is 13.6 liters of gas per day per kg. volatile solids;
the value for the O-30 day period is 10.5 liters/day per kg. V. S. The plot of the rate (liters
per day per kg.) against V. S is shown in Fig. 3-10. At the active growth phasethe value
of this rate is quite constant over the range of about 4 to 8% V. S. The highest rates are
those for more dilute slurries and for shorter fermentation periods, although the limits
have not been determined. In so-called continuous-fed operation, the observed high rate
of gasproduction is probably due to the effect of shorter retention time often adopted.
Rate of Gas Production During Senescence
Fig. 3-10 also gives the rates of biogas production during the senescencephase. The
calculated values are ,closeto 0.2 liters per day per kg. starting material over the range of
3% to 8% V. S. The senescencerate is about one-tenth the active growth rate. It is to be
noted herethat theseresults show that the correction of the observedgas volumes from the
volume of gas coming from the starter is small when the starter employed is already at or
near senescence.
31
I I I
I 1 I I
10 20 30 40
DAY NUMBER
FIG. 3-9 RATIO OF VOLUME OF GAS PER DAV
TO VOLUME OF DIGESTER SLURRY.
2oc
16C
16C
E
z
s 140
5
::
ii!
: 120
3
iii
3
g loo
0
$
if
2 60
8
5
2
f 60
ii
2 40
5
20
FIG. 3-11 GAS PRODUCTION CURVES
1:1.5
1:2
EGUAL MANURE
WEIGHT
EOUAL SLURRY
VOLUMES
DAY NUMBER
1:l
1~16
FROM
:l
:1.5
:2
S--
--a0 E
3
B
-40
E
3
In
ii
;r
--40 E
8
t
%
--20 ::
1
I
t
E
% FRESH DUNG 0 20 30 4b Ii0
% VOLATILE SOLIDS 2 4 6 8 10
FIG. 3-10 RATES OF BlOGAS PRODUCTION DURING
ACTLVE GROWTH AND SENESCENCE IN
RELATION TO DUNG CONCENTRATION.
lo( I-
9c I- -
.3aI-.
70
60
s
5
3 50,
5
0’
2 40
p
ft
p 30,
3
20
10,
FIG. 3-12 GAS PRODUCTION CURVES
FOR CORN STALK AND
RICE STRAW.
0 10 30 40 50 60
C 9Y NUMBER
Ga8Pmluctlon tiom Other Substrates
Fig. 3-l 1givesthe gasproduction curves for poultry manure. The volume of biogas per
kg. of dry manure is plotted here against number of days of fermentation. The curves show
a welldefmed active growth phasebut the biopauseis rather indistinct and mergeswith the
senescencephase. Retention time is therefore not easily determined from the graph. The
shapeof the senescencecurve appears to indicate that the chicken dung was undergoing
a relatively strong fermentation beyond the active phase. This may be due to inadequate
fme grinding of the manure. Further trials should be made also on greater dilutions, with
more stirring and probably the addition of a carbon source since the C/N value for
chicken manureis lower than for pig manure. (SeeChapter 4).
Fig. 3-12givesthe gasproduction curvesfor ground corn stalks and chopped rice straw,
both in admixture with hog manure. The gas curves have well-defined phases.The active
growth phaseshave identical slopes for all these substrate materials with a value of 2.87
liters per day, which is higher than in most of the pig manure experiments. Biopause was
reached latest with 8% ground corn stalks (26 days) followed by 2% ground corn stalks
(22 days); chopped rice straw reached biopause earlier (about 18 days). The senescence
phasestill produced gas at a fairly high rate, due probably to a secondary fermentation. It
is evident that the process of fermentation consisted of a primary process whereby the
more easily fermented compounds underwent decomposition at a high rate; this was
followed by the decomposition of the more difficultly fermentable materials during
senescence,either becauseof their nature (cellulose, lignin) or because of larger particle
sizedueto inadequategrinding.
Desirable Characteristics of a Gas Production Curve of a Batch-fed Digester
The various forms of gasproduction curvesare shown in Fig. 3-6. There are advantages
in having a methane fermentation that proceedsin such a manner that the gas production
curve (gasvolume plotted againstday number) hasthe following characteristics:
1. Three definite, well-defined phasesmay be distinguished: active gas production, bio-
pause and senescence.When this is the case, the optimum retention time becomes also
definite, sothat the number of days of retention in the digesteris well-defined.
2. The slope of the senescentphase should preferably be as small as possible, which
indicates that the discharged sludge will be evolving very little gas and in consequence
have lessodor and require lesssludgeconditioning.
3. The slope of the active gas production phase should be as large as possible and of
a constant value; a wavering value indicates that there are factors (change in tempera-
ture, lack of stirring, overloading, lack of starter, etc.) that are appreciably affecting the
normal operation of the digester.
Corrections on the Measured Gas Volumes
Since the experimental studies involved measurement of gas volumes, the following
corrections areapplicable:
1. Gas coming from the addedinoculum or starter which tendsto increasethe observed
gas volume. According to Fig. 3-10, the rate of gas formation averages2 liters per kg. per
day. The volume of gas from a 20% starter is expectedto be0.36 x 0.2 x 2.0 or 0.144 liters/
33
day but only 4096of the manureactually ‘ferments(seeChapterS),hence0.4 x 0.144or
0.057 liter/day; for a fermentationlasting”‘20days,the volumeof gas coming from the
starteris 1.15liters.
2. Solubilityof CO2 in water.Suchsolubiity is0.034molaror 0.85liter gasperliter of
waterat 25OC,or 1.8litersgasin 3 liters of waterarelost throughsolubility effect.Part of
the CO2continuouslydiffusesout of the solution into the air; hencethe amount of CO2
lost is greaterthancanbeaccountedfor by a meresolubility data.Becauseof suchlossof
CO2, theexperimentallymeasuredvolumeof biogasis smaller by at least 1.8 liters than is
actuallyproducedin theexperiment.
3. Aqueous tension or vapor pressure exerted by water on the gas volume. This value
increaseswith temperatureand is about 32 mm. at room temperature. Atmospheric
pressureis generallyaround 750 mm, hencethe partial pressureis about 718 mm. The
measuredgas volumes are therefore to be multiplied by the factor 0.97 to correct the
volumesfor watervapor.
In summary, the observed biogas volume is larger by 1.15 liters which is the estimated
volumeof gasgiven off by the starter in 20 days. It is smaller by at least 1.8 liters due to
loss of CO2 through its solubility in water at ambient temperature and pressure. The
observed gasvolume tends to be larger becauseof the vapor pressureof water; correcting
for this factor, the biogas volume is 0.97 times that of the observedvolume. All in all, the
corrections are small and more or less cancel each other; hence all gas volumes reported
areactualmeasuredvolumes.
Application of Batch Operation Data to Continuous-fed Operation
The data so far obtained camefrom experimentswhere the digester(fermenter) is given
one charge of slurry for the duration of the fermentation. The active growth, biopause and
senescencephasesare all obtained from such batch operations. It is said that the biogas
installations developedin the then French Algeria by Isman and Ducellier were of this kind.
Later developmentsin many parts of the world have favored a systemwhere the digester
is given fresh material, usually every day, with automatic displacementof an equal amount
of sludge so that this mode of operation has beencalled continuous-fed operation. In such
a case,gasis evolvedin more or lessconstant volume;the slurry is always at active growth
phase except at or near th,eend of the digester where the sludge about to be discharged
should be at biopause or early senescencephase.The slurry therefore is fed at one end of
the digester, goesslowly through the length of the digester, so that by the time this slurry
reachesthe exit end, it is already at biopause or senescencephase.The retention time is the
interval between the feed-in and the discharge. This is the general idea regarding the
continuous-fed mode of operation. Any digester may be operated either batch or
continuous-fed,although there are additional requirements for the latter. For example,
theremust beprovisionso that the slurry fed in one day does not pass out as sludge the
following day.
Obviouslyit is an advantageto havea sufficientlylong digester. The problem of length
canbetackledin two ways.First, avoidthequestionand take anydigester(which should
havea length).Sincemost any digester cannot be stretched or contracted to the correct
lengthstipdatedby theory, the adjustment comesin the form of the daily feed, also called
34
load. A retention time which is basedon batch experiments has to be adopted. Let us say
the time adopted is 25 days. Therefore, for a lOOO-literdigester slurry, the daily load of
slurry would be 1000 liters/25 days or 40 liters/day. By putting in 40 liters of slurry every
day, it will take 25 days for that slurry to reachthe exit end.
Second, this time the question is approached head on. Consider again a lOOO-liter
digester slurry. A retention time basedon bateu experiments must be adopted, say 20 days
this time. Consider the entire digester as consisting of 2Q batches, one for each day. We
can conceive each daily batch to be in a container holding 1000/20 or 50 liters. Each
container must have practical dimensions, say 50 cm. deep, 50 cm. wide and and 20 cm.
“long”. Obviously the length of the desired digester would be 20 times the length, or
400 cm. The complete dimensions of the digester would then be 50 cm. deep, 50 cm.
wide and 400 cm. long. The depth and width may be char_gedto more convenient dimen-
sions but the length should remain the same for 1000 liters slurry and 20 days retention
time.
In the preceding discussion it is evident that the value of the retention time is crucial.
The retention time normally is selectedfrom any day number within the biopause. There is
no way to determine biopause in a continuous-fed digester. The value has to be obtained
from a batch operation.
It is noticed that the rate of gas production in a continuous-fed digester is generally
larger than in batch. The rate of gas production is somewhat higher at the earlier stagesof
fermentation at less dilution and with greater proportion of starter. In a continuous-fed
operation, the fermenting slurry itself acts asstarter; hence,not only is the relative amount
of starter very large, but this kind of starter is also at its most active growth phase.
Consider the case when the fermented or fermenting slurry is used as the diluting
material for preparing slurries. Since this acts also as starter, the advantage is obvious.
This is the situation when there is thorough stirring and it happens in small digesters of
cubical or near cubical shape.In digestersthat are long with small cross section, the daily
load mixesonly with the previous day’s load or the last two days’ load.
TABLE 3-2
Weights of Components in Experimental Slurries of Various
Manure-Water Ratios and Starter Percentages.(All Weights in Kg.)
.
20% starter 25% starter 33% starter
starter soln = 0.54 starter soln = 0.675 starter soln = 0.90
Manure/
H2O manure + H20 = 2.16 manure + H,O = 2.025 manure + Hz0 = 1.8
1:l Manure Water Manure Water Manure Water
1:1.5 1.08 1.08 1.013 1.013 0.90 .90
1:2 0.864 1.296 0.81 1.215 0.72 1.08
1:3 =
I
0.72 1.44 0.675 1.35 0.60 1.20
1:4 0.54 1.62 0.506 1.52 0.45 1.35
0.432 1.728 0.405 1.62 0.36 1.44
1
35
In batch operation, the starter is the smaller component and is addedto the slurry which
is a much larger amount. Thus, when the starter is 20%, the main body of slurry is 80%. In
a continuous-fed operation, the situation is the reverse;the slurry amounts to only the daily
load or only 1/3Othof the entire digester contents (when retention time is 30 days) but the
digester contents act as the starter. It is more realistic to consider, however, that the day’s
slurry input mixes with the previous two days’ slurry in the digester, in which case the
effective percentage of starter is about 33%. Such large proportion of starter promotes
high rates of biogasproduction, ashas beendiscussedearlier.
TABLE 3-3
Rate of BiogasProduction for Three Time Periodsand Three Percentagesof Starter.
(Rates in Liters Gas Per Day Per Kg. Volatile Solids.)
Starter
20%
Manure
Water
1:l
1:1.5
1:2
1:3
1:4
Average
Time period, days
O-20 O-30 O-60
9.4 9.6 5.5
10.6 9.9 5.5
10.9 7.8 4.3
12.8 9.4 5.3
15.5 12.2 6.8
11.8 9.8 5.5
Average 15.5 11.1 6.2
General average 13.6 10.5 5.8
36
Illustration 1-5: Pilot plant batch-fed digesters
Jlldation l-6: Pilot plant conthmm~ d&stem
37
Illustration 1-7: First experimental biogasplant at Maya Farms
llhtdon l-8: Labora-andmoftbtpRotmforbb researchat Maya Farms
38
Chapter IV
Raw Materials for BiogasProduction
The raw material for biogas production is organic matter. Marsh gas originates from the
decomposition of manure, leavesand similar material through the action of bacteria. All
organic matter contains carbon; methane and carbon dioxide are carbon compounds.
Thus the first requirement of a raw material for biogas production is that it must contain
carbon organically bound. This means that such materials as limestone, an inorganic
compound which contains about 12% carbon, will not do.
The conversion of organic matter to biogas is accomplished through the activities of
various kinds of bacteria as discussed in an earlier chapter. The element nitrogen, in
combined form, is needed by bacteria for their life processes and hence must also be
supplied. A deficiency of nitrogen tends to limit the growth and activities of the bacteria. A
large oversupply, however, has been found to be detrimental, causing the liberation of
ammonia. Casesof ammonia toxicity have beenmentioned in literature. What is important
is the quantity of nitrogen in relation to that of carbon. It is the consensus that to be
adequate, the nitrogen should be about equal to 1/3Oth the weight of the carbon, that is
C/N = 30 at most. Among biogas raw materials, the source of nitrogen is the protein
present; proteins in general contain 16% nitrogen. Table 4-1 givesthe nitrogen content of
some known proteins and the C/N values. When the C/N ratios are large, there is too
much carbon. The last column of Table 4-l givesthe value of N x 30 or the weight of C
neededto increasethe C/N ratio to 30.
TABLE 4-l
Elemental Composition of SomeProteins
1
Protein
Gelatin 49.4 6.8 18.0
Fibril . 52.7 6.8 17.0
Hemoglobin 52.7 7.3 17.7
Casein 53.0 7.0 15.7
Gliadin 52.7 6.9 17.7
E1aStiI-l 51.4 7.0 18.6
S
FM
1 5
C/N
I
Weight of C
to make C/N = 30
0.70 25.1 2.74
grams
540
1.10 22.5 3.10 510
0.45 19.5 3.00 531
0.80 22.7 3.38 471
1.03 21.7 3.00 531
0.88 22.1 2.76 558
An idea of the nitrogen content of animal manures, straw, and other possible biogas
producers is furnished by Table 4-2. The approximate valuesof C/N are also given.
The main source of carbon is organic matter, and the carbon compounds in organic
matter arecarbohydrates,fats andproteins.In Table4-3 are given the carbon content of
39
” > .I ,,
:_’ ‘-
‘_’
various materials including that of methane, carbon dioxide and butane for comparison.
The carbohydrates have a carbon content closeto 44%.
Lignin, which is mostly found in wood, has a higher C content but it has beenfound that
it is not easily acted on by bacteria. The fats are very rich in carbon but have not beenwell
studied as biogas material. The compounds that have received much study and have
shown to produce biogas are acetic acid, glycerol, ethyl alcohol, methyl alcohol and other
relatively simplecarbon compounds.
Returning to the C/N requirement, Table 4-l shows that for the protein known as
gelatin,N x 30 = 540; this meansthat a hundred grams of gelatin containing 18 grams N
(18% N) can be mixed with a carbohydrate like cellulose (4414%) to obtain a C/N value
of 30. The weight of the celluloseis calculated asfollows:
Weight of C from 100 gramsof gelatin: 49.4 grams
Weight of C from the cellulosematerial: 540 grams - 49.4 grams = 490.6 grams
490.6
Weight of cellulose(44.4% C) containing 490.6 grams of C: m= 1104 grams
.
