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2/29/2012

Introduction and Principles of


Anaerobic Digestion

Biogas
Faculty of Biotechnology and Biomolecular Sciences
Universiti Putra Malaysia

History of Biogas
ƒ The potential of biogas was discovered in 1890’s.

ƒ 1808 – Sir Humphrey Davy found that methane was present in the gases that is
formed by the Anaerobic Digestion of manure.
ƒ History of Biogas – what is biogas?
ƒ 1884 – Louis Pasteur presents his students work to the Academy of science and tells
how this gas can be used for heating and lighting. His student, Ulysse Gayon,
ƒ Introduction to biogas system in Malaysia performed the anaerobic fermentation of manure and water at 35ºC and obtained
100 liters of Biogas per cubic meter of Manure.

ƒ National Renewable Energy Policy 2009 ƒ 1895 – Biogas is used to light up the streets in Exeter, England.

ƒ 1940 – Biogas development and Applications lie dormant until the Energy shortages
of the Second World War. The war forces people to look at alternative sources of
ƒ Principles to anaerobic digestion energy again.

ƒ 1957 – A British Inventor, Bates, modifies his car to run on Biogas produced from pig
manure. In 1974 he explains the process and benefits thereof in the Documentary
film "Sweet as a Nut". At that stage he has been running his car on Biogas for 17
years.

ƒ 2005 – The Biogas Support program in Nepal wins the Ashden Reward for installing
over 150,000 Biogas Plants in rural areas. And a Biogas powered train starts it's
service in Sweden.

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What is Biogas? Biogas System in Malaysia

ƒ Biogas is the gas that is produced when organic ƒ In Malaysia, the palm oil industry generates the largest
matter like manure or plant material is digested and volume of organic waste in the form of empty fruit
decomposed by anaerobic bacteria. This gas mostly bunches (EFB), mesocarp fibres, palm kernel shells and
also palm oil mill effluent (POME).
comprise
p of Methane and Carbon Dioxide.
ƒ There are only 24 biogas plants operating nationwide,
ƒ Biogas is also called Landfill gas if it is produced at a representing 5.8 per cent of the total palm oil mills in
landfill or swamp or marsh gas. the country. (EFB and POME as feedstock).
ƒ In India, that has numerous biogas plants in the rural
areas, they call it Gober (Gobar) gas. They estimate
that these biogas plants, that run on cow dung, is More information: refer to Newspaper cutting dated 21-
6-11
installed in over two million households.

National Renewable Energy


Policy 2009
The Policy Vision Anaerobic Digestion
Enhancing the utilisation of
indigenous renewable energy
(RE) resources to contribute ƒ Applications: treatment of solid wastes,
towards national electricity
supply security and sustainable including agricultural wastes, animal
socioeconomic development. excrements, sludge from sewage
treatment plants,
l effluent
ffl from
f food
f d and d
beverage industries and urban wastes.
The Objectives

ƒ To increase RE contribution in the national


power generation mix;
ƒ Much more attractive for tropical and
subtropical-climate countries – Why?
ƒ To facilitate the growth of the RE industry;

ƒ To ensure reasonable RE generation costs;

ƒ To conserve the environment for future


generations; and

ƒ To enhance awareness on the role and


importance of RE.

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Table 1

ƒ Biological conversion in aerobic and anaerobic


systems

Figure 1

Principles of Anaerobic Digestion


1. Hydrolysis and acidogenesis
ƒ Hydrolysis of complex particulate material (polymers) into
simpler dissolved materials (smaller molecules)

ƒ Factors affecting hydrolysis rate:

1. Operational temperature

2. Residence time of substrate

3. Substrate composition

4. Particle size

5. pH

6. Concentration of NH4+-N

7. Concentration of products from hydrolysis (eg. VFA)


Figure 2

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2. Acetogenesis
ƒ Soluble products from hydrolysis are
metabolised and converted by ƒ Generation of products appropriate for
methanogenic microorganisms.
microorganisms into simpler compounds
– VFAs, alcohols, lactic acid, CO2, ƒ Products generated: acetic acid, hydrogen and
Hydrogen, ammonia & hydrogen sulfide, CO2.
besides new cells.
cells ƒ Large amount of hydrogen produced and pH
decreases.

ƒ Only hydrogen and acetate can be directly used


ƒ Acidogenesis – carried out by clostridia by methanogenic microorganisms.
group and the family of
Bacteroidaceaea. ƒ At least 50% of the biodegradable COD are
converted into propionic and butyric acids, later
decomposed by action of acetogenic bacteria into
acetic acid and hydrogen.

