KINETICS AND MODELING OF CONVENTIONAL SEPTIC SYSTEMS

TREATING BLACK WATER

by

Eric Ntamukunzi

Thesis proposal submitted in partial fulfillment of the requirements for the

Master degree in Urban Water Engineering and Management

Examination Committee: Dr. Thammarat Koottatep (Chairperson)

Dr. Tineke Hooijmans (Co-Chairperson)
Prof. Ajit Annachhatre
Dr. Sutat Weesakul

Nationality: Rwanda

Previous Degree: Bachelor of Engineering in Civil

Engineering
National University of Rwanda, Rwanda

Scholarship Donor: BMGF

Asian Institute of Technology

School of Environment, Resources and Development
Thailand

October 2013
Table of Contents
Title page ........................................................................................................................................... i
Table of Contents .............................................................................................................................. ii
List of tables ......................................................................................................................................iv
List of figures ..................................................................................................................................... v
List of abbreviations ..........................................................................................................................vi
1. INTRODUCTION ......................................................................................................................... 1
1.1. Background ........................................................................................................................ 1
1.2. Problem statement ............................................................................................................ 2
1.3. Present state of research ................................................................................................... 2
1.4. Research questions ............................................................................................................ 3
1.5. Previous work by other researchers and in AIT ................................................................... 3
1.6. Objectives of the research .................................................................................................. 3
1.6.1. General objective ....................................................................................................... 3
1.6.2. Specific objectives ...................................................................................................... 3
1.7. Scope of the research ......................................................................................................... 3
2. LITERATURE REVIEW .................................................................................................................. 5
2.1. Black water characteristics ................................................................................................. 5
2.1.1. Definition of BW ......................................................................................................... 5
2.1.2. Different values/concentrations of BW constituents ................................................... 5
2.1.3. BOD, COD, TKN, P, BMP .............................................................................................. 6
2.2. Conventional septic tank systems (CSTS) ............................................................................ 7
2.2.1. Definition of CSTS ....................................................................................................... 7
2.2.2. Physical scenarios within a CSTS ................................................................................. 7
2.2.3. CST effluent quality .................................................................................................... 9
2.2.4. Design and maintenance of a CST ............................................................................... 9
2.3. AD processes, kinetics and modelling ............................................................................... 11
2.3.1. Description of AD processes and inhibition within a ST ............................................. 11
2.3.2. Modeling and kinetics............................................................................................... 13
2.3.3. Important physical parameters ................................................................................. 17
3. METHODOLOGY ....................................................................................................................... 21
3.1. Framework for the methodology ...................................................................................... 21
3.2. Collection, Sampling and experimentation ....................................................................... 22
3.3. Analysis ............................................................................................................................ 25

ii
4. EXPECTED RESULTS .................................................................................................................. 26
Time table ....................................................................................................................................... 27
Budget ............................................................................................................................................ 28
References: ..................................................................................................................................... 29

iii
 List of tables

Table Title Page

2.1 Black water composition 5
2.2 The nutrients in the urine mixture, the separated solids, the separated water and the 6
faecal water after the non-diverted urine was deducted and added to the urine mixture,
if 24 h per day were spent at home

2.3 Septic tank effluent quality 9

2.4 Total solids components of "modern" domestic wastewater 11
2.5 Common VFA intermediates and major mechanisms of methane formations 13

2.6 Estimates of Methane Emission Rates from Septic Tank Liquid Surface 13

2.7 Biochemical rate coefficients and kinetic rate equations for particulate and soluble 16
components in the simplified mathematical model

2.8 Comparison of the performance of mesophilic and thermophilic anaerobic digestion 19

iv
 List of figures

Figure Title Page

2.1 Process schematic of properly operating septic tank 7

2.2 Description of settling phenomena in septic tanks per ideal settling theory 8

2.3 Rate of septage (sludge/scum) accumulation (95% of confidence) 10

2.4 Anaerobic degradation phases of organic matter 12
2.5 Schematic overview of the anaerobic dynamic modeling procedure 14
2.6 Relative growth rates of psychrophilic, mesophilic and thermophilic methanogens 17
after Wiegel
3.1 Framework of the methodology 21
3.2 Batch setup for BMP test/Vessels immerged in heated water bath 23
3.3 Lab scale ST for experiments 24