Hence a mixture of 100 grams gelatin and 1104grams cellulose hasa C/N value of 30.
The situation is reversed in the case of rice straw; the C/N value is 51 and the
percentage of carbon and nitrogen are 35.7 and 0.796, respectively. More N should be
availableto reduce the C/N to 30. Since the required C/N ratio is 30 and for straw,
c/N=51;
(C/N) straw 51
(C/N)required = 30 Or l7
The nitrogen content of the straw must be increasedby a factor of 1.7: 1.7 x 0.7 or 1.19
grams. The C/N value in now 30. If ammonium sulfate, 20.2% N, is to be used as N
source,then
Weight of ammonium sulfatecontaining 1.19grams N
1.19
=-or 5.95 grams
0.202
To calculate how much N is neededby celluloseso that C/N = 30, Table 4-3 provides
data. Sincecellulosecontains 44.4% C, 100 grams cellulose need 1.48grams nitrogen. This
may be suppliedby urea which contains 46.6% N, 20% C.
c/JY =
Weight C 44.4 I- 0.2w
WeightN =
= 30, where W is weight of urea
0.466W
W = 3.22grams
Urine maybeusedasthesourceof urea It contains(on theaverage)2% urea(w/v) or
0.02 grams/ml., hencethe volume neededto supply 3.22 grams of urea is:
3*22Rrams= 161 d
0.02grams .
40
Other natural sources of N may be used. For example, hog dung which contains 2.8%
N:
1.50grams
0.028 grams = 53.6 grams hog dung
to supply 1.50grams N which areneededby the cellulose in the precedingcase.
The large amounts of cellulosic materials left over as residuesby crop plants have been
the center of interest in the past, regarding potential for biogas production. The situation
has changedand at present, interest and concern have moved to animal manure becauseof
a relatively new problem - pollution. Increased population together with migration to the
cities has resulted in the commercial-scale raising of food animals. Large numbers are
reared and fed in confmement; this has led to accumulation of manure which has become
a major pollutant. Fresh manure is difficult to dispose of; it is not easy to incinerate, not
only becauseof the amount of water it contains, but also becauseof the foul odor during
burning. Disposal by spreadingrequires large areasof land, Lately there have beenseveral
symposia in the United Statesand elsewhereon the subject of animal waste disposal. It is
now becomingmore and more apparent that oneof the successfuland practical methods is
methane fermentation. There have been found several concomitant benefits besides
pollution control which aredealt with in the succeedingchapter on sludge.
Hog Manure
Of the animal manures, hog dung probably presents a representative problem. Since it
is a singularly good material for biogas production, it will be discussedlengthily. Tabu-
lated in concise form (Table 4-5) are its characteristics. Part I of this table, which gives
the amount of dung in relation to hog weight is useful in making estimates of dung pro-
duction. Although the data are from American observations, nevertheless they can be
taken asa generalguide.
Part II, nutrient composition, shows results obtained from the Maya Farms laboratory
analysis of hog dung. Part III gives calculated values of certain data of importcuce in
biogas production. As has been pointed out earlier, carbon is the key element in biogas
formation. This carbon is a part of the volatile solids which is the non-ash constituent of
the dry matter of the dung. In current publications the yield of biogas is often quoted on
the basis of dry matter; more often, on the basis of volatile .solids. We prefer to use the
carbon content asbasis sincebiogas originates from the carbon in the raw material.
In Part III of Table 4-5 are given the calculated values of the expectedvolume of biogas
from hog dung basedon carbon content. Theseare 200 liters/ kg. fresh dung, 798 liters/kg.
dry matter, and 988.5 liters/kg. volatile solids. These volumes are at the temperature
range of 30*-34°C and at atmospheric pressure. These values set the upper limit of bio-
gasproduction from hog dung.
Hmaau Excreta as Biogas Raw Material
The questionhas often beenaskedas to the possibility of using human excretafor
biogasproduction.This matteris of interestto the personwho wantsto dabblein biogas
41
but hasneither animal dung nor crop residues;the only materials readily and constantly
availableare fm and urine. The questionwas answered in the afknative long ago.
Sewage treatment plants have incorporated the anaerobic digestion step, thereby
producingbiogas.The gasis usedin the treatment plant for generatingelectricity.
The main raw materials for biogas production nowadays are the various animal
manures, also called animal wastesor dung.There appears to be very little study on their
nature and composition,yet they present a pollution problem that can be expected to
continueto increasewith the expanding population. One would expect animal manure to
be a valuable material,considering that reportedly only 16% of the feedgiven to chicken is
recovered aspoultry meat and about 20% of the feed given to pigs is recovered as pork. A
lot of original animal feed is therefore present in the manure, and its utilization is of
importance. The nutrient composition of several animal manures is given in Table 4-2.
There is little information on what compounds are actually present. From available data
(Conception, 1936; Hobson and Shaw, 1967; and others), the main components are the
following:
1. Feed residues,undigested or only partly so, but not absorbed in the digestive tract of
the animal
2. Intestinal bacterial cells which may constitute as much as 40 percent of the total solids
ofthe manure
3. Intestinal secretions
4. Residuesof bacterial action.
Since manure is composed partly of feed that has undergone digestive processesin the
animal, it is a unique material that has already undergone partial proteolytic and amyloly-
tic action (in the case of ruminants, also cellulolytic). The bacteria not only cause fur-
ther chemical changes but also add their cell constituents. The amount of these bacterial
cells is considerable,being reported as 20 to 40% of the dry matter of manure. As is to be
expected,the composition of manure varies with the kind of animal, age, composition of
feed, etc. As far as methane production is concerned, the information needed is what
components are sourcesof gas.According to Maya Farms studies,which are discussedin
Chapter 5, the main sources are the carbohydrates. The relative weights of components
of hog manure are shown in Table 4-4.
Regarding the production of biogas from organic matter, it is to be noted that the gas
production curves exhibit a characteristic of not dying off abruptly. Gas is produced at a
steady rate from the start, up to a falling rate (about l/lOth of previous rate) but not to
zero rate. This may be interpreted as continuing gas production from more resistant
substrates, probably cellulose and lignin. The less resistant substrates are likely the
starches,sugarsand similar compounds. So far our substrate materials have not included
the fats and oils, hence no statement can be made about them. Peanut (or ground nut) oil
meal was reported as an excellentmethane-producing material in India.
It appears that in biogas formation from most organic matter like pig manure, the
process consists of two parts: the rapid conversion to gas of the more vulnerable
components, chiefly the carbohydrates, followed by a comparatively slower gas
42
production from the less fermentable materials at about one-tenth the former rate. The
rapid rate lasts anywhere between 15 to 25 days, depending on severalfactors; the slower
rate persists for some time, extending even beyond 60 days. An estimate on the relative
amounts of organic matter conversionto biogas will be shown in Chapter V.
TABLE 4-2
The Carbon/Nitrogen Ratio, Total Solids and Volatile
Solids of SomeBiogas-Producing Materials
Biogas-producing
materials
Total solids
Volatile solids
W)
(% of total) C/N
% of T.S.
s
A. Animal Dung
1. Hog
2. Carabao
3. cow
4. Chicken
5. Duck
6. Pugo
Household Wastes
25 80.7 38.3 2.8 J3.7
15 80.5 37.0 1.6 23.1
16 77 35.8 1.8 19.9
48 77.4 35.7 3.7 9.65
53 23.6 21.9 0.8 27.4
30 81.8 33.7 5.0 6.74
1. Night soil
2. Kitchen waste
C. Crop Residues(air-dry)
1. Corn stalk
2. Rice straw
3. Corn cobs
4. Peanuthulls
5. Cogon
6. Bagasse
15 90 47.7 7.1 6.72
‘.31 92 54.3 1.9 28.60
86 92 43.9 1.2 56.6
89 79 35.7 0.7 51.0
82 96 49.9 1.0 49.9
90 95.5 52.7 1.7 31.0
- 92.8 1.07 -
- 95.5 0.40 -
D. Others
1. Kangkong 4 84 33.5 4.3 7.8
2. Water lily 5 77 33.0 2.9 11.4
3. Grasstrimming 15 87 39.2 2.5 15.7
”
43
Material
Glucose 40 6.7 53.3
sucrose 42.1 6.4 51.5
Starch 44.4 6,2 49.4
Cellulose 44.4 6.2 49.4
Hemicellulose 45.4 6.1 48.5
Lignin 62.69 5-6.5 26-33.5
Fats 76.79 11-13 10-12
Coconut oil 73.3 11.6 15.0
Acetic acid 40.0 6.7 53.3
Methane 75.0 25.0 0.0
Carbon dioxide 27.3 0.0 72.7
Glycerol ‘e 39.1 8.7 52.2
Ethyl alcohol 52.2 13.0 34.8
Methyl alcohol 37.5 12.5 50.0
Butane (LPG) 82.8 17.2 0.0
Propane (LPG) 81.8 18.2 0.0
TABLE 4-3
Carbon Content of SelectedMaterials
Related to BiogasProduction
H
(%I
0
(%)
Weight of N to
make C/N = 30
(grams)
1.33L/
1.40
1.48
1.48
1.51
2.07-2.3
1.53-2.63
2.44
1.3.3
-
1.30
1.74
1.25
-
-I1
100gramsglucose umtain 40 grams C and need 1.33grams N so asto havea C/N value of 30.
TABLE 4-4
RelativeWeights(Grams)of Componentsof Hog Manure
Moisture = 75
Raw Dung = 100
Dry P
Ash = 4.825
Matter = 25
Volatile
solids =
20.175
Carbon = 9.575
Non-carbon = 10.60
Dry Matter = 100
(in manure)
Ash = 19.3
Volatile
c
Carbon = 38.3
Solids = 80.7
.
Non-carbon = 42.4
c
Carbon = 47.46
Volatile Solids = 108
Non-carbon = 52.54
.
Biogas
Biogas
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Biogas

  • 1. A project of Volunteers in Asia 3IdllThePhilipPine Exper;-e?',.:: bJ. * 2; D. Maramba, Sr. 7, .*, J.,,-2d by: %erty Flour Mills, Inc. claya Farms Division Liberty Building, Pasay Rd. Legaspi Village, Makati Metro Manila, The Philippines Available from: Liberty Flour Mills, Inc. Maya Farms Division Liberty Building, Pasay Rd. Legaspi Village, Makati Metro Manila, The Philippines Reproduced by permission of Liberty Flour Mills, Inc. Reproduction of this microfiche document in any form is subject to the same restrictions as those of the original document.
  • 2.
  • 3.
  • 5.
  • 6. BIOGAS AND WASTE RECYCLING THE PHILIPPINE EXPERIENCE FelixDI Maramba,Sr. B.S.,M.S.,D.Sc.(honor/s emma) ContributingAuthors EnricoD. Obias,B.S.Ch.E. JulianBanzon,B.S.Chem.,Ph.D. CalixtoTaganas,B.S.C.E. RuthD. Alumbro,B.S.,M.S. AlejandroA. Judan,Jr.,B.S.B.A.,CP.A. Maya FarmsDivision Liberty Flour Mills,Inc. Metro Manila,Philippines . .. ill
  • 7. _- Copyright 19% bY Felix D. Maramba, Sr. All rights reserved.No part of this publication may be reproduced or transmitted in any form or by any means,electronicor mechanical, including photocopy, recording or any information storageand retrieval system,without the written permissionof the senior author. Printed by &I RRGAt PRINTING COMPA,NY iv
  • 8. In memory of two Filipino scientist-technologists Manuel L. Roxas and BienvenidoMa. Gonzales Who laid the foundation for Philippine agro-industrial development V
  • 9. PREFACE When Liberty Flour Mills, Inc., decided to establishMaya Farms, an h&grated hve- stock farm, meat processing and canning operation in the Antipolo Hills of Rizal pro- vince, Philippines, pollution control was an integral part of the planning. After the NW- ious alternative methods were studied, anaerobic fermentation was chosen and adopted. The choice was made on the basisof what I had previously seenof the biogas plants in India and Taiwan. The biogas practitioners in India were enthusiastic about the biogas fuel for cooking and lighting, and in Taiwan, about the savings in their fertilizer bills. However, what particularly impressedme was the absenceof foul odor and flies. It was evident that the 4ution of the problem involved expertise in chemistry, microbiology, engineering,etc. II. ,Jastherefore decidedthat a group of specialistswould work together in a crashdevelopmentprogram. We read whatever literature we could gather on biogas and started our experiments. Later, I made another trip, this time to Europe, the United States,Australia and India, to learn more, principally on the various designsand methods of operation. Chapter VII showsthe most common designs.We tried a number of biogas plants which we thought would be applicable,properly modified to fit local conditions, becausewe found no single designthat would meet varied requirements.Chapter VI is devotedto the discussionof suitabledesignsfor different conditions. The biogas plants which we established,successfullycontrolled the air pollution from the tons of manure produced daily by 10,000 pigs. But though *+ biogas plants greatly reduced the pollutional characteristics of the manure, the voluminous sludge still posed the problem of water pollution. Becauseit contained traces of toxic substances,it could not be applied as fertilizer in large doses.Intensive and expensiveefforts of Maya Farms to solve the problem resulted in the development of the sludge-conditioning plant dis- cussedin Chapter VIII. Sludgeconditioning not only eliminated the toxicity to fish and crops but it also im- proved the fertilizer performance far beyond what the chemical analysis would indicate. An unexpectedbonus of great significance was our discovery that the solids recovered from the sludge could be processedinto an excellent animal feed material. We found later that the dri& sludgewas rich in vitamin B12, a growth-promoting factor in animal feeds. Results of f-g trials would also indicate the presenceof other unidentified growth factors (UGF). Sludge conditioning may well be Maya Farms’ most significant contribution to bio- gas technology. The value of the recoverable feed materials alone, without considering the biogas, biofertilizer, and pollution control, makesthe whole system a profitable ven- ture. The utilization of the sludge as fertilizer and as a source of feed materials is dis- cussedin Chapters XIII and XIV. Chapter XV covers the function of the biogas works * for pollution control. 0 vii
  • 10. Maya Farms has adopted the term “biogas works” to distinguish a biogas opera- Lionwith sludgeconditioning from a biogasplant operation.The biogasworks, or opera- ting combiiation of the biogasplant and sludge-conditioningplant, is discussedin Chap- ter IX. After the oil embargoin 1973,we startedexperimentingon the industrial usesof bio- gas. First it was used as a substitutefor LPG (liquefied petroleum gas). We found that the biogasmay be used in any appliancesintended for LPG, with minor adjustments, The EngineeringDivision of Liberty Flour Mills, Inc. started manufacturing appliances specifically intended to use biogas: gas stoves,refrigerators, lechon oven, etc. It made adjustmentson mantle lamps and water heatersto usebiogas.It convertedcharcoal flat irons to use biogas. Biogas was used successfullyto run internal combustion engines to pump water from deepwells, to operatethe feed-mixingplant, and to operatean elec- tric generatorthat runs the freezersat night. We also usedthe biogasto fire a boiler, but wedid not haveenoughgasto do all theseatthe sametime. After finding so many usesof biogas,our next aim was to find ways to increasethe daily production and to reduce the costs of construction and operation. The hundreds of trials on laboratory scaleand pilot scalebiogasplants paid off handsomely.We were able to increasethe production capacity of the biogas plant by 70-80% with more effl- cient stirrers, and by reducing the retention time of the waste slurry inside the digester from SO-60days to 23-30 days. By improving the quality of our starter, we were also able to produceflammablebiogas the day after charging the digesters,where it used to take4 to 6 daysbeforegoodgaswasobtained. Reductionof the retentiontime to one-halfincreasedthe biogasproduction and at the sametime doubledthe manure-processingcapacity of the biogas plants. In other words, the capital outlay requiredto construct biogasplants to disposeof the sameamount of manurewas reducedto one-half.To find other ways of cost reduction, we tried various designsof the biogasplant. We built modified versionsof the India single-walledvertical digesterwith floating gasholder,the Taiwan double-walledhorizontal digesterwith float- ing gasholder,the China cylindrical digesterwith fured-domegasholder.We built conti- nuous-fedand batch-fed,integratedtype and split type biogasplants. We built digesters with singlechamber and double chamber,in double rows, in triple rows and in clusters. We built them above ground and underground.We endedup with our own designsof both batch-fedandcontinuous-feddigesters. Becauseof the great potential of biogas operations in waste recycling, our research and developmentwork spilled over into a recycling system.We not only recycled the manure, but also converted the bones, blood and meat scrap in the meat processing plant into feed materials.Then we tried mixir g the corn stover and rice straw with the manureslurry. Gas production was improved but the stover and straw required drying, crushing and chopping which consumedtoo much energy. Instead of giving them up entirely, we looked for a better way of usingthem. We fed them to ruminants and got the manureof the ruminants for the biogasplant. Thus the stoversand strawstogether with the weedsstill helpedproduce meat before reaching the biogas plant. The inedible por- tion of thecrop residueswerecompostedto serveassoil conditioner. To fmd other ways of recycling our excessliquid sludge,we also experimentedon producingchlorella asa protein sourcefor the hog feeds,but the high costsof harvesting ... vu1
  • 11. and drying chlorella made its production cost much higher than the cost of other avail- ableprotein sourceslike soybeanoil meal and fishmeal.Instead,we decidedto grow the algaein fishpondssothat the fishcanfeedon themdirectly. Seeingall the benefitswe weregetting out of the recycling operations,it did nclt t+e long to realize the socio-economicimpact if such recycling systemscould be praet.icG throughout the country. Part IV discussesthis matter and presentspossibleapplications of a recycling systemof farming, introducesthe variedroles that biogascan play in rural developmentandshowsthebeginningof biogaspracticein the Philippines. This book is a summary of our experiences- of our attemptsto solve one problem, that of pollution, and of how the solution evolvedinto a sort of wonder pill for the mo- dem world’s major headaches:pollution, the energy crisis, food shortage and under- employmentof the farmers.Aside from solvingour pollution problem,the biogasworks turnedout to be a rich sourceof a fuel gas,organicfertilizer and feedmaterials.The so- lution did not comeeasily.Therewere failures and near misses,financial gamblestaken and sometimeslost, but in the process,we havelearneda lot, and are still learning.We feelweshouldsharethis stockof knowledgewith others. Late in 1976, President Ferdinand E. Marcos directed the Energy Development Board (now Ministry of Energy) to embark on a crash program to use biogas as a substitutefuel. In this connection,he instructed the Director of Animal Industry to es- tablish model biogasworks in their stock farms: at least one in every region within six months,one in eachprovince within one year, then in every town whereit has a breed- ing station. The Maya Farms was chargedwith the task of training governmenttechni- cianswho would take care of constructingand operatingbiogasworks and propagating theiruse.We arehappyfor havingbeengiventhis opportunity. Felix D. Maramba,Sr.
