Anaerobic Wastewater Treatment

8-Environmental factors I: solids, pH, nutrients,

Prof.Dr.ir. Jules B. van Lier
alkalinity
16-19 July 2012

FACTORS THAT AFFECT THE APPLICABILITY OF ANAEROBIC TREATMENT

• Composition and fluctuations of organic compounds (SS, biodegradability)

• Waste water strength + fluctuations

• Temperature + fluctuations

• Availability of nutrients (N, P, micro-nutrients)

• Buffer capacity / pH

• Presence of alternative electron acceptors (SO4--, NO3-, etc.)

• Risk of formation of inorganic precipitates

• Risk of formation of scum layers and/or flotation layers

• Presence of toxic compounds

• Odor problems

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FACTORS THAT AFFECT THE APPLICABILITY OF ANAEROBIC TREATMENT

• Composition and fluctuations of organic compounds (SS, biodegradability)

• Waste water strength + fluctuations

• Temperature + fluctuations

• Availability of nutrients (N, P, micro-nutrients)

• Buffer capacity / pH

• Presence of alternative electron acceptors (SO4--, NO3-, etc.)

• Risk of formation of inorganic precipitates

• Risk of formation of scum layers and/or flotation layers

• Presence of toxic compounds

• Odor problems

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Impact of Influent Suspended Solids (SS)

Accumulating SS dilutes active methanogenic biomass in sludge bed

Active bacterial granule

Inert suspended solids

1 g VSS 1 g VSS

ACT= 1000 mg COD/g VSS.d ACT= 273 mg COD/g VSS.d

Influent = soluble COD Influent = soluble COD + SS
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Impact of influent suspended solids on applicable loading rate
Applicable organic volumetric loading rates in relation to operational
temperatures for a soluble and a partially soluble waste water in
granular sludge UASB reactors (hydraulic load not restrictive)

temperature organic volumetric loading rate (kg.m-3.day-1)

(°C) waste water with less waste water with
than 5% SS-COD 30-40% SS-COD

15 2 - 3 1.5 - 2
20 4 - 6 2 - 3
25 6 - 10 3 - 6
30 10 - 15 6 - 9
35 15 - 20 9 - 14
40 20 - 27 14 - 18

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High solids content: SRT prime design criterion!

SRT is directly linked to the amount of viable, active biomass in the
system:

SRT (d) = Xreactor · V / (Qeffl · Xeffl. + Qexcess-sludge · Xexcess-sludge),

with X = concentration of viable biomass in kg/m3 (e.g.methanogens).

V = reactor volume (m3)
Q = flow m3/d

SRT is determined by:

- incoming suspended solids

- solids digestion in the reactor
- filtering capacity sludge bed (upflow velocities + sludge characteristics)
- growth and decay of new sludge
- sludge retention in the settler (upflow velocities)
- withdrawal of excess sludge
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SRTmin.  3 * Td (doubling time) of critical biomass (e.g. methanogens)

3
 Required SRT for Hydrolysis in Reactor

180
SRT for stabilized sludge [days]

160

140

120

100

80

60

40

20

10 15 20 25 30 35 40 45

Temperature [°C]

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FACTORS THAT AFFECT THE APPLICABILITY OF ANAEROBIC TREATMENT

• Composition and fluctuations of organic compounds (SS, biodegradability)

• Waste water strength + fluctuations

• Temperature + fluctuations

• Availability of nutrients (N, P, micro-nutrients)

• Buffer capacity / pH

• Presence of alternative electron acceptors (SO4--, NO3-, etc.)

• Risk of formation of inorganic precipitates

• Risk of formation of scum layers and/or flotation layers

• Presence of toxic compounds

• Odor problems

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Temperature

• Affects metabolic activity of bacteria

• Affects transfer and solubility of gases

• Affects settleability of biological solids

• Reaction decreases with decreasing temperature (Arrhenius)

• Final degradation extent is proportional to temperature

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Bacterial Classification on Growth

Temperature
I psychrophilic <20°C
II mesophilic 20-40 °C
III thermophilic >45°C

(arbitrary borders)

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Digestion rate at mesophilic temperatures

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Differences in growth rate mesophiles -

thermophiles

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 Temperature effects on immobilized sludge systems

- Maximum activity determined by

mass transfer limitation
- Under optimum conditions only outer
layer is active
- Decrease in temperature affects
bacterial conversion rate but
‘granule activity’ is not affected
35ºC
30ºC
25ºC
S

d
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FACTORS THAT AFFECT THE APPLICABILITY OF ANAEROBIC TREATMENT

• Composition and fluctuations of organic compounds (SS, biodegradability)

• Waste water strength + fluctuations

• Temperature + fluctuations

• Availability of nutrients (N, P, micro-nutrients)

• Buffer capacity / pH

• Presence of alternative electron acceptors (SO4--, NO3-, etc.)