v
List of abbreviations

WWTP: Wastewater treatment plant

CSS: Conventional septic systems

BW: Black water

GW: Grey water

AD: Anaerobic digestion

g.p-1y-1: Grams per capita per year

CSS: Conventional Septic System

CST: Conventional Septic Tank

AnMO: Anaerobic microorganisms

CSTS: Conventional septic tank systems

HRT: Hydraulic retention/resident time

OLR: Organic loading rate

VFA: Volatile fatty acid

BOD: Biochemical oxygen demand

COD: Chemical oxygen demand

TKN: Total Kjeldahl Nitrogen

BMP: Biomethane Potential

vi
 CHAPTER 1

1. INTRODUCTION

1.1.Background

The Conventional Septic tank system has been utilized for long and is still in use as a
standard technology to treat/stabilize black water and generally household wastewater in
many villages and cities due to the low cost of construction, operation and maintenance with
easy disposal of low amount of sludge. BW being a wastewater coming uniquely from toilets
and thus comprises urine, faeces, toilet paper and flushing water. BW contains most of the
nutrients, around half of the domestic COD load, the major part of the pathogens; this reason
makes inevitable the treatment for the environment protection (Otterpohl, 2002; Vinnerås et
al. 2006).

Today about 2.4 billion people in rural and urban areas do not have access to adequate
sanitation services. Within 20 years, it is expected that an additional 2 billion will live in
towns and cities, mainly in developing countries, demanding sanitation. Still over 90% of
sewage in developing countries is discharged untreated, polluting rivers, lakes and coastal
areas (Langergraber et al., 2004)

To emphasize the importance of these CST even in developed countries, many examples are
found in literature. As an illustration, the septic tank is the essential component of the small
scale decentralized wastewater management option utilized by approximately 25% of the US
population (Seabloom, Bounds, Loudon, 2004)

The CST systems technology is even more attractive as the initial capital cost of installing
piped sewerage networks often makes centralized systems too expensive to be an affordable
or viable option. Yet, when a community builds a piped network, it is not always
accompanied by a wastewater treatment system: 90% of the wastewater in developing
countries discharges into receiving water bodies untreated. Other disadvantages of
conventional forms of centralized sanitation include large operation and maintenance costs,
high rates of water consumption, frequent service to the wealthy and neglect of the poor. In
developing countries, CSTS offer a viable alternative to conventional systems for dispersed
rural populations and informal urban/peri-urban settlements due to its low cost and limited
use of technology (P. Alekal, 2005).

For the residential dwellings existing in a variety of forms, such as single and multiple family
households, apartment houses, cottages or resort residences, isolated villages and hamlets; a
well designed septic tank has virtually all the advantages of a sewer connection.

However, the effluent from a septic tank still contains high concentrations of pathogenic MO,
BOD, nitrogen and phosphorus which are a compromising problem for the discharge in the
receiving environment. (ES Reviews No.7/8, 1982). That problem is even worse because of its
susceptibility when the engineering and environmental parameters changes; it’s affecting
severely the effluent quality. Thus, The onsite anaerobic digestion of WW, due to low
consumption of energy and low sludge production, smaller space requirements and lower

1
overall costs, is more suitable for remote areas and villages (Demirel and Yenigun, 2002; Ahn
et al., 2001; Ligero et al., 2001; Lema and Omil, 2001; Lettinga and Hulshoff, 1991,
Luostarinen et al.2006).

By using the modelling we can enhance comprehension in terms of temperature effect, the
OLR, the required HRT, MO effect, within the system and the conceptual ideas to be
considered for the events happening in the reactor. The problem of information not appearing
for a pilot scale is resolved by modelling and feasible solutions can be explored evenly
without other studies. The modelling of the reactor operation is supplemented with
hypothetical computer simulations to illustrate the influence of the above parameters on the
anaerobic septic reactors. The hydraulic residence time is an important engineering parameter
to consider as input to the model at the same extent as temperature, characteristics of sludge,
sludge retention time, flow pattern, inhibition factors, biochemical processes, etc. The
optimum range of values can be achieved after the model calibration, validation and
simulations.