  • 12. ACKNOWLEDGMENT The help of the following technical men, who are all involved in the researchand de- velopmentwork on biogasat Maya Farms,is gratefully acknowledged: Domingo Bautista,B.S.M.E. RegisteredMechanical Engineer Dr. Patrocinio Santos,Ph.D. Formerly Microbiologist of the National Institute of Science& Technology Dr. Leopold0Castillo, Ph.D. Animal Nutritionist of theUP. College of Agriculture Dr. Mario Tongson,D.V.M. Chief Parasitologistof theU. P. College of Veterinary Medicine FidelJunatas,B.S.&E. RegisteredSanitary Engineer PacificoPangilinan,B.S.E.E. RegisteredElectrical Engineer Hector Gatchalian, B.S.Chem. RegisteredChemist RomeoA. Icasas,B.S.A. Animal Husbandman Dr. Leopold0Capistrano,D.V.M. Veterinarian Alfred0 Hemaez,B.S.A. Formerly Agronomist of theBureauof Plant Industry FelipeAgdeppa,B.S.H. Soil Technologistof theBureauof Soils Agustin Mangila, B.S.A.,LLB. Agricultural Economist RamonDizon, B.S.M.E. RegisteredMechanical Engineer Home AppliancesManufacturer EstrellitaS.Tala, B.S.Ch. E. ChemicalEngineer Meynardo Maghirang, B.S.Ch. E. ChemicalEngineer RositaImmaculata, B.S.Chem. Chemist ZenaidaS.Hemandez,B.S.Med. Tech. Laboratory Technician More thanksare due : to the difYerent embassiesin the Philippines for their help in gathering information on the researchand application of biogas in thair respectivecountries; : to the Philippine embassiesabroad for furnishing us with biogas literature; : to the Ministry of Energy and the National ScienceDevelop- mentBoard for their encouragement; : to the National Pollution Control Commission for their valuable suggestions; : to the National ResearchCouncil of the Philippines for making possibletlle publication of this book. X
  • 13. CONTENTS Preface Acknowledgment Part1 - ScientificAspects Chapter I II III IV V Part II - BiogasTechnology Chapter VI VII VIII IX X XI Nature andHistory of Biogas BiochemistryandMicrobiology Laboratory andPilot Plant Experiments RawMaterials for BiogasProduction TheSludge Fundamentalsof BiogasPlant Design BiogasPlant DesignsAround theWorld Sludge-ConditioningPlant Designs BiogasWorks Designs Planningand Establishingthe BiogasWorks OperatingBiogasWorks PartIII - Utilization andEconomics Chapter XII BiogasasFuel XIII SludgeasFertilizer XIV Sludgefor FeedandOther Uses xv BiogasWorks for pollution Control XVI TheEconomicsof BiogasWorks PartW - WasteRecycling‘I’hroqh the BiogasWorks Chapter XVII RecyclingSystemof Farming XVIII Rural Developmentthrough WasteRecycling XIX BiogasWorks in Practice Socio-EconomicImpact of BiogasWorks 143 145 153 159 165 171 181 185 193 201 213 Glossaryof Terms 218 Bibliography 223 Ill&X 221 Vii X 3 5 11 21 39 47 61 63 73 87 101 l 115 131 xi
  • 14. LIST OP TABLES 3-1 Relativevolumeof digesterspaceto containonekilogramof hog manurein variousmanure-waterratios s 3-2 Weight of componentsin experimentalslurries of various manure-water ratiosandstarterpercentages 3-3 Rateof biogasproduction 4-1 Elementalcompositionof someproteins 4-2 C/N ratio, total solidsand volatile solidsof somebiogas-producingmate- ri3lS 4-3 Carboncontentof selectedmaterialsrelatedto biogasproduction 4-4 Relativeweightsof componentsof hogmanure 4-5 Characteristicsof hogmanure 5-1 Compositionof sludgein relationto daysof fermentation 5-2 Mineralcompositionof a sampleof total sludge 5-3 Mineral compositionof the solid and the liquid portions of a sampleof sludge 5-4 Percentagesof constituentsremainingin sludgeand percentageconverted to biogas 5-5 Theoreticalmaximumvolume of biogasproduciblefrom one kilogram of material 5-6 Conversionpercentageof hogmanureto biogas 10-l Approximatedaily manureavailablefrom di&rent animals and the daily biogasproduction 10-2 Biogasconsumption 10-3 Kind of manurerequirement,gasproductionandcostof biogasplant f2-I Compositionof biogasandthecommonfuelgases Page 31 35 36 39 43 44 44 45 48 48 48 54 55, 57 116 117 118 146
  • 15. se j ~$3,. s 12-2 Heatingvalueof biogasandthecommonfuelgases 12-3 Heatingvalueof otherenergysources 13-1 Plot fertilize!experimentonrice 15-l Quality standardsfor differentclassificationsof water 15-2 Characteristicsof wastewaterfrom different sampling stations at Maya Farms 15-3 Qualitativedescriptionof odors 15-4 Threshold odor numbersof wastewaterat different sampling stations at Maya Farms 16-1 Comparativecostsof constructionof smallbiogasplants 146 147 155 169 169 170 170 173 ... Xl11
  • 16. 4 : 3-l 3-2 3-3 3-4 3-5 3-6 3-7 3-8 Effect of ageof starter on gasproduction 3-9 Ratio of volume of gasper day to volumeof digesterslurry LIST OF FIGURES Page Laboratoryset-upfor study of biological production of methane 22 Typicalbiogasproduction curve 24 Gas production curvesfor various manure-waterratios 26 Gas production curves on equal slurry volume and equal manure weight basis 27 Gasproduction curvesfor storedpig manure 29 Gasproduction curvesfor varying starterpercentage 29 Relation of percentageof starter and number of days to produce 50 liters of biogas 29 29 32 3-10 Rates of biogas production during active growth and senescencein relation to dungconcentration 3-11 Gas production curvesfrom chicken manureslurries 3-12 Gas production curvesfor corn stalk andrice straw 5-l Changesin percentagecomposition of sludge during methane fermentation of hogdung 5-2 Changes in weight of components of siudge during methane fermentation of hogdung 5-3 Percent reduction in weight of protein, fat, total carbohydrates, volatile solidsandtotal weighi 5-4 Percentdistribution of total weight loss 6-l Integratedbiogasplantflowsheet 32 32 32 53 53 56 56 70 706-2 Splitcontinuous-fti biogasplant xiv
  • 17. 7-I 7-2 7-3 7-4 7-5 7-6 7-7 7-a 7-9 7-10 7-11 7-12 7-13 7-14 7-15 7-16 7-17 7-18 7-19 7-20 7-21 7-22 biogas1plant 6-4 Night soilbiogasplant Gobar gasplant, with overflowoutlet (Patel) Gobar gasplant, with pipeoutlet Manuregasplant with latrine (Gotaas) BelurMath gobargasplant Taiwansinglestagebiogasplant Taiwan 2-stagemethanegenerator Chinabiogasplant Anaerobicdigestionof pig waste Darmstadtsystem Schmidt-Eggersglusssystem Webersystem,cow dungtype Bihugas-Anlage(Poetsch) Ducellier-Ismansystem Gartner-Ikonoff system Drum digesterfor fibrousmaterials(Buswell-Boruff) Gasgeneratingplant for vegetablewastes(Burke-Jacobs) Organicdigester(Fry) Methanerecoverydigester(Chan) Sanamatictank (Co&hard) Kenyabatchdigester Continuousorganicwastedigester(Araneta) Garbagefermentationtank (Valderia) 1 ’ : xv 71 71 78 I& 33 78 79 79 79 79 80 80 80 80 81 81 81 81 82 82 82 82 83 83
  • 18. 7-25 ‘7-26 7-27 7-28 7-29 7-30 7-31 l-32 8-l 8-2 8-3 9-l 9-2 9-3 9-4 9-5 9-6 9-l 9-8 9-9 Methanegasproducingdevice(C&-Velasquez) Night soil digester(Maya Farms- Bautista) Horizontal continuous-fedbiogasplant(Maya Farms-Obias) Continuous-feddigesterfor livestockfarms(Maya Farms-Taganas) Batch-feddigestersfor agro-industrialoperations(Maya Farms-Maramba) Floatingdomegasholderfor split typebiogasplants Continuous-feddigesterfor slaughterhouses(Maramba-Taganas) Vertical continuous-fedbiogasplant(Maya Farms-India) Fixeddomecontinuous-fedbiogasplant(Maya Farms-China) Double-walledcontinuous-fedbiogasplant (Maya Farms-Taiwan) Singlepondsludge-conditioningplant Doublelagoonsludge-conditioningplant Multi-lagoon sludge-conditioningplant Family farm biogasworks flowsheet Crop-livestockbiogasworks flowsheet Agro-pulp biogasworks flowsheet Livestockbiogasworks flowsheet Feedlotbiogasworks flowsheet Integratedmeat-processingbiogasworks flowsheet Agro-industrial biogasworks flowsheet Slaughterhousebiogasworks flowsheet Cooperativebiogasworks flowsheet 9-10 Night soil biogasworks flowsheet 1l- 1 Floor plan for compostbunk xvi 83 83 84 84 84 84 85 85 85 85 98 99 100 106 107 108 109 110 111 112 113 114 114 139
  • 19. 17-1Recyclingchart, Maya Farms 19-i Sta Barbarabiogaspiant 19-2 BAI biogasplant 19-3 PAC biogasplant 19-4 UPCA biogasplant 183 206 206 206 206 xvii
  • 20. l-l l-2 l-3 l-4 l-5 l-6 l-7 l-8 1-9 2-l 2-2 2-3 2-4 2-5 2-6 2-7 2-8 2-9 2-10 2-11 2-12 2-13 LIST OF ILLUSTRATIONS Microbiology laboratory at Maya Farms Microbiological assayof vitamin B12 Pollutioncontrol laboratory Experimental laboratory digesters at Maya Farms Pilot piaint batch-fed digesters Pilot plant continuous-fed digesters First experimental biogas plant Laboratories and one of the pilot plants for biogas research at Maya Farms Animal manure and crop residues are the biggest potential sources of biogas Eiogas works at Maya Farms Industrial scale biogas plant Gasholders for the fourth biogas plant unit under construction at Maya Farms Settling basins Sludge-conditioning canals with overflow dams Waterwheelaerator Solid sludgedrier . Detoxifier Incinerator Compostbunk Biogasplant Sludge-conditioningplant Biogasworks with a windmill ... XVlll 2 19 19 22 37 31 38 38 46 60 72 86 95 95 95 96 96 97 97 105 105 140
  • 21. @ST, - 2>:: (.,‘ b ” ” 3-l ‘_ 3-2 3-3 3-4 3-5 3-6 3-7 3-8 3-9 4-l 4-2 4-3 4-4 4-5 4-6 4-7 4-8 4-9 4-10 4-11 4-12 4-13 4-14 4-15 Biogas-powereddeepwellpump Biogas-poweredfeedmill Biogas-heateddrying room Pigbrooderandpoultry brooderconverted to use biogas Cookingwith biogasat Maya Farms canteen Lechon roasters Crop drier Fertilizer test plots Crop field and fishponds Waste recycling at Maya Farms Biofertilized vegetableson trellis Harvesting tilapia at Maya Farms Fishponds and crop fields Biogas-powered 60 kva electric generator at Maya Farms IPOPI charcoal-fed trucks Windmill Solar heater Rice hull firing chamber Biogasplant in Calasiao,Pangasinan Sta.Barbarabiogasworks Biogasplant at BAI breedingstation Night soilbiogasplantat Liberty FoundationDormitory India model Chinamodel 142 150 151 151 152 153 154 158 158 180 191 191 192 198 199 199 199 200 209 210 210 211 211 212 xix
  • 22. 4-17 Maya Farmhousemodel 4-18 Biogasfor householdappliances 4-19 Ducksfeting on scum 212 2i2 217 217 xx
  • 23. P4RT I SCIENTIF‘IC ASPECTS Chapter I Nature and History of Biogas II Biochemistry and Microbiology III Laboratory and Pilot Plant Experimerits IV Raw Materials V Sludge
  • 24. Illustration I- 1: Microbiology laboratory.