• Risk of formation of inorganic precipitates

• Risk of formation of scum layers and/or flotation layers

• Presence of toxic compounds

• Odor problems

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 Nutrients

• Need to be present in the right quantities

• Indispensable for good process performance

• Macro-nutrients are needed in larger quantities

• Nitrogen
• Phosphorous
• Calcium
• Magnesium
• Sulphur

• Micro-nutrients (trace elements) are only needed in very small

quantities
• e.g. certain heavy metals

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Requirement Anaerobic Sludge for Macro and Micro Nutrients (heavy

metals)
Based on elemental composition of methane bacteria (Scherer, 1983)
Element Concentration Element Concentration
mg kg-1 dried cell mg kg-1 dried cell

Macronutrients: Micronutrients:

N 65000 Fe 1800
P 15000 Ni 100
K 10000 Co 75
S 10000 Mo 60
Ca 4000 Zn 60
Mg 3000 Mn 20
Cu 10

Conversion factors for methane bacteria cell:

g VSS*1.41 = g COD
g TS*0.825 = g VSS
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 Presence and availability of nutrients
The requirement for N and P can be calculated from the cell
composition. (i.e. 10-12% N and appr. 2% P)

substrate = mixture of volatile fatty acids

growth yield = 0.02 - 0.05 g/g
COD : N : P = 1000 : 5 : 1
C : N : P = 330 : 5 : 1

Level of micro-nutrients
mostly sufficient in agro-
substrate = non-acidified carbohydrates industrial wastewater;
growth yield = 0.10 - 0.15 g/g
For sewage: no problem!
COD : N : P = 350 : 5 : 1
C : N : P = 130 : 5 : 1

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Trace metal requirements

• Fundamental role in microbial growth and metabolism

• Can be toxic in higher concentrations

• Cell composition of micro-organism provides idea of needed

quantities

• Present as metal centre in enzymes or as cofactor

• Different requirements for different processes
• Often these metals are irreplaceable by other metals

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Examples of required trace metals

• Examples of metals in enzymes of anaerobic organisms:

• Cobalt
• Nickel
• Tungsten
• Molybdenum
• Selenium
• Iron
• Copper
• Zinc

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Example of trace metal - Cobalt

Catalytic centre in corrinoid of the enzyme methyltransferase
(corrinoid also referred to as cobalamin or vitamin B12)

• Corrinoids can contain up to 98% of

total cobalt present in organism
Co+

• Content of cobalt in methanogens and

homoacetogens depends on species,
substrate and cultivation condition

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Example of trace metal - Nickel
In cofactor F430 of the enzyme methyl-CoM reductase

• Nickel is also present in many other

enzymes, e.g.:
• urease,
• hydrogenase,
• carbon monoxide dehydrogenase
Ni+

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Addition of trace metals

• The form in which metals will be present depends on:

• chemical properties of the metal
• concentrations of anions
• concentration of complexing agents present
• pH

• Examples of wastewaters with usually sufficient amounts of trace

metals:
• domestic sewage
• agro-industrial wastewater (not all)

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FACTORS THAT AFFECT THE APPLICABILITY OF ANAEROBIC TREATMENT

• Composition and fluctuations of organic compounds (SS, biodegradability)

• Waste water strength + fluctuations

• Temperature + fluctuations

• Availability of nutrients (N, P, micro-nutrients)

• Buffer capacity / pH

• Presence of alternative electron acceptors (SO4--, NO3-, etc.)

• Risk of formation of inorganic precipitates

• Risk of formation of scum layers and/or flotation layers

• Presence of toxic compounds

• Odor problems

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EFFECTS OF pH ON ANAEROBIC DIGESTION

• Direct
• effect on enzyme activity
(charge / tertiary structure of proteins)

• Indirect
• affecting toxicity of various compounds (H2S, NH3, VFA)
• affecting the availability of nutrients
(e.g. by affecting the solubility)
• affecting the availability of substrates (e.g. at pH<6.1, milk
proteins coagulate which makes them less available)
• affecting the availability of CO2
(very low pCO2 at pH>8.0.)

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 pH RANGE METHANE DIGESTION

Hydrolysis
Acidogenesis
Acetogenesis

Methanogenesis
acetate
hydrogen

4 5 6 7 8 9

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Buffer systems

Buffering capacity: capacity of solution to resist pH changes (e.g. added

H+ will be neutralised by buffer system)

N.B.:term for buffering capacity with respect to acids: alkalinity,

Especially brought by bicarbonate

Buffer system is usually brought by: mixture of weak acid and its conjugate
base. The optimum pH of a buffer depends on the pKa/pKb value of the
acid/base applied

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Buffer capacity

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BUFFERS IN AWWT
“Useful” buffers are active in the neutral pH range (6 – 8).