1.2.Problem statement

It is well established that a properly designed septic tank performs efficiently in the removal
of settleable matter and its settleable biochemical oxygen demand (BOD) components (ES
Reviews No.7/8, 1982).

Unfortunately some factors are compromising the performance of this system; the instability
is the result of complex mechanisms of the system and its behaviour. In addition to the non-
stable system, high concentrations of nutrients (Ammonia, phosphates) are released in the
effluent which can contribute, depending on the concentration and volume, to the
eutrophication in the receiving environment. The temperature and HRT seems to be
important parameters affecting the performance of the ST.

While many different anaerobic models have been devised over the years, their use by
engineers, process technology providers and operators has been very limited. Two of the
limiting factors have likely been the wide variety of models available and often their very
specific nature (D.J. Batstone et al, 2002).

1.3.Present state of research

The application of the anaerobic treatment process in waste management includes septic
tanks (for on-site systems). These applications are in various stages of development, from
proven technologies (e.g. septic tanks and sludge stabilization), to several developing
technologies (W. Parawira, 2004)

The Anaerobic digestion is proven to be a robust and efficient technology for the energetic
valorization of various types of biomass; including organic wastes (J. Lauwers et al., 2013),
reason why many researchers are focusing on the optimization of energy recovery but also
the performance of the these CSTS.

2
 1.4.Research questions

- How is the effluent quality from the conventional septic tank treating black water?
- What are the characteristics of black water?
- What is the optimum amount of methane produced during the overall AD process of
black water under mesophilic conditions (around 400C)? In other words, what is the
hydrolysis rate/bio-degradability of BW within a ST operated at mesophilic
conditions?

1.5.Previous work by other researchers and in AIT

In AIT the related research is focusing on the susceptibility of conventional septic systems
treating black water due to bio-chemical, physical, environmental and engineering
parameters. The ongoing researches focus on optimization and modeling for better design and
control of these systems seen their importance as a cheap solution to the sanitation problems
in developing countries.

1.6.Objectives of the research

1.6.1. General objective

Develop an understanding of the dynamic behaviour of conventional septic tanks for

optimizing the existing processes and extend potential application in designing, monitoring
and control requirements.

1.6.2. Specific objectives

- To gather a data set on the response of a conventional septic tank in terms of methane
production. As result for AD process, this process shows the overall performance of
the ST;
- To compile a mathematical model describing the observed process responses: set up a
model, calibrate and validate it;
- To utilize the modelling and data set to optimize the performance of the system;
- By using modelling; determine critical areas for further research on operation and
control of septic systems;

1.7.Scope of the research

This research is carried out in AIT where the experiments have to be made. The black water
used is a combination of urine, faeces and flushing water collected from households
surrounding AIT. From the batch experiments, using the BMP, the amount of methane is
determined. The batch tests are carried out using the vessels/septum bottles in the laboratory
where the temperature and all experimental conditions are set up. The temperature to be
considered for this research is 400C.

3
In the lab scale experiments, many parameters will be determined (BOD, COD, TS, VSS,
VFA, TKN, CH4) and the samples will be taken from the household black water collected for
this issue. Obtained values will be used as inputs for determination of the kinetic coefficients
to build a mathematical model which makes easier the behaviour prediction of the system.
The Monod model, first order kinetics, will be utilized for this point; the calibration will be
done using the data from two lab scale septic tanks operating at ambient and 400C
temperatures.

4
 CHAPTER 2

2. LITERATURE REVIEW

2.1. Black water characteristics

2.1.1. Definition of BW

The wastewater generated at household level consists of black water (BW) and grey water
(GW). Usually the BW is highly concentrated in terms of nutrients, organic matter and
pathogens.