  • 25. PART I SCIENTIFIC ASPECTS The initial difliculty to becontendedwith whena piggerywassetup at Maya Farms in 1972 was ecologicalin nature. The hog farm polluted the drainagecreek and diffused odors. A good number of possiblesolutions were considered.One was to dry the pig manureand sellit as fertilizer. However,therewould be high energyrequirementsduring the long rainy months,to say nothing of the unpleasantsteamingodors arisingfrom the forceddrying. Another methodproposedwasstandardsewagetreatment,but calculations showedthat the cost would be high. Still another method consideredwas anaerobic fermentation,but there was no availablerecordedexperienceto go by. The potential to produce methanegas was presentand this at a time when the supply of energy was becomingevenmorecritical thanthat of food. Literatureon methanewasamplebut not on methanefermentation.Hugequantititesof methanehad by now beenalreadymined in many regionsof the world. This natural gas occurs in nature, and is often associatedwith petroleum oil. In contrast to thesehuge natural deposits,decaying straw, leaves and other organic matter buried in muddy stagnantwaters,producethe samemethanegasby action of microorganisms;hencethe namesswampgas,marshgas,muck gas.In someswamps,the gasignites,very likely due to another naturally produced gas, phosphine,which is self-igniting when it comes in contactwith air. (Suchpergolicsubstanceskeepmodernjet enginesalwaysaflame.)These eeriebluishdancingflamesshimmeringin swampswerecalledignisfatuus by theRomans, thedeceivinglight, for a personwho is fascinatedby the flameis lured farther andgetslost in the tracklessswamps.Eventoday, in Englishdictionariesand encyclopedias,the word or term “will-o-wisp” remains.In still anotherform, methaneappearsasthe eternalflame burningin shrinesof diversecults and beliefs.Methanegasis not the only legacyhanded down to usby naturethrough eonsof time duringwhich organicmatter wasconvertedto productswearenow dependenton for energy.The presentreservesof coal, petroleumoil andnaturalgasmay betracedbackto the plantsandanimalsthat existedin agespast.The remainsof theseprehistoric living organismswere convertedby high temperature,high pressureand microorganismsoverthe long geologicalperiodsto our present-daysources of energy. It is now almost certain that the methanein natural gas was formed throu.ghthe bacterialdecompositionof organicmatter, vegetationand otherorganismsthat lived eons ago. At the presenttime this decomposingprocessis still going on. A few years ago, a garbagedump near the Rizal Coliseumin the City of Manila emitted an inflammable gasduring attemptsto sink awellfor water. In the Philippines,there hasbeenas in many countries,sporadicinterestin biogas.In 1965 M. Felizardo went to Europe on an official mission for the Philippine Coconut Administration; he returned with an unusually enthusiasticreport on the experienceof Germanyon biogas.Work on biogasstartedsoonafter: Eusebio,Alicbusan,the groupsat 3
  • 26. Pampanga Agricultural School, the Bureau of Animal Industry, the Economic DevelopmentFoundation, and Maya Farms. Patentsbeganto appear: Valdeda, Cadiz, Velasquez,Araneta,etc. It is to be noted that during the oil embargo in 1973, interest shifted to energy production, and the pollution control aspectwas kept in the background.But eventually the animal raisers,especiallyof hogs and poultry, found themselvesstaring into the real- ities of the pollution evil, and anaerobicfermentationagainregainedattention asa means of control.
  • 27. Chapter I Nature and History of Biop MethmiE:is the simplest member of a large family of chemical compounds called hydrocarbons. They contain only the elementscarbon and hydrogen. The first six membersof thisfamily are: Methane CH4 Butane C4H10 Ethane C2H6 Pentane C5H12 Propane C,H, Hexane CeH 14 Methaneis a gasat our ambienttemperatureand pressure.It is a colorless,odorlessgas about half asheavyas air. It is characterizedby a critical temperatureof - 82OCand a critical pressureof 45.8 atmospheres.In other words, methane liquefies only if the temperatureis at or lower than - 82OCandrequiresat leasta compressionpressureof 45.8 atmospheres.By contrast, butane(lighter fluid) can be obtained as a liquid at ambient temperaturesandat pressuresslightly higherthan atmospheric.Liquefiedpetroleumgasor LPG is butane or propane or a mixture of both. Butane and propane have critical temperatureshigh enoughso they can exist as liquid at ambienttemperatures.The next higherhydrocarbonis pentane;it is a liquid anda componentof gasoline- from methane to ethaneto propaneto butaneand to pentane,the critical temperaturesincreaseand the gasesbecomeeasierto liquefy. It canbeseennow why compressionalonewill not liquefy methane.However,methane can becompressedto a gssvolumeso smallasto be comparableto a liquefiedgasas far asvolumereductionis concerned,but certainproblemsarise: 1)the tank containermust be extra strong, thick, heavy and of specialconstruction; 2) a costly high compressor systemis necessary;3) expensivegaspressurereductiondevicesareneededfor everytank whenthecompressedgasis used. There8fe many advantagesto be gainedin transporting methaneas a liquid evenwith the smm requirementof maintaininga temperatureof at most - 82OCand a pressureof at least 45.8 atmospheresthroughout the time of transport and storage.The volume of the gqu& however,is approximatelyonly l/600& that of the gas at 25OCand this is an advantagein storage.The problemsmet in handlinggasesat suchcryogenictemperatures havebeenquite satisfactorily solvedin the developmentof spacerockets.But would it be economical to apply this knowledge to methane? Let us quote from a well-known magaxine: Thii schemewas the subjectof successfulexperimentsin 1959when the converted Me&me P&NW ma& seventrips from Louisiana to England.Each cargo of 2000 coldtonswarmedup into 100million cubicfeetfor London’sgassystem.Franceand Englandarenow buildingmethanetankers. Methane burns in air with a pale, faintly luminous, very hot flame. The heat of combustionis 978 BTU per cu. ft. Its auto ignition temperatureis 650°C. The explosive 5
  • 28. those over 5.53% methaneand those lower than 14%. Methane, unlike carbon dioxide, is very sparingly solublein water. Hydrogen constitutes 25% of methanein contrastto 16.7%in pentaneor 11.11%in water; evenammoniacontainsonly 17.6%hydrogen.By making methanereact with steamof high temperatures,the hydrogen output is doubled:CH4 + 2H20 + CO2 + 4H 2. Carbon black,fluffy material of colloi- dal finenessand usedto make rubber tough and resistant to wear, is obtained by crack- ing methane.Other industrially important products synthesizedfrom methaneare methyl chloride, chloroform, carbon tetrachloride, methyl alcohol, formaldehyde, nitromethane and others. As mentioned earlier, one large use of methane is to supply hydrogen for fertilizer (ammonia)manufacture. Methane is nowadays industrially produced by destructive distillation of bituminous coal(coal gasproduction) andby coal carbonization. From recordsthat are at presentavailable,it is apparentthat this gasnow calledbiogas has beenobservedand studied since ancient times. After the time of the Romans, the Greeks and the Chinese,and much later with the ushering in of the scientific era, there appearsto havebeena continuing interest on the subject leadingto the presentdegreeof utilization of thisgas. History of Biogas One of the earliestto mention biogas was Van Helmont in 1630,in a communication aboutan inflammablegasemanatingfrom decayingorganic matter.Van Helmont wasone of the early observersand interpreters of natural phenomenawho nowadays would be called“sc&nists”. In 1667a man by the nameof Shirley describedthis gas more precise- 1Y;he is now generally consideredas its discoverer (Sathianathan, 1975). An Italian, Alessandro Volta, (from whom the electrical unit, volt, was denved) wrote a letter on Nol,timber 14,1776,about a combustiblegasevolvedwhenthe bottom sediments of ponds nearthe town of Como, northern Italy, and in Lake Verbano, werestirred. He found that the gasexplodedwhen mixed with air and ignited; he even determined the proportions of gasto air that gavethe loudestexplosion. In I870 JosephPriestley, a namewell-known in the history of chemistry, reported an “air” (that is, a gas) that was produced by the decay of substanceswhen submerged in water. The first allusionto animal manurecomesfrom Humphrey Davy, who reportedearly in the nineteenth century the presenceof this combustible gas in fermenting farmyard manure. Davy is known for the invention of the miner’s safety lamp. Even today the principle involved in that lamp may be usedas the simple methodto avoid explosionsin circumstanceswherea gas(like biogas)is likely to beignited. It was in 1804 when John Dalton establishedthe chemical constitution of methane. Dalton is consideredthe father of modem atomic theory. It is to be noted that this gas methane attractedthe attention of the famousscientistsof that day. Not only chemistslike John Dalton, Humphrey Davy, and JosephPriestley,but also thosewhom we now clas- sify as physicists like Alessandro Volta, and William Henry becameinterested in the muck gas. It was William Henry who deducedthe probable identity of the then synthe- tic illuminating gasasmethane.This wasin 1806. 6
  • 29. It appearsthat by that time, the physical scientists (physicists and chemists) had advancedknowledgeabout biogas,as far as their disciplinesallowed, and from there the microbiologists took over. Louis Pasteur himself devoted some time to look into the processbut it wasone of his studentsby the nameof Bechampwho in 1868,tried to show that microorganismswere involved in the production of methanefrom organic matter. It appearsthat Bechampwas not able to give a very convincing proof for it and credit is usually givento Tappeinerwho worked during the years 1882to 1884.Another studentof Pasteur,Gayon, produced so much gasthat Pasteurentertainedthe idea of usingthe gas for illumination and heating. With the chemicalconstitution furedby John Dalton, the microbiological nature of the prxess demonstratedby Bechampand Tappeiner,and the starting sourcematerial shown to beorganicmatter by a numberof observersit would do well to considerat this point the more applieddevelopment. It is reportedin literature that as early as 1896,gas from sewagewas already usedfor lighting a streetin Exeter, England. That a combustible and potentially useful gas could be obtainedfrom human feces,must havebeenamply demonstratedin India, for in 1900 a methane(biogas)generatingplant from humanwasteswasconstructedin a leperasylum in Matunga, India (Sathianathan, 1975). This was the HomelessLepers’ Asylum, now known as the Acworth Leprosy Hospital in Wadals, India. This is also mentioned by Boruff and Bushwell in 1930.It is likely that the asylum was pesteredby the obnoxious odor of their wastes,resultingin the confinementof this pollutant and later the discovery of a practicalway to usetheevolvedgas. The production of biogasin quantity from cellulosicmaterialscameevenlater than that from human wastes.It appearsthat in 1914 the Dutch tried to produce biogasfrom the wasteof straw board manufacture.This wasin Indonesiawhenit was still the Dutch East Indies. After World War I, in 1918,the British becameinterestedin the production of methane from farm wastes.This seemsnot to haveprosperedfor a numberof reasonsthat will be discussedIater. In 1930 Boruff and Bushwell from Illinois in the United States published articles about the production of methanefrom farm residueslike cornstalk. Up to 1952Bushwell was still publishing articles on the subject.Jacobs and also Levine (well-known for his bacteriologicalendoagar medium)both from Iowa State, alsoin the United States,were much concernedabout the generation of this gaseousfuel in relation to the enormous amountsof availablefarm cellulosicwastes. In theyearsaround 1940,many municipal sewagetreatmentplants in the United States and elsewherewere already employing anaerobic“digestion” as part of the treatment of municipal waste,and thereby generatingmethanewhich was usedto generateelectricity for the plant. This indicated that for pollution control, the anaerobicdigestionprocessis proveneffective,with additionalbenefitsin theform of a supplyof a usefulgas. The French in North Africa, betweenthe years 1940-S1, are reported to have made extensiveefforts to developso-calledmethanedigesters.Thereis ample literature on their work in Frenchjournals. The designsand prototypes were developedby G. Ducellier and M. Ismanin thethen FrenchNorth Africa asearly as 1937. 7