3. Methanogenesis Aceticlastic methanogens

ƒ Final phase, degradation of organic ƒ 60-70% of all the methane production


compounds into methane and CO2 by
methanogenic archaea. ƒ Methanosarcina pervails > 10-3 M acetate, while
Methanosaeta prevails < 10-3 M acetate.
ƒ Two main groups of microorganisms:
ƒ The organisms belonging to Methanosaeta are
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1. Acetate-using
Acetate using microorganisms (aceticlastic developed in the form of filaments,
filaments important in
methanogens) – form methane from acetic formation of bacterial texture present in granules.
acid or methanol
ƒ The organisms belonging to Methanosarcina are
2. Hydrogen-using microorganisms developed in the form of coccus, forming “packages”.
(hydrogenotrophic methanogens) – form
methane methane from hydrogen and CO2 Hydrogenotrophic methanogens
ƒ Methanobacterium, Methanospirillum and
Methanobrevibacter.

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4. Sulfate reduction
ƒ Sulfate or sulfite present in reactor can be used by
sulfate-reducing bacteria (SRB).
ƒ End product is hydrogen sulfide.
ƒ Microorganism: Desulfobulbus sp. and Desulfomonas
sp.
sp
ƒ In the absence of sulfate, anaerobic digestion occurs
according to Figure 2.
ƒ With presence of sulfate, metabolic routes change as
shown in Figure 3. SRB compete with fermentative,
acetogenic and methanogenic microorganisms for
substrate available, causing decrease in methane
production.
Figure 3

Methane formation
ƒ Two mechanisms for methane formation:
1. Cleavage of acetic acid and
2 Reduction of CO2
2.
In the absence of hydrogen,

CH 3 COOH ⇒ CH 4 + CO 2

Microbial group involved : aceticlastic methanogenic organisms


Figure 4

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ƒ With hydrogen, methane is formed from reduction of CO2

CO2 + 4 H 2 ⇒ CH 4 + 2 H 2O
Microbial group involved: hydrogenotrophic methanogenic organisms ƒ Methane produced is quickly separated from the
liquid phase due to its low solubility in water.

ƒ This results in high degree of degradation of liquid


The overall composition of biogas produced varies
according to the environmental conditions prevailing in wastes, once gas leaves the reactor to the
the reactor. gaseous phase.

Anaerobic digestion of domestic sewage, ƒ As for CO2, much more soluble in water, and
leaves the reactor partly as gas and partly
Methane = 70-80% dissolved in liquid effluent.
CO2 = 20-30%

Estimation of methane production considering chemical Estimation of methane production considering the
composition of waste degraded COD
The Buswell stoichiometric equation is used for a given
chemical composition of the wastewater:
CH 4 + 2O 2 ⇒ CO 2 + 2H 2 O

(16 g ) + (64 g ) ⇒ (44 g ) + (36 g )


⎛ a b 3d ⎞
Cn H a Ob N d + ⎜ n − − + ⎟ H 2O 1mole of methane requires 2 moles of O2 for complete
⎝ 4 2 4 ⎠
oxidation to CO2 and water. Therefore, every 16 g of
methane produced and lost to the atmosphere
⎛ n a b 3d ⎞
⇒ CH 4 + ⎜ − + + ⎟CO2 + (d )NH 3 corresponds to removal of 64 g COD from waste.
⎝2 8 4 8 ⎠
Under normal temperature and pressure, this corresponds
to 350 ml of CH4 for each gram of COD degraded.

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Therefore,
COD
Exercise 1
=
CH
V CH 4
4
K (t )
Where,

VCH4 = volume of methane produced (L)

CODCH4 = load of COD removed from the reactor and converted into methane (g
COD)

K(t) = correction factor for the operational temperature of the reactor (g COD/L)

P × K
K (t ) =
R × (273 + T )
Where,

P = atmospheric pressure (1 atm)

K = COD corresponding to one mole of CH4 (64g COD/mole)

R = gas constant (0.08206 atm.L/mole oK)

T = operational temperature of the reactor (oC)

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ƒPreliminaries
ƒNutrients
Environmental Requirements ƒTemperature
ƒpH, alkalinity and volatile acids
ƒToxic materials and their control

Preliminaries
ƒ Nutritional and physical conditions enable the selection of organisms
better adapted to the environment, which may vary quickly and
frequently due to changed in the supply of nutrients or in the physical
Nutrients
conditions. ƒ Established from chemical composition of the
ƒ Both physical and chemical characteristics of environment affect microbial cells; determined nutrient requirements
microbial growth. based on empirical composition of the microbial
cells.
ƒ Anaerobic digestion is susceptible to strict control of environmental
conditions, as the process requires an interaction between ƒ The chemical composition of the methanogenic
fermentative and methanogenic organisms. microorganisms is presented in Table
ƒ A successful process depends on an accurate balance of the
ecological system.