 2
H 2CO3 / HCO3 / CO3 NaAc / HAc
pKa = 6.3 pKa = 10.3 pKa = 4.8

 2 
H 2 PO4 / HPO4 NH4 / NH3
pKa = 7.2 pKa = 9.3

H2 S / HS 
pH = pKa + log (A-/ HA) pKa = 7.1

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Buffer index
Buffer indexes as a function of pH for acid/base systems likely to occur in
anaerobic treatment plants

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Alkalinity

• Capacity of the wastewater, or reactor liquid, to take up protons

• Assessment: amount of acid needed to titrate the sample until pH of 4.0

• At pH=4.0 all inorganic carbon is present as CO2 → minimum buffer

index

• Original sample pH ~ 7.0 → alkalinity practically equivalent with the

concentration of bicarbonate → bicarbonate alkalinity

• If other weak acids (VFA!) are present → total alkalinity

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 Bicarbonate alkalinity

Bicarbonate is generated in the digestion process itself (metabolism

generated alkalinity)

CH3COO- Na+  CH4 + HCO3-

If a solution of 5 g NaAc is digested the produced alkalinity is 5/82 = 60

mmol or 60 meq HCO3-.

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CO2 / HCO3- / CO32- as a function of pH

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 HENRY’S LAW

CO2 (g)

CCO2(l) = H . PCO2

CO2 (l)
+
H2O CO3- + 2 H+

H2CO3 HCO3- + H+

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PREDICTING THE pH


[H ]  [HCO3 ]
Ka  [H ]  [HCO3 ]

[H2CO3*] [H2CO3*]   KH  PCO2
Ka
[H2CO3*]  KH  PCO2

KH  PCO2  Ka
[H ]  
[HCO3 ]
Where; KH=(H*R*T)-1= henry’s constant (M atm-1)
H=henry’s factor =[CO2]g/[H2CO3]aq=1.2
R=0.082057 atm deg-1M-1
T= degrees Kelvin (°C+273)
PCO2= partial pressure CO2 atm= (%CO2)/100
Ka= dissociation constant H2CO3=10-6.3
[HCO3 -]=bicarbonate alkalinity (M)=[ALK]-[VFA]

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  K H  PCO2  Ka
[ HCO3 ] 
[H  ]

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Role biogas CO2 and reactor alkalinity on

reactor pH

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 Metabolism Generated Alkalinity (digestion of protein)

C3H7O2N  2H2O  CH4  2CO2  NH3

 
C3H7O2N  2H2O  CH4  CO2  HCO3  NH4 (pH = 7)

Assume wastewater contains 2 g/l proteins (~C3H7O2N)

MW= 89 g
1 mole C3H7O2N => 1 mole NH4+-N
2/89 mole =>2/89 mole NH4+-N, or 22 mmole or 22 meq NH4+-N
This will “bind” 22 meq HCO3-

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Metabolism Generated Alkalinity

Sulphate and sulphite

4H 2  SO42  CO2  HS   HCO3  3H 2O


CH3COO  SO42  2HCO3  HS 


2CH3COO  4HSO3  3HCO3  4HS   3H 2O  3CO2

Note: reactor pH = 7-8

Anions have cationic counter-ions

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Metabolisms that do not generate
Alkalinity

• Carbohydrates
• Sugars
• Organic acids
• Aldehydes
• Ketones
• Esters

Generally: If no cation is released from the organic compound then

no alkalinity is generated

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Anaerobic Conversion of Organic Matter

Organic Polymers
proteins carbohydrates lipids
Hydrolysis
Mono- and oligomers
amino acids, sugars, fatty acids
Acidogenesis

Volatile Fatty Acids

Lactate
Ethanol
Acetogenesis

H2 / CO2 Acetate

Methanogenesis
CH4 / CO2

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 Kinetic Properties Acidifiers / Methanogens

Process Rx Y Ks -max
gCOD/g g VSS/g mg Day-1
VSS/d COD COD/l

Acidogenesis 13 0.15 200 2.0

3 0.03 30 0.12
Methanogene
sis

Overall 2 0.03 – - 0.12

0.18
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Overloading may lead to process deterioration: The vicious circle

Methane Poor
Capacity Buffering
Exceeded Capacity

Methanogenic Toxicity
VFA Increasing
increases

pH Unionized VFA
decreases increasing

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 Reactor Monitoring

In order to prevent process deterioration by pH drop, reactor

monitoring is of prime importance

COD gas

Anaerobic
COD influent COD effluent
reactor
Effluent VFA !!

COD sludge

CODinfluent = CODeffluent + CODgas + CODsludge

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