  • 30. Work on biogasdevelopmentin Germany is well summarizedby Tietjen (1975) from about 1951. There were three groups that developedprocedures: a) Strell, Goetz and Liebmann at Munich, b) Reinhold and Noack at Darmstadt, c) Schmidt and Eggersgluss at Allerhop. Later,otherprocedureswereworkedout: the Honhenheim,the SystemBerlin and the Poe&h. There was parallel work in East Germany. In general,the conclusion was: “the aspect of energy balance was judged as unfavorable because of climatic conditions...” Gas from sewagewas another matter since proper sewagetreatment and disposalcould not be evaded.Tietjen reports that in 1951,48 sewagetreatment plants in West Germany provided more than 16 million cu. m. of sewagegas,3.4% of which was utilized for powerproduction, 16.7%for digesterheating, 28.5% was deliveredto the city gassupplysystemand 51.4%wasusedasmotor fuel for vehicles. At the latter part of World War II; Germany and the Nazi-occupied areas found themselvesin a deep crisis with respect to fuel for vehicles.Not only the enginesfor transport of people,food andmerchandisebut alsothe farm machinery,like tractors, were sorely in need. Methane (actually biogas) was generated from manure using several hurriedly developeddigesters.The gas, which could not be liquefied under pra&d conditions, was compressedat 3,000 psi and chargedinto pressuresteel“bottles”. Such bottleswerefilled with gastheequivalent of 10gallonsof gasolineand thus servedasfuel during the crisis. This experienceof Germany showsthat it is possibleto run the farms through the energy coming from farm waste. It may be cheaperto use petroleum fuel nowadays but not for long becauseof the present worsening of the energy crisis. A handicapof thecolder climatesis the requirementof relatively high temperature,certainly higherthan 26OCandpreferably30°C to 35°Cfor thebiogasproduction. After World War II, there was extensivedevelopmenton biogas generationin many countries: South Africa, Rhodesia, Kenya, Uganda, Russia, Australia, Italy, Korea, Taiwan, Japan,Israel, United States,India, andthePhilippines. In 1965 Chung PO of Taiwan published a pamphlet on two designs of family-size digestersandtheusenf the sludgefor fertilizer andchlorella culture.(The so-calledTaiwan designappearsin anotherchapter.) A greatdealof significant work on biogashasbeendonein India, but this work reached the outsideworld only in morerecenttimeswhenalmost every country becameinterested in the subject.An authoritative reviewof developmentsin India is given by BashbaiPate1 in a paperpresentedin the ESCAP-NIST BiogasUtilization Workshop in 1975.Research on Biogas(Gobar gas)was undertakenin India since 1939but it was not until 1951 that therewas a real start in its use.Developmentshoweverwere slow and disappointinguntil- 1961 whenthe Indian Khadi and Village IndustriesCommissiontook over. By 1973-74, some7000biogasplants had alreadybeeninstalled,and the numbermore than doubledby 1974-75.One reason for this expansion of biogas plants was the improvement in the design, construction and operation of practical digesters. Furthermore, sufficient knowledgewas obtained for the utilization of the gas not only for cooking but also for lighting and running engines.Successmay also be attributed to the very competent scientistsinvolved,suchasJ. Pate1and Ram Bux Singh,amongothers.The extensivework on biogas in India may be divided into three phases:experimentation, 1937-1950; pilot studies,1950-1963;andfull operationalstage,from 1964. 8
  • 31. In the raising of animals in confinement,made necessaryby an ever-increasingmeat- eating population, the disposalof animal wastespresentsa pressing pollution problem. Hence large numbers of studieson the subjectwere reported each year in the countries af%ected,mostly in the United States.The solution to problemsof animal wastetreatment or disposalor utilization becamethe object of studiesin academicand researchinstitu- tions. It becamethe subjectof thesesresearchfor the master’sand evenfor the doctoral degree.Seminars,regional and international conferences,and symposia have been or- ganizedon a subject which has,within a brief period, beenfound to be of double value: a solution to this particular kind of pollution and at the sametime a good energysource with the extra benefitsof organic fertilizer as a by-product. Nor is this the end of the be- nefits,aswill beshownin a separatechapter. 9
  • 32. Chapter II BiochemistryandMicrobiology t thereis no longerany doubt about the microbiological origin of biogas.The m decayingleaves,straw, grass,etc. that are submergedin stagnant of animal manure,either alone or with straw (farmyard manure). amity in the rumen or stomach of so-calledruminant animals. In eachcasebacteriaha&been shownto beassociatedwith biogasformation. Organic Matter ‘ Organicmatteris the materialbfwhich living organismsarecomposed.In this category are, therefore, the materials that constitute plants and animals. The chemical element which is found in all organic matter is carbon; however, not aii materiais containing carbonareorganicmatter, asfor examplelimestone(CaC03) andcalcium carbide(CaC,). The principal componentsof organic matter arecarbohydrates,fats and proteins,and a rather heterogeneousgroup wewill designatehereasphenolicssincethey arein someway related to phenol.Among the phenolics are lignin and tannin. Thesetogether with other minor groupslike chitin andresinsarefound to be more resistantto microbiological action than the first three groups. The biggestgroup are the carbohydrateswhich comprisethe celluloses,hemicelluloses,starches,and sugars.It must be remelmberedthat organicmatter is a very complex material and there are not only difficulties in classification but also inadequateinformation. A simplified scheme of the composition and fate of organic matter in methane fermentationis shownin thefollowing diagram: r)I- e I %L ,- Carbotydm~es --)6iogm & Vo&e solids F&s d I Proteins - Sludge Biogas is observedto arise from the bacterial decompositionof organic matter. The more knowledgegainedabout a process,the more likely the processcan be improved or manipulatedto the advantageof mankind. For this reasonthere have beenattempts to gain asmuchinformation aspossibleabouthow organic matter is changedto biogas.Since the processis microbiological, it is natural that one of the fist studiesmadewasto isolate andidentify the specifickind of bacteria andtheparticuiar materialor chemicalcompound 11
  • 33. “acted upOn; this latter is called the substrate. Thus in the fermentation of sugar, the microorganism is yeast.,the substrate is sugar and the products are ethyl alcohol and carbon dioxide. This alcoholic fermentation has been studied very well; it is known, for example,that the sugaris convertedto alcohol not in one biochemicalstep, but through a successionof changesbrought about by enzymespresentin yeast.The overall processcan be summarizedthus: Sugar-alcohol + carbon dioxide. This can be written as a chemicalreaction,andby employingthe methodsof chemistry wemay say that 100grams sugar(glucose)give 51.1gramsalcohol and 48.9gramscarbon dioxide. The conversionof glucoseto alcoholis then 51.1%. This is a theoreticalmaximum,hencea valuablepieceof information to have. Additionally, because of our precise knowledge of alcoholic fermentation,andof a successionof biochemicalstepsthat finally leadto the production of alcohol, it is possible(and this hasbeendoneon an industrial scale)to detour the process suchthat glyceroland not alcoholis the final mainproduct. Such basicknowledgeis lacking in the biogasconversionprocess.The searchfor such knowledgeis madevery difficult becauseit turns out that severalmicroorganisms,and not only one, are involved in methaneproduction. To compound the difficulty, it has been found that manychemicalcompoundsin the “parent” organic matter (not sugarsaloneas in alcoholic fermentation)can serveas substratefor biogasproduction. We havetherefore a rather complex case of many kinds of microorganisms, acting upon many kinds of chemicalcompoundsin theproduction of methanegas. The substrateor raw materialsknown to be acted upon by the methane bacteria are very simple compounds.They fall into three groups: (1) fatty acids containing 1 to 6 carbon atoms;(2) alcohols containing 1 to 5 carbon atoms (both straight and branched- chain); and (3) the gasescarbon dioxide, hydrogen and carbon monoxide. Additional compoundswhich arebelievedto be alsoprobably actedupon by the methanebacteriaare the long chainfatty acids,somedicarboxylic acids,acetone,2, 3-butyleneglycol and even somearomaticcompoundslike benzoicacid, Sinceorganic matter is largely composedof cellulose,starches,gums,pectins,etc. and theseare rather complex compoundsthe questionarisesas to how theseare convertedto biogas.The inferencethereforeis that the complexcompoundsare changedto the simple compoundswhich in turn giverise to biogas.According to H. A. Barker (1956), the con- versionof thesecomplexcompoundsto methaneis a multi-stageprocessin which bacteria that cannot form methane most likely convert these substratesto simple compounds which are then transformed by the methanebacteria to biogas. Symbolically, the series of changes,maybewritten thus: m-qv() bacteris 3CH 3COOH bacteria 3CH, + 3CO2 carbohydrate ) organic acid biogas Sincethe processof biogasproduction involvesat leasttwo distinct kinds of bacteria,it appears that the use of a single pure culture of a bacterium, as practised in most fermentativeprocesses,is not calledfor. As far aspresentknowledgegoes,a mixedculture is necessary.To complicate matters, even the production of methanefrom. an already simp!ecompoundhas been found to require Mere-+IaCspeciesof methanogenicbacteria, dependingon the !&d of this simplecompound.Barker found that evenfor the complete 12
  • 34. ~;~,““y., _ *;q+ ~ +$ > ‘5, fermentationof so simple a compound as vale& acid (C4H&OOH), as many as three ~” speciesof methanebacteriamay berequired. This rather severeselectivityof substrateby eachspeciesof methane-producingbacteria hasgivenriseto thedescriptiveterm“extreme substratespecificity”. TheoriesRegardingthe Origin of Methane A chemical explanation of methane formation may be shown in the formation of methanefrom aceticacid asa caseof decarboxylation: CH,COOH-- CH, -t CO, From formic acid, decarboxylationgivesCO2 + hydrogen which are gasesalsofound in biogas: HCOOH-H2 + CO2 If this bioconversion, as methane formation is often called, is always a process of decarboxylation, then gasesother than methanewill be formed from organic acids as indicatedin thefollowing chemicalequations: CH3COOH r,C02 + CH4 methane C2HSCOOH ~------+C02 + C2H, ethane C3H,COOH =,COz + C3H8 propane C4H,COOH ,co2 + GH,, butane Actual observationindicatesthat only methaneis formed, irrespectiveof the kind of acid. It is thereforelikely that eventhesesimpleacids are further converted,first to one kind of compound which then becomes the immediate precursor of methane. This explanation,the Van Niel carbon dioxide reduction theory, postulatesthat CO 2 and H 2 are the immediateprecursors of methaneand that the carbon dioxide is reducedby the hydrogenin theprocess.In the bioconversionto methane,the first stepthen is production of CO 2andH 2from the acid;the secondstepis thechemicalreductionof the CO 2by the Hz to form methaneasillustratedbelow: Step1 CH3COOH + 2H20 ,-/ 2C02 + 4H, Step2 CO2 + ‘tH2 P CH4 + 2H20 Overall CH,COOH P CO2 + CH4 13
  • 35. That this chemicalexplanationmay be true is indicated by studies which have shown that as much as 70% of biogas comes from the acetic acid present in the substrate. Bacteriawhichare normally found in the intestinal tract may also be found free-living in thesoil andtheseform largeamountsof aceticacid. The stepwiseformation of CH4 from formic acid may beasfollows: Step1 QHCOOH L, ‘tco2 + 4H2 step2 c02+ 4H2 c-> CH4 + 2H20 Overall 4HCOOH - CH4 + 3CO2 + 2H20 From othersimplecompounds,the formation of CH4 may begiven asfollows: 1. From a primary alcohol: 2C2HsOH + CO 2 - CH, + 2CH,COOH 2. From a secondaryalcohol: 4CH,CHOHCH3 + CO2 w CH4, I- 4CH$OCH, + 2H20 3. From a higherfatty acid: 2C4H,COOH + CO2 + 2H20 CH4 + 2CH3COOH + 2CH3CH2COOH 4. Frommethanol: 4CH3OH ,-> 3CH4 + CO2 + 2H20 It will b2 noted that CO2 is a reactant in the fast three reactionsgiven above,but not in the !astreaction It hasbeenpostulatedthat the origin of methaneis CO;! and the pro- cessinvolvesstepsthat arewell known in chemistry. +2H co2 - HCOOH +2H +2H +2H 0-p HCHO 11111+ CH,OH S-W CH4 -H20 -Hz0 The processstarts with the reduction of CO2 by hydrogento produce formic acid, then to formaldehydeto methanoland finally to methane.Actual experiments,however,have failed to showthat this sequenceof eventsactually takesplace.Barker thereforesuggests that the initial reductive stepis not by hydrogen but by a hydrogen carrier probably in combiied form representedby XH. The reductive steps,comparableto the CO2 reduc- tion procc=ssearliergiven,arethen: +2H +2H +2H CO2 - XCOOH --H 0 XCHo2 -XCH,OH -d XCH, 2 03 CH4 + XH Thehydrogencarrier is regeneratedandrecycledasillustrated above. 14
  • 36. The formationof CH4 &n methanoland from aceticacid may also be shownto involvethe carrierXH andthusmakepossiblea unifiedtheoryasto the mechanismof formrtion of CH,, but in thesetwo latter casesthe oxidant is not CO2 althoughthe reductantisthesame,XH. Thecompleteschemeof Barkeris asfollows: ~xH+co~-xcocm I +Z:H -ho XCHO -Hz0 -XH+Cl=l~OH 1 - co2 -XH+cM~COOH - 2H I +2kl XCb42OH +2H -I420 - XCH~ I +2H m&e - Xkl+cHq The theory then is that complex chemical compounds are biodegradedto simpler compounds and ultimately to CO2, CH30H or CH&OOH; theselatter compounds, through theactionof methanogenicbacteria,yield methanethrough aninitial reactionwith a hypothetical compound XH. Obviously the compound XH must be found or demonstratedto exist.It appearsthat theburdenof proof was assignedasa thesisfor a Ph. D. degree.The student, ThressaStadtman, successfullyunearthedsufficient evidenceto showthat XH is a cobalt-containingcompoundthat exhibits vitamin B12activity. Adding support to the possibleinvolvementof vitamin B12in methanefermentationis the finding that sludgesfrom methanefermentersare quite rich in this vitamin, thus opening a new potentialof usefulnessof thebioconversionprocess. The presentoverallpicture of theprocessof biogas(or methane)formation from organic matteristhenasfollows: 1. The agent of change (from organic matter to biogas) consistsof two groups of bacteria: the methane-formingand the nonmethane-formingbacteria. Theselatter act on the complex organic compounds in the substrate (raw material), such as cellulose,starch, proteins, fats, etc., converting them to more soluble compounds largely by hydrolysis: the carbohydratesto simple sugars,the fats to fatty acids andglycerol,the proteinsto proteoses,peptones,etc. 2. This initial change is followed by a conversion of these compounds la.rgely to acids of one to six carbon atoms, to alcoholsof one to five carbons and to other similarly simplecompounds.Free oxygen is not neededin the processand is even harmful. 3. The methanogenicbacteria act on these acids, alcohols, etc.; the final metabolic products are CH4 and CO2 (biogas). These bacteria demand strict anaerobic conditions;evenmildoxidizing substanceslike nitrates mustbeabsent.