ƒ Special attention should be given to methanogenic microorganisms,


as they are considered highly vulnerable to changes in environmental
conditions.

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According to Lettinga et al. (1996), the min nutrient requirements


can be calculated by the following expression:

Table 1

TSS
Where:
Nr = S 0 ⋅ Y ⋅ N bac ⋅
VSS
Nr = nutrient requirement (g/L)
S0 = concentration of influent COD (g/L)
Nbac = concentration of nutrient in the bacterial cell
(g/gVSS)
TSS/VSS = total solids/volatile solids ratio for the bacterial cell
(usually 1.14)

ƒ For biological treatment processes to be successful,


the inorganic nutrients necessary for microbial (a) Nitrogen
growth should be supplied in sufficient amounts.
ƒ Inorganic nutrient required in large concentrations for microbial
growth.

ƒ The following
g nutrients, in decreasing
g order of ƒ Under anaerobic conditions, nitrogen in the forms of nitrite and
nitrate
it t isi nott available
il bl ffor growth,
th as it is
i reduced
d d to
t nitrogen
it
importance, are necessary for nutritional stimulation and released to atmosphere.
of methanogenic microorganisms: nitrogen, sulfur,
phosphorus, iron, cobalt, nickel, molybdenum, ƒ Ammonia and the fraction of organic nitrogen released during
degradation are the main sources of nitrogen used by
selenium, riboflavin and vitamin B12.
microorganisms.

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ƒ Biomass with low yield coefficient (Y~0.05 gVSS/g COD)


(b) Phosphorus
e.g. degradation of volatile fatty acids
Microbial incorporation of phosphorus = 1/5 to 1/7 of that
COD:N:P = 1000:5:1 established for nitrogen.
C:N:P = 330:5:1
Utilise phosphorus in the form of inorganic orthophosphate,
ƒ Biomass with high yield coefficient (Y~0.15 gVSS/g COD) mediated by enzyme phosphatase.
e.g. degradation of carbohydrate
COD:N:P = 350:5:1
C:N:P = 130:5:1

(c) Sulfur Temperature


Sulfur is necessary for protein synthesis.
Use sulfide as source of sulfur; some use cysteine. ƒ The microbial formation of methane may occur in wide
temperature range (0 to 97oC).
If inorganic sulfate is present, it is reduced to sulfide, which then
reacts with serine amino acid to form sulfur containing cysteine ƒ Two ideal temperature levels have been associated with
amino acid
anaerobic digestion, one in the mesophilic range (30
(30-35
35oC),
On one hand, the presence of sulfates can limit the another in the thermophilic range (50-55oC).
methanogenesis, because sulfur-reducing bacteria compete
for substrates such as hydrogen and acetate. ƒ Most of the anaerobic digesters have been designed in
On the other hand, the methanogenic organisms depend on the mesophilic range.
production of sulfides for growth.
ƒ Although high temperatures are desired, maintaining
uniform temperature in the reactor may be more important
(the usual limit is about 2oC per day).

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According to Henze and Harremoes (1983), the maximum


bacterial growth rate decreases 11% per oC, for anaerobic
digesters operated at temperatures below 30oC, as shown by
following expression (van Haandel and Lettingga, 1994):
pH, alkalinity and volatile acids
The pH affects the process in two main ways:

1. Directly:affecting, for example, the enzymes’ activity

Where,
K (t ) = K 30 × 1 . 11 (T − 30 ) by changing their protein structure, which may occur
drastically as a result of changes in pH.

2. Indirectly: affecting the toxicity of a number of


K(t) = growth rate for the temperature (T) compounds

K30 = growth rate for t = 30oC The methane-producing microorganisms have optimum
growth in the pH range between 6.6 and 7.4.
T = temperature (oC) pH below 6.0 and above 8.3 should be avoided, as they
can inhibit methane-forming microorganisms.

The acid-producing bacteria have an optimum growth rate


in pH range between 5.0 and 6.0.