Black water is a mixture of faeces, urine and flush water. A large fraction of the main
components of domestic wastewater, viz. organics, nutrients (nitrogen, phosphorus, and
potassium), pathogens, pharmaceuticals residues and hormones are originally present in a
very small volume of faeces and urine.
2.1.2. Different values/concentrations of BW constituents

The concentration of black water can be influenced by the choice of human excreta collection
system and the life style while Grey water is a voluminous stream characterized by lower
concentrations (and even absence) of some components in comparison with black water (K.
Kujawa & G. Zeeman, 2006). The table 1 below shows concentrations of organic matter and
nutrients for domestic BW:

Table 2.1: Black water composition; all values given in mgl-1(Ellen van Voorthuizen et al.,
2008)

Urine is the first contributor for the nutrients where the second largest contributor of nitrogen
and phosphorus to household wastewater is faeces. (B. Vinnerås, H. Jönsson, 2002)

5
Table 2.2: The nutrients in the urine mixture, the separated solids, the separated water and
the faecal water after the non-diverted urine was deducted and added to the urine mixture, if
24 h per day were spent at home (g p-1y-1) (B. Vinnerås, H. Jönsson, 2002)

Most of the organic material, nutrients and pathogens in domestic wastewater are in BW:
51% of COD, 91% of nitrogen, 78% of phosphorus (Luostarinen et al., 2006).

2.1.3. BOD, COD, TKN, P, BMP

The COD (chemical oxygen demand) test is used to determine the oxygen equivalent of the
organic matter that can be oxidized by a strong chemical oxidizing agent (potassium
dichromate) in an acid medium. The COD of a waste, in general, will be greater than the
BOD5 (biological oxygen demand measured at 5 days) because more compounds can be
oxidized chemically than can be oxidized biologically and because BOD 5 does not equal
ultimate BODu. The COD test can be conducted in about three hours. If it can be correlated
with BOD5, it can be used to aid in the operation and control of the wastewater treatment
processes.

Total Kjeldahl nitrogen (TKN) is a measure of the total organic and ammonia nitrogen in the
wastewater. TKN gives a measure of the availability of nitrogen for building microbial cells,
as well as the potential nitrogenous oxygen demand that will have to be satisfied.

Phosphorus (P) may appear in many forms in wastewater. Among the forms found are the
orthophosphates, polyphosphates, and organic phosphate. Together, these are referred to as
"total phosphorus (as P)” (Mackenzie L. Davis, 2010).

In the laboratory the analysis will be conducted with standardized methods (APHA 2005).

Dietary consumption of heavy metals, especially those such as lead, mercury and cadmium
that are nonessential, is low, leading to low concentrations in the excreta. A rule of thumb
which is often given is that more than 90% of the heavy metals consumed, both ingested and
inhaled, are excreted in the faeces. The main proportion of heavy metals consumed passes
through the intestines without being metabolized. Major sources of heavy metals in the solid
biodegradable waste and wastewater flows are dust, dyes and cutlery. This is one of the
reasons why the major proportion of the heavy metals is found in the black water. These
metals are forming insoluble complexes in the ST and accumulate (B. Vinnerås et al., 2002).

The biomethane potential (BMP) is a standard method used to measure the amount of
methane produced by a given amount of substrate. To conduct this analysis the vessels with a
volume between 100mL and 1000mL have to be used. The inoculums should be fresh from
sludge reactors, then degassed in order to deplete the residual biodegradable organic material
present in it.

6
 2.2.Conventional septic tank systems (CSTS)
2.2.1. Definition of CSTS

A Water-tight, covered receptacle designed and constructed to receive the discharge of

sewage from a building sewer, separate solids from liquid, digest organic matter and store
digested solids through a period of detention, and allow the clarified liquids to discharge for
final disposal (ES Reviews, 1982).

STs are used for wastewater with high concentrations of settleable solids from households
especially in black water. A well constructed and maintained septic tank can remove 70 to
90% of BOD (L. Sasse, 1998).

Figure 2.1: Process schematic of properly operating septic tank (adapted from Victor A.
D’Amato, PE et al., 2008)

This system is used worldwide whereas it is compact, robust and in comparison to the cost of
its construction, extremely efficient. It is basically a sedimentation tank in which settled
sludge is stabilized by anaerobic digestion. Dissolved and suspended matter leaves the tank
more or less untreated.

2.2.2. Physical scenarios within a CSTS

The treatment principles, namely the mechanical treatment by sedimentation and the
biological treatment by contact between fresh wastewater and active sludge complete each
other in the CST. When the flow is smooth and undisturbed, the optimal sedimentation takes
place and the storage space is for the very complex physical, chemical, and biological
processes occurring.