  • 37. 4. The mechanismof formation of biogas from simple coqwunds is not yet very clearbut there is evidencethat a vitamin B 12 compoundis involved, hencethe ap- parentenrichmentof this vitamin in thesludge. 5. A decreasein pH as a result of acid formation inhibits the growth of the methane- forming bacteria, therefore acid formation must proceedslowly and in step with the methane-forming process. The maintenance of a proper range of pH is of courseattained through the presenceof buffers which are generatedin the ferment- ting medium. 6. It is apparent that the rate of acid formation will dependon the rate of the con- versionto biogas; that is, acid is allowed to form only about as fast as it is con- vertedtoCH4andC02. The Bacteriain BiogasProduction Pig manure, by itself, generatesbiogas spontaneously,although it takes quite some time for this to happen. Hobson and Shaw (1967), using a M-liter digester initially filled with water, added pig manure gradually so that the water was replacedin about 4 weeks’time. By then the total solids was 2%. Operating as a continuous-fedsystem, pig manurewas addeddaily at the rate of 0.03 lb. per cu. ft. per day. At regular time in- tervalstheydeterminedthekind andnumberof bacteria.Their resultswereasfollows: First week: Total countwas5 x lo6 to 5 x 10’ /ml. The number of amylolytic bacteria (starch decomposers)was greater than 4 x 1oQnl. Third week: By this time the methanogenic bacteria (methane producers) began to appear, numbering about lo3 /ml. and they increased in number with increasingtime. Fourth to fifth weeks: The cellulolytic bacteria (cellulose decomposing), num- bered lo4 to 105 /ml. The proteolytic bacteria (protein-decompos- ing) alsoappearedat aboutthis time at greaterthan 4 x lo4 /ml. Ninth week: The methanogenicbacteriareached10’ /ml. In another study of the bacteria in pig dung the following results were obtained by HobsonandShaw(1967)in a slurry of 4% “settable solids”: Total count at start: Anaerobic,6.4 x lo8 /ml. Aerobic, about 2.4 x lo8 /ml. The nonmethanogenicbacteria were found to be principally the noncellulolytic and thecellulolytic bacteria. I. Noncellulolytic bacteria. 1. Streptococci,facultatively anaerobic,constituting 43 to 47% of all isolates.Non- proteolytic and nonamylolytic, probably play a role in maintaining the anaero- bit condition in digesters. 16
  • 38. : 2. Bact&ds, constituting 20 to 80% of the anaerobic bacteria. Gram-negative pleomorphicrods, shortto medium length; some are coccobacilli, mostly amy- lolytic.‘Fcrment mono- and disaccharidesaa well as glycerol producing pro- pionic, aceticandbutyricacids. 3. Clostridia. The most activeproteolytic bacteria,foundbelongto threegroups: A. Amylolytic; very similar to Clostridium butyricum; fermentation pro- ductsareaceticandbutyric acids. B. Proteolytic; fermentsugarsforming aceticandisovalericacids. C. Proteolytic but do not fermentsugar. II. Cellulolytic bacteria, a heterogenousgroup present in lo4 to 10’ /ml. were iso- lated.One isolatewas a Gram-positiverod, generallycurved, often in short chains.From cellulose, it produced mainly propionic acid, occasionally acetic as well as traces of formic and succinic. Other isolateswere Gram-negativecoccobacilli or rods of various morphologies.They form volatileacidsfrom cellulose. III. Other bacteria isolated in small quantities were lactobacilli, staphylococci, gly- cerol-fermentersandlipolytic bacteria. The methanogenicbacteria beganto appearon the third week and by the 9th week they reacheda count of lo6 /ml. Of acids testedas substrates,only formic and butyric acids were converted to methane.The organism was classified as Methanobacterium formicicum, a Gram-negativerod of variable length. It producesmethanefrom a mixture of CO and hydrogen gasesor from formate, but not from acetate,propionate, isobuty- rate, valerate, isovalerate, succinate, pyruvate, glucose, ethanol, propanol, butanol or isobutanol. The methanogenic bacteria possess the following general characteristics (Barker, 1956): 1. Strictly anaerobic; not only molecular oxygen but also compounds that easily give oxygen like the nitrates must be absent. In Barker’s studies (1956), pure cultures of these bacteria were obtained successfully for the first time only by usingsodiumsulfideto removethe lasttracesof oxygen. 2. Require a pH range for growth of 6.4 to 7.2 (other authors put the optimum pH at 7.2 to 8.2). However, one speciesgrows at pH 8-9, and in peat bogswhere thepH is about4, somemethaneis alsoformed. 3. Utilize ammoniumsaltsasnitrogen source. 4. No known need for nutritional factors (probably amply supplied by commonly usedsubstrates).This is in contrast to otherorganismslike yeast. 5. Producemethaneasa major metabolite. 6. Exhibit extreme substratespecificity; thesebacteria are able to utilize only a few very simplecompounds. In accordance with known microbiological techniques, attempts have been made to grow in strict isolation, each speciesof bacterium that producesmethane.This has proven to be very difficult; hencethere are only very few that are definitely confvmed to bemethaneproducers. 17
  • 39. p’ ,,, ,,_ I I Barker(1956)classifiedthemethanogenicbacteriaasfdlows: Family: Methanobacteriaceae A. Rod-shapedcells i. Nonsporulatiqg Methunobucterfum 1. Mikuxfonnicfcum -------- CO, H, , formate’-/ 2. Mkt. propionicum ---- propionate 3. M&act. sohngenii----------------- acetate,butyrate 4. M&t. ruminantiud~ -------- CO2 , H 2 II. Sporulating: Methanobacillus 1. Mbac. omelianskii ----------------- H.2, primary and secondaryalcohols B. Sphericalcells I. Cellsnot in sarcinaarrangement:Methunococcus 1 l MC* m& - ~~~~~~~~~~~~~~~~~~~ - ---- ----- acetate, butyrate 2. MC.vannielif--------------------------- forma@,H 2 II. Cellsin sarcinaarrangement: Methanosurcinu 1aMs. bark&i --------------------------- CH3OH, acetate,CO, H2 2. Ms. methanica------------------------ acetate,butyrate Methane Production in the Rumen - Pertinent to this discussionon methaneproducers are the results of studies on the microflora of the rumen. Hungate and co-workers (through Thimann, 1963) have shown that the rumen contains many organisms close- ly relatedphysiologically, mostly short rod, oval or coccus,which actively ferment cel- lulose to organic acids like acetic and propionic. Methane results from the secondary fermentationof theseacidsby methanogenicbacteria which have beenfound present up to 2 x 10” /ml. in rumen fluid. A cow reportedly gives as much as 700 liters of gas in a day. Need for a Massive Amount of Starter Since both methanogenicand nonmethanogenicpopulations are neededfor biogas production, it is therefore evident that not only should thesetwo kinds of bacteria be present,but they should also be in the optimum proportion. This proportion is no doubt presentin an actively fermenting digester,no more than 20 days old, and constitutes the bestseedor starter. Additionally such a starter has already developedsufficient buf fers to maintain the pH at the desiredvalue. An actively fermenting material also gene- rates hydrogen sulfide (and probably other soluble sulfides) which brings about the highly anaerobiccondition demandedby the methane-producingbacteria. It is now un- derstandablewhy a massiveamount of inoculant or starter, no less than 20% of total starting slurry, is insuranceagainstdigesterfailure. L/ Knownsubstrates. -2/ Addedto Barker’slist. 18
  • 40. Ilbtmtion l-2: Rdicmbiological uuy d vita& B,z Illustration 1-3: Pollution control laboratory 19
  • 41. Chapter III Laboratory and Pilot Plant Experiments (All the experimentsdescribedin this chapterwereconductedin the laboratory at Maya Farms.) It is highly desirableto get the highestpossibleconversionof hog manureto biogasand the minimum amount of the sludgeby-product. Sinceeventually the sludgewill have to bedisposedof, largequantitiesmay presenta problem.The fermentingmixture of manure and water shouldbe asconcentratedas possible.From the beginning,it was clear that the specificoperatingconditions would haveto beworked out and this would bebetterdonein a laboratory whereconditions of operation are smallerand easierto control than in large. installations. For useasa “digester”, (as the fermentationtank is called in literature on biogas),the ordinary gallon bottle proved to be suitable. It is easily available, being of local manufacture and often used as container for many liquid food commodities. It is inexpensive,andsincecost is a matter of concernwhen up to a hundredsuch bottlesmay beneededat onetime, it is thereforeadequatefor the task on hand.A chargeof 2.7 liters of digesterslurry into the 3.8~liter(onegallon) bottle leavesa safeheadspaceof about 1.0 liter. The heightof the slurry in the bottle in relation to the diametergives a 1:1 ratio, CL very desirableattribute for anaerobicfermentation. The charge of 2.7 liters of slurry is large enoughfor good reproduciMity amongthe five replicatesthat are always run. The usual, although minor, difficulty in inserting severalpiecesof glasstubing into a rubber stopper is not met since the gallon bottle accepts a large stopper and can easily accommodate3 to 4 piecesof glasstubing. Laboratory Set-up for Methane Fermentation The set-upis shownin Fig. 3-1.There aret!!ee one-gallonbottles.Bottle A servesasthe digester;bottle B is the gas holder and bottle C is the water-overflow collector, empty at the start. The digester(A) is chargedwith 2.7 liters of the preparedexperimentaldigester slurry, a mixture of hog manure,water and starter.Bottle B is filed completelywith water. The rubber stoppers fitted with the interconnecting glass tubing are inserted into the bottles, preferably wired in place since gas pressure is developed.In operation, gas generatedin A pushesout an equalvolume of water from B to C. The volume of gascan be determinedfrom the volumereading in C which has beenpreviously calibrated. Bottle C may beomittedif a drain canbe provided for tubed in which caseBottle B will haveto be’markedin liters.The digesterslurry chargedin Bottle A doesnot usually generatemore than 3 liters of ga$ in 24 hours; hencethe water in bottles B andC neednot be attendedto more than once a day. The gas collected is allowed to escapeinto the air after due measurementof its volume or tier samplesaretakenfor analysis;B is refilled with water collectedin C becausethis.wateris already saturatedwith the gas.Solubility correction for gas volume is thus diminished. Bottle A is briefly shaken once a day to loosen up gas
  • 42. lhstration I-1: Experimental laboratory digesters at Maya Farms -------- tml ----------=-_---_----_--!-1-z---_----- =I -----_--_-------- C Fig. 3- I : Laboratory set-up for study of biological production of methane 22
  • 43. :: bubblesin the slurry. Gas bubblesare entrappedin the slurry especiallyin thick slurries. The fermentation room has shelvesto accommodatea hundred three-bottle set-upsand adjoinsa heateddrying room; thetemperaturein the fermentationroom is thus kept at 3lo + 3OCthroughout the year. The fermentation room is preferably well-enclosedwith a &ntrolled air exit, a smallventilatingfan fixed on a convenientwall. To setup a fermentationrun, a digesterslurry is made by dispersingfresh hog m.anure in water, placingthe mixture into bottle A and addingthe starter.If the desiredratio of hog manureto water is 1:1 and the starter is 25%, then the weight of the starter is 0.25 x 2.7 kg. or 0.675 kg. sincethe digesterslurry totals 2.7 kg. The weight of the manure and the water is 2.7 kg.- 0.675 kg. or 2.025kg. andhence,manureweightis 1.0125kg. In general the relationshipis: digesterslurry = manure + water + starter. The water for making the slurry is unchlorinated;the startercomesfrom an actively-fermentinghog manureslurry in its 20th to 25thday of fermentation.The volumeof gasevolvedis measuredeveryday. The Gas ProductionCurve The plot of the cumulative gasvolume againsttime (day number)is the gasproduction curve, Fig. 3-2. Its appearanceis similar to the well-known growth curve of bacteria. However, theinitial lag phaseis not in evidenceprobably becauseof the massiveamount of inoculant (starter). Gas is measurablewithin 24 hours and continuesto increase;this portion of the curve is the logarithmic phase.In due time the increase in gas volume slackens.The curve makesa bendand continuesto increasebut at a much reducedrate. This part of the curve is the “senescencephase”;the “biopause” phaseis the sectorwhere the logarithmic phasechangesover to senescence.In Fig. 3-2 the logarithmic or active growth phase lasts 22 days, followed by the biopause of about 6 days, after which senescencetakes over. This is the general shapeof a typical gas production curve for methanefermentation. It will benoticedin Fig. 3-2 that the rate of gasproduction in the growth phaseis much higher than that in the sencticencephase.The change-overtakes place during biopause. Thereis reasonto operatea fermenter(digester)only up to biopausebecauseof thedecline in gasproduction thereafter.The retention time is the number of days that the fermenting slurry is retainedin the digester.Sincein the presentexamplethe biopauselasts six days, the operator of the fermentermay selecthis retention time within this period. It is to be noted that retentiontime may also be selectedor adopted.The operator may wish, with reason,to adopt a retention time earlier than biopausealthough he will be losing gas.He may also prefer a retention time after biopausein which casehe will be wasting digester spacebecausehis digesterproducesgas inefficiently after biopause.The time when bio- pauseoccursisthereforeimportant. The active growth phaseand also the senescencephaseare very closeto being linear. Assumingthis to be the case,it is possibleto calculatethe rate of gasproduction in each phase.For thegrowth phaseof 22 days,therateis: 54.7liters 22 days = 2.5liters per day 23
  • 44. 70I- - 60 4 3 5o 2 3 0 m q 40 fz z t m $ 30 L -t a 20 10 I f av=54.7 z At 22 2.48 I/da / I I I I I I I I I I I 0 10 20 30 40 50 60 DAY NlJMl3ER FIG. 3-2 TYPICAL BIOGAS PRODUCTlON CURVE
  • 45. “ ,c.i For the senescencephase,taking thegasvolumebetweenthe 32ndand 60th days,the rate is: (68.6- 65.0) (50- 32) = 0.20liter perday. Therate of gasproduction duringthe growth phaseis more than tentimesthe rateduring senescence. The rate of gasproduction during the growth phaseis a good index for the study of conditionsfor methanefermentation.It is to benotedhoweverthat besidesthe ratein liters of gasper day, anotherinformativeratio is the numberof liters of gasper kg. of manure. Thevariousmethodsthat maybeusedin reportinggasproductionareshownbelow: Gasvolume,liters Gasperday,liters Gasperkg.manure Gasperkg.perday TheProportionof Manaveto Water Time Periodin Days Q-20 O-30 O-60 48.0 64.5 71.4 2.40 2.15 1.19 47.4 63.7 70.5 3.37 2.12 1.12 The raw material for fermentation in the experimentsis hog manure. Foi biogas production,the questionsthat ariseat the start are: (1) how muchdilution with water is neededand (2) how much starter is used. To provide answersto these questions,the following manure-watermixtures or slurrieswereprepared: 1:1, 1:1.5, 1:2.,1:3 and 1:4 usingfreshmanure,i.e.collectedwithin 24 hours,anduntreateddeep-wellwater. Thetotal volumeof the slurry was kept at 2.7 liters (approx. 2.7 kg.) in order not to overloadthe gallon jar digester.Each bottle was seededwith a vigorously fermenting starter, the &v,Ql&iqt Qf j&7&h WZlf ndillatwl Ctl 8s to fiLm&iS_h_ st,m-ei ql~v&~t &l 205!/nj 25% and 33%..WI--~‘“-v- YY (l/5, l/4 and l/3) of the 2.7 liters of slurry. The amount of starter is calculatedfirst: 20% x 2.7 kg.; 25% x 2.7, and 33% x 2.7 kg. In a 1:2 manure/waterslurry, the weight . 2.16of manureis (+ or 0.72 kg. and that of water is 0.72 x 2 or 1.44 kg. The weights, of starter, manure,and water for the experimentsare calculatedin the samemanner and aretabulatedin Table3-2. All the experimental“digesters” gavemeasurablevolumesof gaswithin 24 hours.The amountof gaswas measuredeveryday. The plot of gasvolumesin liters againsttime in days are given in Fig. -3-3. In all casesthe characteristic gas production curve was obtained,eachhaving a well-definedactive growth phase,a biopauseand a senescence phase.Thelowestpercentageof starter employed,namely 2096,appearedto be adequate. The ratesof gasproduction of slurriesof equalvolume(blutdserent manure-waterratios) aredifferentfrom *theratescalculatedat equalmanureweightsfor the samemanure-water ratios.Whencomputedon equalweightbasis,i, e.per kg. of manure,the curvesappearin the reverseorder as in the experimentalresultswhich are on equalslurry volumeof 2.7 liters (Fig. 3-4).It can be seenfrom the graphthat the volumeof gasper kg. of manureis larger, the moredilute the slurry. However,the 1:l slurry givesmoregasper day for the samedigesterspacethan a moredilute slurry becauseof the largerweight of raw material (manure)in the*1:1slurry but lessgason equalweightof manurebasis. 25
  • 46. UJ > K-J LITERS BIOGAS CUMULATIVE 0 WI > N LITERS BIOGAS CUMULATIVE LITERS BIOGAS CUMULATIVE
  • 47. 80 60 >” i= 5 3 50 z 2 2 CD 4o 0 G iii w I== 30 2 20, 10’ 0 1:2 1:3 1:4 FIG. 34 GAS PRODUCTION CURVES ON! EQUAL SLURRY VOLUME AND EQUAL MANURE WEIGHT BASIS. - EQUAL WEIGHT BASIS EQUAL VOLUME BASIS I I I I I I I I I I 1 10 20 30 40 50 60 DAY NUMBER 27