ƒ Sudden pH changes (pH shocks) can adversely affect the process, and
recovery will depend on a series of factors, related to the type of damage
caused to the microorganisms (either permanent or temporary).
Toxic materials and control
ƒ Several organic and inorganic compounds can be toxic or
The recovery will be quicker if: inhibitors to the anaerobic process.
Acid pH shock
ƒ Toxicity by salts is usually associated with cation, and not with
1. The pH drop was not significant. anion of the salt.
2. The p
pH shock had a short duration.
ƒC
Cation
ti t i it ffollowing
toxicity ll i iincreasing
i order
d off iinhibition,
hibiti b
based
d on
3. The VFA concentration during the pH shock remained low. molar concentration: Na+ (0.32 M), NH4+ (0.25 M), K+ (0.15 M),
Ca2+ (0.11 M) and Mg2+ (0.08 M).

Alkaline pH shock ƒ Concentration of free ammonia above 150 mg/L are toxic to
methanogenic microorganisms, while max safety limit for
1. The pH rise was not significant.
ammonium ion is about 3,000 mg/L.
2. The pH shock had a short duration,

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ƒ Sulfides in the form of H2S > 200 mg/L become very toxic.

ƒ Toxic elements and compounds such as chromium, nickel, zinc,


copper, arsenic and cyanides are highly toxic inorganic toxins.

Control methods for toxic materials:

ƒ Removal of toxic material present


•Design of Anaerobic Reactor (UASB)
ƒ Dilution below the toxic limit

ƒ Formation of insoluble complexes or precipitation


•Operation Control
ƒ Antagonisms of toxicity by means of the use of another
compound

Design of Anaerobic Digester Table 2

(UASB as example)

Table 1

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Operational Control of the Start-up of Anaerobic


Treatment System Reactor
Three main treatment system control activities: Can be achieved in 3 different manners:
1. Operation: refers to the daily or periodic activities ƒ By using seed sludge adapted to the wastewater to be
necessary to assure a good and stable
treated: the start-up of the system occurs fast, in a
performance of treatment system
satisfactory, as there is no need for acclimatisation of sludge
2. Maintenance: refers to activities to maintain the
structures in the treatment plant in good ƒ By using seed sludge not adapted to the wastewater to be
conditions treated:goes through acclimatisation period, including a
microbial selection phase
3. Information: refers to communication, preferably
in writing, between the different people involved, ƒ With no use of seed sludge: most unfavourable form to start-
creating, at the same time, a record of the
up the system, time required for retention and selection of
operation and maintenance of the treatment
system large microbial mass can be very long (4 to 6 months)

Procedure preceding the start-up of a reactor

Characteristic of seed sludge

The common objectives to be achieved in the operation of high- Qualitative and quantitative characterisation, including
rate anaerobic processes are: parameters:pH, bicarbonate alkalinity, VFA, TS, VS, and SMA.

Control of solids retention time, the prevention against


accumulation
l ti off iinertt suspended
d d solids
lid iin reactor
t and
d Characteristic of raw sample (waste to be treated) qualitative
development of favourable conditions for mass transfer. and quantitative

Estimate volume of seed sludge necessary for the start-up

It can be estimated based on characteristic analyses of sludge


and influent (raw sample)

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Feeding of reactor with raw sample


Procedure during the start-up of an anaerobic reactor
ƒ After the end of rest period, begin feeding of reactor with
Inoculation of reactor wastewater, until it reaches app half of its useful volume

Can be done with the reactor either full or empty, preferably ƒ Leave the reactor unfed for a 24 hour period. At the end of this
the reactor empty to reduce sludge losses during transfer period, and prior to beginning the next feeding, collect sample
process and analyse the sample: temperature
temperature, pH
pH, alkalinity
alkalinity, volatile
acids and COD.
Follow the following procedures (for empty reactor)
Acceptable values:pH 6.8-7.4 and volatile acid below
ƒ Transfer seed sludge to reactor, ensuring that it is
discharged into the bottom of reactor. Avoid turbulence 200 mg/L (as acetic acid)
and excessive contact with air. Continue the feeding process if all parameters are within
ƒ Leave sludge at rest for an appropriate period of 12 to 24 acceptable ranges.
hours, allowing its gradual adaptation to local temperature.

Table 3

ƒ Continue the filling process of the reactor, until it reaches its


total volume (level of the sedimentation tank weirs)

ƒ Leave reactor unfed again for another 24h. Then, collect new
samples for analyses stated above.

ƒ If parameters are within the ranges, feed reactor continuously


in accordance with amount of seed sludge used and flow
percentage to be applied.

ƒ Implement and perform routine monitoring of treatment

ƒ Increase influent flow gradually, initially every 15 days, in


accordance to system response. This interval can be increased
or reduced depending on the results obtained.

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