Biological treatment is optimized by quick and intensive contact between new inflow and old
sludge, particularly when the turbulent flow occurs. The way the new influent flows through

7
the tank decide which treatment effect predominates. With smooth and undisturbed flow, the
supernatant (the water remaining after separation with settleable solids) leaves the septic tank
rather fresh and odourless, implying that degradation has not started yet. With turbulent flow,
degradation of suspended and dissolved solids starts more quickly because of intensive
contact between fresh and already active biomass. However, since there is not enough
“calmness” for sedimentation, more suspended solids are discharged with the effluent due to
the turbulence. The effluent stinks because active solids that are not completely fermented
leave the tank (L. Sasse, 1998).

In BW, a heavy scum consisting of matters lighter than water normally forms near the inlet as
top layer. A larger portion of the floating scum consists of sludge particles which are released
from the bottom and driven to the top by gas production. New sludge from below lifts the
older scum particles above the water surface where they become lighter due to drying.
Therefore, scum accumulates and must be removed regularly. Scum does not harm the
treatment process as such, but it does occupy tank volume (Seabloom et al., 2004; L. Sasse,
1998).

While generally thought as a very simple concept, the septic tank is actually a very complex
physical, chemical and biological processing unit. The septic tank provides for the separation,
storage, and digestion of suspended solids as well as for the growth, reproduction and death
of large numbers of anaerobic organisms. BOD removals of 50 to 60 percent and total
suspended solids removals between 60 to 80 percent are easily accomplished (Seabloom et
al., 2004).

The figure 2 below shows the sedimentation phenomena in a ST:

Figure 2.2: Description of settling phenomena in septic tanks per ideal settling theory (Victor
A. D’Amato, PE et al., 2008)

8
Generally the ST should have more than one tank; the first is more voluminous as the amount
of sludge settled there is high. The other chambers play the role of calming the turbulence
and enhance the treatment. Periodical disludging is required (3 years for example depending
on the regulations locally, period from 1 to 3 years is also applicable) to remove the
accumulated settleable solids and floating scum.

2.2.3. CST effluent quality

The effluent quality of a CST can be summarized in the table 3 below. The range values
compiled from two authors are given.

Table 2.3: Septic tank effluent quality (Thammarat K. et al., 2011)

Typically, the ST is weak in terms of pathogens removal. The use of chemicals in toilet
cleaning at normal or recommended levels do not appreciably impact septic tank
performance, but these chemicals have severe detrimental effects when disposed off down the
drain or otherwise used at higher than recommended levels (Victor A. D’Amato, PE et al.,
2008).

2.2.4. Design and maintenance of a CST

 Factors to be considered for design

The following data is indispensable to the design of a ST:

- Daily wastewater flow; this gives idea on the volume of the tank considering the fixed
HRT (in hours or days, but generally not less than 1 day) and the sludge loading
rate/accumulation calculated from the number of users. The sludge accumulation
depends upon the materials used for anal cleansing as well as the volume of
blackwater received by the tank;
- Proper placement of inlet and outlet devices and adequate sludge and scum storage
space to prevent the discharge of sludge or scum in the effluent;

9
 - Since the digestion process is anaerobic, no direct ventilation is necessary. However,
provision should be made for the escape of the gases produced in the tank (L. Sasse,
1998).

The literature is giving more details on the standard dimensions for ST, the material to be
used for construction (concrete, bricks, etc). Generally, different sizes are given by
multiplication of the individual number with and the average WW production.

To increase the efficiency a multi-baffled septic tank can be constructed; the space needed
and the cost will increase in that case. This ST can be used for anaerobic degradation of
suspended and dissolved solids.
 Maintenance of CST and Solids Accumulation Rates

Anaerobic tanks would need to be de-sludged at calculated intervals (1 to 3 years). After that
period the sludge volume is high and there is a need of more space in the ST. Treatment is not
interrupted during de-sludging. Normally, sludge is drawn from anaerobic digester with the
help of portable sludge pumps, which discharge into movable tanks (L.Sasse, 1998).

Predicting scum and sludge accumulations in order to determine septage pumping intervals is
possible using data collected in various studies of septic tanks. The study most commonly
cited is by Weibel, Bendixen and Coulter for the U.S. Public Health Service (1955). Sludge
and scum accumulation rates, established with a high level of confidence (usually 95
percent), are used to estimate the frequency of septage removal, see figure below.