  • 48. Thereis a beliefthat storageof pig manurefor a few dayswould enchanceits biogas- producingcapability. The experimentaltrials of manurestoredat 0, 1 day and 3 days are shown in Fig. 3-5 and indicate that fresh or one day old manure is best for biogas production. Amount of Starter Sincetheproduction of methaneis a fermentationprocess,the amount of the inoculant or starteris of prime importance.Literature on the subjectis meager.It is practicalto use as starter, a portion of a successfulmethanefermentationfrom the activatedsludgein sewagetreatmentworks. In someprocedures,the manure slurry is allowed to ferment without benefitof an addedstarter. To determinethe amount of starter, the apparatus consistedof thepreviously-described3-bottleset-up;thedigesterslurry wasfutedat 2.7 kg. manure-waterratio at 1:l andthe starteramountvariedto correspondto 0, 5, 10, 15,20, 25 and33%of 2.7kg.Theweightsinvolvedin kg.wereasfollows: digesterslurry = manure + water + starter for 0% starter: 2.7 = 1.35 + 1.35 + zero for 5% starter: 2.7 = 1.28 + 1.28 + 0.135 for 10%starter: 2.7 = 1.21 + 1.21 + 0.270 for 15%starter: 2.7 = 1.15 + 1.15 + 0.405 for 20%starter: 2.7 = 1.08 + 1.08 + 0.540 for 25%starter: 2.7 = 1.01 + 1.01 + 0.675 for 33%starter: 2.7 = 0.90 + 0.90 + 0.90 The figureswere arrived at by calculating as follows: Weight of starter: 5% of 2.7 kg. = 0.135 kg. Weight of manureand water: 2.7 kg. - 0.135 kg. = 2.565 kg. Weight of manureor weightof waterfor a 1:1(w/w) ratio isonehalf of 2.565kg. or 1.28kg. Theresultsof this experimentaregivenin theform of gasproductioncurvesin Fig. 3-6. It is easilyseenthat a slurry without addedstarteris a very poor performer.An inoculant is essentialto good gas production. Increasingthe amount of addedinoculant improves performanceup to 20% after which the gasproduction curvesappearnormal with well- defmedgrowthphase,biopause,and senescencephase.From this experiment,it seemsthat the startermustbe at least20% of the weightof the digesterslurry. A digestercontaining 1000 liters of slurry inocultitedwith 1.0 liter of starter is not likely to perform well. It should be noted that the substratematerial, hog manure, is not given a pre-sterilizing treatment;henceit is teemingwith many kindsof organismsthat caneasilyoverwhelmthe bacteriain thestarterif thesebacteriaconsituteonly averysmallproportion. The betterperformanceof fermentationemployinglarger amountsof starter is further shownin thefollowing tabulation. Starter,% (A) 5 10 15 20 25 33 Liters gasproduced,20 ~YS 09 15 18 28 38 47 54 Days to produce50 liters lw (C) 60 45 31 25 21 19 28
  • 49. 90 60 70 560 F 5 g50 0 2 8 zw cn E = 30 20 10’ FIQ. 3-6 GAS PRODUCTION CURVES FOR STORED PIG MANURE PRODUCTION CURVES STORED PIG MANURE v DAY NUMBERDAY NUMBER I 1 I I I i 0 7c 6C 5( 4t 3c ZC 10 0 90 60 70 60 E am z s 40, % In 3 30. P B 5 20, 10. 10 20 30 40 50 60 70 P lb r40 PERCENTAGE OF STARTER FIG. 3-7 RELATION OF PERCENTAGE OF STARTER AND NUMbER .OF DAYS TO PRODUCE 60 LITERS BIOGAS. 0 10 20 30 40 50 60 70 DAY NUMBER FID. 3-6 DAS PRODUCTION CURVES FOR VARYING 1DDT / (c) 23 DAY STARTER go- - / BO- - / 70-- / BO-- 60- - /T (8) 30 DAY STARTER IAI 60 DAY STARTER 40-- 30-- 20-- FIG. 3-S EFFECT OF AGE OF fi / STARTER ON GAS PRODUCTION DAY NUMBER I 1 I I i SYARTER PERCENTAQE 0 10 20 30 40 50 60
  • 50. With 20 days fermentation time, the 20% starter gave twice as much gas as the 10% starter.This 2:l relation is also apparent in the 33% and 15% starter, The value B/A is fairly constant; so is the value of A x C. The plot of starter percent (A) against the 20-day gas (B) is shown in Fig. 3-7. It is seenthat the higher the percentageof starter, the better is gas production. The extreme case will be the situation where all fermenting slurry is used as starter. It is hardly conceivable that this arrangement can be made practical, but it is what actually happensin a continuous-fed digesterwhich will bediscussedlater. Ageof Starter The starter or inoculum should come from a vigorously fermenting slurry; the slurry should be at the active growth phase. In one set of the laboratory experiments, starters coming from slurries that had pndergone fermentation for 23 days, 30 days and 60 days were used as starters (five replicates each). The results, as shown in Fig. 3-8, indicate the greater gas production rate as well as relatively larger volume of biogas (30-day period) produced by the 23-day old starter. Gas Productionat a ConstantVolume of DigesterSlurry and at a ConstantWeight of Manure In the laboratory experimentson the effect of dilution of the manure on gasproduction, the weights of hog manure had to be varied, since the volume of the digester spaceis ne- cessarily constant at 2.7 liters. Gas production for this kind of situation is given in the set of curvesin Fig. 3-4. The impression is that the more dilute slurries, like 1:4 manure-water mixtures, give a poor performance. When gasproduction figures are calculated on the per kilogram of manure basis,there is a very striking change in the order of performance. The starred lines of Fig. 3-4 show this. On a constant weight basis,that is, on the p;‘erkg. basis, the most dilute slurry gives the larger volume of gas. For comparing efficiencies of gas production from a given material, a comparison based on the yield of one kg. of the material under varying conditions appears logical. For comparison of actual digester performance we cannot neglect the imposed condition of a constant volume of digester slurry. This discussion brings relative advantages and disadvantages in employing dilute slurries. With the option of operating a digesteron thin slurry such as 1:4, one can expect to get a high conversion of manure to gas on the per kg. basis.The retention time is short; experimentsindicate a period as short as 15 days or even less,and thus the slurry will go through the digester rather quickly in continuous-fed digesters. Pumps may be used to move the slurry, which is a great convenience. However, there will be a voluminous amount of sludgeto disposeof. Since this sludgeis quite well “digested”, it will beexpected to require lessconditioning to get it ready for further utilization. The other option is to useasthick a slurry aspossible, 1:1or even thicker. The material will be difficult to move with pumps. The volume of gas produced per day will be high although the conversion efficiency per kg. manure will be rather low and the post-digestion time will be longer. The digester space per unit weight of manure will be small and retention times wiIl be longer, about 30-40 days, The relative volumes of digester needed when employing various dilutions are shown in Table 3-l. A 1:4 slurry occupies 2.5 times the volume of a 1:1 slurry, although both slurries contain the sameinitial weight of manure. 30
  • 51. RelativeVolumeof DigesterSpaceto Contain OneKilogramof Hog Manurein Varying Manure- WaterRatios.(Starter2096,Digester Slurry 2.7 Liters) Manure-waterratio (dilution) 1:l 1:2 1:3 1:4 Weightof manure,kg. 1.08 0.72 0.54 0.432 Digesterspace(slurry)liters 2.7 2.7 2.7 2.7 Relative digesterspace 1.0 1.5 2.0 2.5 Ratio of Volume of Gas/Day to Volume of Digester Slurry A useful and simplerule of thumb usedto check on performance of working digestersis that the value of the ratio of gas volume per day to digester slurry volume, is about 1. Fig. 3-9 givesplots of theseratios in relation to day number of digesteroperation. From the 5th to the 15th day of operation, the ratio gas volume per day to slurry volume is about 1.5. After 20 daysthe ratio decreasesto lessthen 1.This is to be ascribedto senescence.Of the three dilutions studied, 1:1,l: 1.5and 1:2, the last gavethe smallestvalues.A gwd working digester therefore has a volume ratio of gas to slurry of at least 1:2 (for slurries of 1:l to 1:2). Rates of BiogasProduction While the total volume of biogas evolved during the active growth phase is useful information, the rate at which the gas is produced is equally of value. The rate may be calculated in liters of gas per day per kg. of starting material. The weight of volatile solids (W&j or the non-ash dry matter, is often used by scientific workers instead of the dry matter content. Table 3-3 givestheserates averagedfor each of the following time periods: O-20,0-30,0-60 days, and for three starter percentages.The 20-day period comesnearest to the period of active growth, that is, from the start to biopause. The rates are highest in the O-20 day period and progressively decreasein the longer periods. The decreaseis due to the onset of the senescencephase (low rate period). The general average rate of bio- gas formation for the O-20day period is 13.6 liters of gas per day per kg. volatile solids; the value for the O-30 day period is 10.5 liters/day per kg. V. S. The plot of the rate (liters per day per kg.) against V. S is shown in Fig. 3-10. At the active growth phasethe value of this rate is quite constant over the range of about 4 to 8% V. S. The highest rates are those for more dilute slurries and for shorter fermentation periods, although the limits have not been determined. In so-called continuous-fed operation, the observed high rate of gasproduction is probably due to the effect of shorter retention time often adopted. Rate of Gas Production During Senescence Fig. 3-10 also gives the rates of biogas production during the senescencephase. The calculated values are ,closeto 0.2 liters per day per kg. starting material over the range of 3% to 8% V. S. The senescencerate is about one-tenth the active growth rate. It is to be noted herethat theseresults show that the correction of the observedgas volumes from the volume of gas coming from the starter is small when the starter employed is already at or near senescence. 31
  • 52. I I I I 1 I I 10 20 30 40 DAY NUMBER FIG. 3-9 RATIO OF VOLUME OF GAS PER DAV TO VOLUME OF DIGESTER SLURRY. 2oc 16C 16C E z s 140 5 :: ii! : 120 3 iii 3 g loo 0 $ if 2 60 8 5 2 f 60 ii 2 40 5 20 FIG. 3-11 GAS PRODUCTION CURVES 1:1.5 1:2 EGUAL MANURE WEIGHT EOUAL SLURRY VOLUMES DAY NUMBER 1:l 1~16 FROM :l :1.5 :2 S-- --a0 E 3 B -40 E 3 In ii ;r --40 E 8 t % --20 :: 1 I t E % FRESH DUNG 0 20 30 4b Ii0 % VOLATILE SOLIDS 2 4 6 8 10 FIG. 3-10 RATES OF BlOGAS PRODUCTION DURING ACTLVE GROWTH AND SENESCENCE IN RELATION TO DUNG CONCENTRATION. lo( I- 9c I- - .3aI-. 70 60 s 5 3 50, 5 0’ 2 40 p ft p 30, 3 20 10, FIG. 3-12 GAS PRODUCTION CURVES FOR CORN STALK AND RICE STRAW. 0 10 30 40 50 60 C 9Y NUMBER
  • 53. Ga8Pmluctlon tiom Other Substrates Fig. 3-l 1givesthe gasproduction curves for poultry manure. The volume of biogas per kg. of dry manure is plotted here against number of days of fermentation. The curves show a welldefmed active growth phasebut the biopauseis rather indistinct and mergeswith the senescencephase. Retention time is therefore not easily determined from the graph. The shapeof the senescencecurve appears to indicate that the chicken dung was undergoing a relatively strong fermentation beyond the active phase. This may be due to inadequate fme grinding of the manure. Further trials should be made also on greater dilutions, with more stirring and probably the addition of a carbon source since the C/N value for chicken manureis lower than for pig manure. (SeeChapter 4). Fig. 3-12givesthe gasproduction curvesfor ground corn stalks and chopped rice straw, both in admixture with hog manure. The gas curves have well-defined phases.The active growth phaseshave identical slopes for all these substrate materials with a value of 2.87 liters per day, which is higher than in most of the pig manure experiments. Biopause was reached latest with 8% ground corn stalks (26 days) followed by 2% ground corn stalks (22 days); chopped rice straw reached biopause earlier (about 18 days). The senescence phasestill produced gas at a fairly high rate, due probably to a secondary fermentation. It is evident that the process of fermentation consisted of a primary process whereby the more easily fermented compounds underwent decomposition at a high rate; this was followed by the decomposition of the more difficultly fermentable materials during senescence,either becauseof their nature (cellulose, lignin) or because of larger particle sizedueto inadequategrinding. Desirable Characteristics of a Gas Production Curve of a Batch-fed Digester The various forms of gasproduction curvesare shown in Fig. 3-6. There are advantages in having a methane fermentation that proceedsin such a manner that the gas production curve (gasvolume plotted againstday number) hasthe following characteristics: 1. Three definite, well-defined phasesmay be distinguished: active gas production, bio- pause and senescence.When this is the case, the optimum retention time becomes also definite, sothat the number of days of retention in the digesteris well-defined. 2. The slope of the senescentphase should preferably be as small as possible, which indicates that the discharged sludge will be evolving very little gas and in consequence have lessodor and require lesssludgeconditioning. 3. The slope of the active gas production phase should be as large as possible and of a constant value; a wavering value indicates that there are factors (change in tempera- ture, lack of stirring, overloading, lack of starter, etc.) that are appreciably affecting the normal operation of the digester. Corrections on the Measured Gas Volumes Since the experimental studies involved measurement of gas volumes, the following corrections areapplicable: 1. Gas coming from the addedinoculum or starter which tendsto increasethe observed gas volume. According to Fig. 3-10, the rate of gas formation averages2 liters per kg. per day. The volume of gas from a 20% starter is expectedto be0.36 x 0.2 x 2.0 or 0.144 liters/ 33
  • 54. day but only 4096of the manureactually ‘ferments(seeChapterS),hence0.4 x 0.144or 0.057 liter/day; for a fermentationlasting”‘20days,the volumeof gas coming from the starteris 1.15liters. 2. Solubilityof CO2 in water.Suchsolubiity is0.034molaror 0.85liter gasperliter of waterat 25OC,or 1.8litersgasin 3 liters of waterarelost throughsolubility effect.Part of the CO2continuouslydiffusesout of the solution into the air; hencethe amount of CO2 lost is greaterthancanbeaccountedfor by a meresolubility data.Becauseof suchlossof CO2, theexperimentallymeasuredvolumeof biogasis smaller by at least 1.8 liters than is actuallyproducedin theexperiment. 3. Aqueous tension or vapor pressure exerted by water on the gas volume. This value increaseswith temperatureand is about 32 mm. at room temperature. Atmospheric pressureis generallyaround 750 mm, hencethe partial pressureis about 718 mm. The measuredgas volumes are therefore to be multiplied by the factor 0.97 to correct the volumesfor watervapor. In summary, the observed biogas volume is larger by 1.15 liters which is the estimated volumeof gasgiven off by the starter in 20 days. It is smaller by at least 1.8 liters due to loss of CO2 through its solubility in water at ambient temperature and pressure. The observed gasvolume tends to be larger becauseof the vapor pressureof water; correcting for this factor, the biogas volume is 0.97 times that of the observedvolume. All in all, the corrections are small and more or less cancel each other; hence all gas volumes reported areactualmeasuredvolumes. Application of Batch Operation Data to Continuous-fed Operation The data so far obtained camefrom experimentswhere the digester(fermenter) is given one charge of slurry for the duration of the fermentation. The active growth, biopause and senescencephasesare all obtained from such batch operations. It is said that the biogas installations developedin the then French Algeria by Isman and Ducellier were of this kind. Later developmentsin many parts of the world have favored a systemwhere the digester is given fresh material, usually every day, with automatic displacementof an equal amount of sludge so that this mode of operation has beencalled continuous-fed operation. In such a case,gasis evolvedin more or lessconstant volume;the slurry is always at active growth phase except at or near th,eend of the digester where the sludge about to be discharged should be at biopause or early senescencephase.The slurry therefore is fed at one end of the digester, goesslowly through the length of the digester, so that by the time this slurry reachesthe exit end, it is already at biopause or senescencephase.The retention time is the interval between the feed-in and the discharge. This is the general idea regarding the continuous-fed mode of operation. Any digester may be operated either batch or continuous-fed,although there are additional requirements for the latter. For example, theremust beprovisionso that the slurry fed in one day does not pass out as sludge the following day. Obviouslyit is an advantageto havea sufficientlylong digester. The problem of length canbetackledin two ways.First, avoidthequestionand take anydigester(which should havea length).Sincemost any digester cannot be stretched or contracted to the correct lengthstipdatedby theory, the adjustment comesin the form of the daily feed, also called 34
  • 55. load. A retention time which is basedon batch experiments has to be adopted. Let us say the time adopted is 25 days. Therefore, for a lOOO-literdigester slurry, the daily load of slurry would be 1000 liters/25 days or 40 liters/day. By putting in 40 liters of slurry every day, it will take 25 days for that slurry to reachthe exit end. Second, this time the question is approached head on. Consider again a lOOO-liter digester slurry. A retention time basedon bateu experiments must be adopted, say 20 days this time. Consider the entire digester as consisting of 2Q batches, one for each day. We can conceive each daily batch to be in a container holding 1000/20 or 50 liters. Each container must have practical dimensions, say 50 cm. deep, 50 cm. wide and and 20 cm. “long”. Obviously the length of the desired digester would be 20 times the length, or 400 cm. The complete dimensions of the digester would then be 50 cm. deep, 50 cm. wide and 400 cm. long. The depth and width may be char_gedto more convenient dimen- sions but the length should remain the same for 1000 liters slurry and 20 days retention time. In the preceding discussion it is evident that the value of the retention time is crucial. The retention time normally is selectedfrom any day number within the biopause. There is no way to determine biopause in a continuous-fed digester. The value has to be obtained from a batch operation. It is noticed that the rate of gas production in a continuous-fed digester is generally larger than in batch. The rate of gas production is somewhat higher at the earlier stagesof fermentation at less dilution and with greater proportion of starter. In a continuous-fed operation, the fermenting slurry itself acts asstarter; hence,not only is the relative amount of starter very large, but this kind of starter is also at its most active growth phase. Consider the case when the fermented or fermenting slurry is used as the diluting material for preparing slurries. Since this acts also as starter, the advantage is obvious. This is the situation when there is thorough stirring and it happens in small digesters of cubical or near cubical shape.In digestersthat are long with small cross section, the daily load mixesonly with the previous day’s load or the last two days’ load. TABLE 3-2 Weights of Components in Experimental Slurries of Various Manure-Water Ratios and Starter Percentages.(All Weights in Kg.) . 20% starter 25% starter 33% starter starter soln = 0.54 starter soln = 0.675 starter soln = 0.90 Manure/ H2O manure + H20 = 2.16 manure + H,O = 2.025 manure + Hz0 = 1.8 1:l Manure Water Manure Water Manure Water 1:1.5 1.08 1.08 1.013 1.013 0.90 .90 1:2 0.864 1.296 0.81 1.215 0.72 1.08 1:3 = I 0.72 1.44 0.675 1.35 0.60 1.20 1:4 0.54 1.62 0.506 1.52 0.45 1.35 0.432 1.728 0.405 1.62 0.36 1.44 1 35
  • 56. In batch operation, the starter is the smaller component and is addedto the slurry which is a much larger amount. Thus, when the starter is 20%, the main body of slurry is 80%. In a continuous-fed operation, the situation is the reverse;the slurry amounts to only the daily load or only 1/3Othof the entire digester contents (when retention time is 30 days) but the digester contents act as the starter. It is more realistic to consider, however, that the day’s slurry input mixes with the previous two days’ slurry in the digester, in which case the effective percentage of starter is about 33%. Such large proportion of starter promotes high rates of biogasproduction, ashas beendiscussedearlier. TABLE 3-3 Rate of BiogasProduction for Three Time Periodsand Three Percentagesof Starter. (Rates in Liters Gas Per Day Per Kg. Volatile Solids.) Starter 20% Manure Water 1:l 1:1.5 1:2 1:3 1:4 Average Time period, days O-20 O-30 O-60 9.4 9.6 5.5 10.6 9.9 5.5 10.9 7.8 4.3 12.8 9.4 5.3 15.5 12.2 6.8 11.8 9.8 5.5 Average 15.5 11.1 6.2 General average 13.6 10.5 5.8 36
  • 57. Illustration 1-5: Pilot plant batch-fed digesters Jlldation l-6: Pilot plant conthmm~ d&stem 37
  • 58. Illustration 1-7: First experimental biogasplant at Maya Farms llhtdon l-8: Labora-andmoftbtpRotmforbb researchat Maya Farms 38
  • 59. Chapter IV Raw Materials for BiogasProduction The raw material for biogas production is organic matter. Marsh gas originates from the decomposition of manure, leavesand similar material through the action of bacteria. All organic matter contains carbon; methane and carbon dioxide are carbon compounds. Thus the first requirement of a raw material for biogas production is that it must contain carbon organically bound. This means that such materials as limestone, an inorganic compound which contains about 12% carbon, will not do. The conversion of organic matter to biogas is accomplished through the activities of various kinds of bacteria as discussed in an earlier chapter. The element nitrogen, in combined form, is needed by bacteria for their life processes and hence must also be supplied. A deficiency of nitrogen tends to limit the growth and activities of the bacteria. A large oversupply, however, has been found to be detrimental, causing the liberation of ammonia. Casesof ammonia toxicity have beenmentioned in literature. What is important is the quantity of nitrogen in relation to that of carbon. It is the consensus that to be adequate, the nitrogen should be about equal to 1/3Oth the weight of the carbon, that is C/N = 30 at most. Among biogas raw materials, the source of nitrogen is the protein present; proteins in general contain 16% nitrogen. Table 4-1 givesthe nitrogen content of some known proteins and the C/N values. When the C/N ratios are large, there is too much carbon. The last column of Table 4-l givesthe value of N x 30 or the weight of C neededto increasethe C/N ratio to 30. TABLE 4-l Elemental Composition of SomeProteins 1 Protein Gelatin 49.4 6.8 18.0 Fibril . 52.7 6.8 17.0 Hemoglobin 52.7 7.3 17.7 Casein 53.0 7.0 15.7 Gliadin 52.7 6.9 17.7 E1aStiI-l 51.4 7.0 18.6 S FM 1 5 C/N I Weight of C to make C/N = 30 0.70 25.1 2.74 grams 540 1.10 22.5 3.10 510 0.45 19.5 3.00 531 0.80 22.7 3.38 471 1.03 21.7 3.00 531 0.88 22.1 2.76 558 An idea of the nitrogen content of animal manures, straw, and other possible biogas producers is furnished by Table 4-2. The approximate valuesof C/N are also given. The main source of carbon is organic matter, and the carbon compounds in organic matter arecarbohydrates,fats andproteins.In Table4-3 are given the carbon content of 39
  • 60. ” > .I ,, :_’ ‘- ‘_’ various materials including that of methane, carbon dioxide and butane for comparison. The carbohydrates have a carbon content closeto 44%. Lignin, which is mostly found in wood, has a higher C content but it has beenfound that it is not easily acted on by bacteria. The fats are very rich in carbon but have not beenwell studied as biogas material. The compounds that have received much study and have shown to produce biogas are acetic acid, glycerol, ethyl alcohol, methyl alcohol and other relatively simplecarbon compounds. Returning to the C/N requirement, Table 4-l shows that for the protein known as gelatin,N x 30 = 540; this meansthat a hundred grams of gelatin containing 18 grams N (18% N) can be mixed with a carbohydrate like cellulose (4414%) to obtain a C/N value of 30. The weight of the celluloseis calculated asfollows: Weight of C from 100 gramsof gelatin: 49.4 grams Weight of C from the cellulosematerial: 540 grams - 49.4 grams = 490.6 grams 490.6 Weight of cellulose(44.4% C) containing 490.6 grams of C: m= 1104 grams . Hence a mixture of 100 grams gelatin and 1104grams cellulose hasa C/N value of 30. The situation is reversed in the case of rice straw; the C/N value is 51 and the percentage of carbon and nitrogen are 35.7 and 0.796, respectively. More N should be availableto reduce the C/N to 30. Since the required C/N ratio is 30 and for straw, c/N=51; (C/N) straw 51 (C/N)required = 30 Or l7 The nitrogen content of the straw must be increasedby a factor of 1.7: 1.7 x 0.7 or 1.19 grams. The C/N value in now 30. If ammonium sulfate, 20.2% N, is to be used as N source,then Weight of ammonium sulfatecontaining 1.19grams N 1.19 =-or 5.95 grams 0.202 To calculate how much N is neededby celluloseso that C/N = 30, Table 4-3 provides data. Sincecellulosecontains 44.4% C, 100 grams cellulose need 1.48grams nitrogen. This may be suppliedby urea which contains 46.6% N, 20% C. c/JY = Weight C 44.4 I- 0.2w WeightN = = 30, where W is weight of urea 0.466W W = 3.22grams Urine maybeusedasthesourceof urea It contains(on theaverage)2% urea(w/v) or 0.02 grams/ml., hencethe volume neededto supply 3.22 grams of urea is: 3*22Rrams= 161 d 0.02grams . 40
  • 61. Other natural sources of N may be used. For example, hog dung which contains 2.8% N: 1.50grams 0.028 grams = 53.6 grams hog dung to supply 1.50grams N which areneededby the cellulose in the precedingcase. The large amounts of cellulosic materials left over as residuesby crop plants have been the center of interest in the past, regarding potential for biogas production. The situation has changedand at present, interest and concern have moved to animal manure becauseof a relatively new problem - pollution. Increased population together with migration to the cities has resulted in the commercial-scale raising of food animals. Large numbers are reared and fed in confmement; this has led to accumulation of manure which has become a major pollutant. Fresh manure is difficult to dispose of; it is not easy to incinerate, not only becauseof the amount of water it contains, but also becauseof the foul odor during burning. Disposal by spreadingrequires large areasof land, Lately there have beenseveral symposia in the United Statesand elsewhereon the subject of animal waste disposal. It is now becomingmore and more apparent that oneof the successfuland practical methods is methane fermentation. There have been found several concomitant benefits besides pollution control which aredealt with in the succeedingchapter on sludge. Hog Manure Of the animal manures, hog dung probably presents a representative problem. Since it is a singularly good material for biogas production, it will be discussedlengthily. Tabu- lated in concise form (Table 4-5) are its characteristics. Part I of this table, which gives the amount of dung in relation to hog weight is useful in making estimates of dung pro- duction. Although the data are from American observations, nevertheless they can be taken asa generalguide. Part II, nutrient composition, shows results obtained from the Maya Farms laboratory analysis of hog dung. Part III gives calculated values of certain data of importcuce in biogas production. As has been pointed out earlier, carbon is the key element in biogas formation. This carbon is a part of the volatile solids which is the non-ash constituent of the dry matter of the dung. In current publications the yield of biogas is often quoted on the basis of dry matter; more often, on the basis of volatile .solids. We prefer to use the carbon content asbasis sincebiogas originates from the carbon in the raw material. In Part III of Table 4-5 are given the calculated values of the expectedvolume of biogas from hog dung basedon carbon content. Theseare 200 liters/ kg. fresh dung, 798 liters/kg. dry matter, and 988.5 liters/kg. volatile solids. These volumes are at the temperature range of 30*-34°C and at atmospheric pressure. These values set the upper limit of bio- gasproduction from hog dung. Hmaau Excreta as Biogas Raw Material The questionhas often beenaskedas to the possibility of using human excretafor biogasproduction.This matteris of interestto the personwho wantsto dabblein biogas 41
  • 62. but hasneither animal dung nor crop residues;the only materials readily and constantly availableare fm and urine. The questionwas answered in the afknative long ago. Sewage treatment plants have incorporated the anaerobic digestion step, thereby producingbiogas.The gasis usedin the treatment plant for generatingelectricity. The main raw materials for biogas production nowadays are the various animal manures, also called animal wastesor dung.There appears to be very little study on their nature and composition,yet they present a pollution problem that can be expected to continueto increasewith the expanding population. One would expect animal manure to be a valuable material,considering that reportedly only 16% of the feedgiven to chicken is recovered aspoultry meat and about 20% of the feed given to pigs is recovered as pork. A lot of original animal feed is therefore present in the manure, and its utilization is of importance. The nutrient composition of several animal manures is given in Table 4-2. There is little information on what compounds are actually present. From available data (Conception, 1936; Hobson and Shaw, 1967; and others), the main components are the following: 1. Feed residues,undigested or only partly so, but not absorbed in the digestive tract of the animal 2. Intestinal bacterial cells which may constitute as much as 40 percent of the total solids ofthe manure 3. Intestinal secretions 4. Residuesof bacterial action. Since manure is composed partly of feed that has undergone digestive processesin the animal, it is a unique material that has already undergone partial proteolytic and amyloly- tic action (in the case of ruminants, also cellulolytic). The bacteria not only cause fur- ther chemical changes but also add their cell constituents. The amount of these bacterial cells is considerable,being reported as 20 to 40% of the dry matter of manure. As is to be expected,the composition of manure varies with the kind of animal, age, composition of feed, etc. As far as methane production is concerned, the information needed is what components are sourcesof gas.According to Maya Farms studies,which are discussedin Chapter 5, the main sources are the carbohydrates. The relative weights of components of hog manure are shown in Table 4-4. Regarding the production of biogas from organic matter, it is to be noted that the gas production curves exhibit a characteristic of not dying off abruptly. Gas is produced at a steady rate from the start, up to a falling rate (about l/lOth of previous rate) but not to zero rate. This may be interpreted as continuing gas production from more resistant substrates, probably cellulose and lignin. The less resistant substrates are likely the starches,sugarsand similar compounds. So far our substrate materials have not included the fats and oils, hence no statement can be made about them. Peanut (or ground nut) oil meal was reported as an excellentmethane-producing material in India. It appears that in biogas formation from most organic matter like pig manure, the process consists of two parts: the rapid conversion to gas of the more vulnerable components, chiefly the carbohydrates, followed by a comparatively slower gas 42
  • 63. production from the less fermentable materials at about one-tenth the former rate. The rapid rate lasts anywhere between 15 to 25 days, depending on severalfactors; the slower rate persists for some time, extending even beyond 60 days. An estimate on the relative amounts of organic matter conversionto biogas will be shown in Chapter V. TABLE 4-2 The Carbon/Nitrogen Ratio, Total Solids and Volatile Solids of SomeBiogas-Producing Materials Biogas-producing materials Total solids Volatile solids W) (% of total) C/N % of T.S. s A. Animal Dung 1. Hog 2. Carabao 3. cow 4. Chicken 5. Duck 6. Pugo Household Wastes 25 80.7 38.3 2.8 J3.7 15 80.5 37.0 1.6 23.1 16 77 35.8 1.8 19.9 48 77.4 35.7 3.7 9.65 53 23.6 21.9 0.8 27.4 30 81.8 33.7 5.0 6.74 1. Night soil 2. Kitchen waste C. Crop Residues(air-dry) 1. Corn stalk 2. Rice straw 3. Corn cobs 4. Peanuthulls 5. Cogon 6. Bagasse 15 90 47.7 7.1 6.72 ‘.31 92 54.3 1.9 28.60 86 92 43.9 1.2 56.6 89 79 35.7 0.7 51.0 82 96 49.9 1.0 49.9 90 95.5 52.7 1.7 31.0 - 92.8 1.07 - - 95.5 0.40 - D. Others 1. Kangkong 4 84 33.5 4.3 7.8 2. Water lily 5 77 33.0 2.9 11.4 3. Grasstrimming 15 87 39.2 2.5 15.7 ” 43
  • 64. Material Glucose 40 6.7 53.3 sucrose 42.1 6.4 51.5 Starch 44.4 6,2 49.4 Cellulose 44.4 6.2 49.4 Hemicellulose 45.4 6.1 48.5 Lignin 62.69 5-6.5 26-33.5 Fats 76.79 11-13 10-12 Coconut oil 73.3 11.6 15.0 Acetic acid 40.0 6.7 53.3 Methane 75.0 25.0 0.0 Carbon dioxide 27.3 0.0 72.7 Glycerol ‘e 39.1 8.7 52.2 Ethyl alcohol 52.2 13.0 34.8 Methyl alcohol 37.5 12.5 50.0 Butane (LPG) 82.8 17.2 0.0 Propane (LPG) 81.8 18.2 0.0 TABLE 4-3 Carbon Content of SelectedMaterials Related to BiogasProduction H (%I 0 (%) Weight of N to make C/N = 30 (grams) 1.33L/ 1.40 1.48 1.48 1.51 2.07-2.3 1.53-2.63 2.44 1.3.3 - 1.30 1.74 1.25 - -I1 100gramsglucose umtain 40 grams C and need 1.33grams N so asto havea C/N value of 30. TABLE 4-4 RelativeWeights(Grams)of Componentsof Hog Manure Moisture = 75 Raw Dung = 100 Dry P Ash = 4.825 Matter = 25 Volatile solids = 20.175 Carbon = 9.575 Non-carbon = 10.60 Dry Matter = 100 (in manure) Ash = 19.3 Volatile c Carbon = 38.3 Solids = 80.7 . Non-carbon = 42.4 c Carbon = 47.46 Volatile Solids = 108 Non-carbon = 52.54 .