These curves represent the gallons per person that have accumulated at any given time in
years, so they can be used to project pumping intervals for any occupancy and size or shape
tank, including compartmented tanks.

Figure 2.3: Rate of septage (sludge/scum) accumulation (95% of confidence) (Bounds, T.R,
1997)

10
The amount of solids in different households wastewater can be presented in the table below:

Table 2.4: Total solids components of "modern" domestic wastewater (L. Sasse, 1998)

2.3.AD processes, kinetics and modelling

2.3.1. Description of AD processes and inhibition within a ST
The AD of complex substrates containing carbohydrates, proteins and lipids such as domestic
wastewater is a multi step process of series and parallel reactions as presented in Figure 3.
These biochemical and physicochemical processes are commonly classified into the
following major four stages where the end products are CH 4, CO2 and H2O.

- Disintegration and hydrolysis: Complex organic matter (proteins, carbohydrates,

and lipids) is broken down within an extracellular process into organic material with
smaller particles which can be further hydrolyzed (disintegration). Particulate organic
matter is converted by extracellular enzymes to monomeric or dimeric components,
such as amino acids, single sugars and long chain fatty acids (LCFA). Such
compounds can pass through the cell membrane (hydrolysis). These hydrolytic
enzymes are secreted by microorganisms, present in the bulk liquid or attached to
particulates;
- Acidogenesis: Hydrolysis products are fermented or anaerobically oxidized to
volatile fatty acids, VFA (e.g. acetate production by homoacetogenesis bacteria),
propionate, butyrate, valerate, etc), alcohol and ammonia;
- Acetogenesis: Alcohol and VFA are converted to acetic acid or hydrogen and carbon
dioxide;
- Methanogenesis: Acetic acids, carbon dioxide and hydrogen are converted to
methane and carbon dioxide by acetoclastic methanogens (C. Wendland, J. Lauwers
et al, 2013; Y.J. Chan et al., 2009; Seghezzo L., 2004). Dissolved hydrogen is a key
variable in the digestion process: high concentrations inhibit the
acidogenesis/acetogenesis phases while it is a necessary component in
hydrogenotrophic methanogenesis. Therefore, hydrolysis is often considered as the
rate limiting step for anaerobic digestion (Sari Luostarinen, 2005). When the
acidogenesis rate is more than methanogenesis we have increase of VFA. Generally,
the alkalinity of domestic wastewater is high enough to provide a stable AD process.

At the beginning of the AD process, the fats remain intact. Generation of organic acids is
accompanied by a reduction in pH and potential inhibition of further bacterial
decomposition. Breakdown of amino-acids liberates ammonia which has a tendency to
raise the pH to a favorable level for methanogenesis bacteria. Anaerobic digestion in the
settled sludge layer generates gas bubbles that potentially carry microorganisms as they

11
 rise, seeding the liquid zone between the sludge and scum layers and facilitating
decomposition of the soluble organic material in the bulk liquid. In properly operating
septic tanks, three distinct vertically oriented layers should form: a floating scum layer, a
relatively clear layer in the middle, and the lower settled sludge layer. The clear zone is
generally anoxic, containing bound oxygen, with moderate oxidation reduction potential,
while the sludge and scum layers are more strictly anaerobic, containing no free or bound
oxygen and exhibiting a highly negative oxidation reduction potential. The clear zone is
anoxic due in part to the introduction of oxygen-rich influent into that zone. It may take
several years to develop volatile organic acid and metabolite concentrations suitable for a
stable methanogenic population and optimum digestion, depending on the design of the
tank and the characteristics of the WW feed.

Small amount of nutrients is removed by settling of solids; the biological uptake is

occurring. However because some of the accumulated solids will subsequently be
digested, a portion of the associated nutrients will be resolubilized, restricting the total
reductions achievable. Total nitrification, denitrification and ammonia volatilization in ST
do not appear to have been quantified. Thus, the STS don’t remove a significant amount
of nutrients (N and P) (Victor A. D’Amato, PE et al., 2008).

The principal of anaerobic degradation process can be shown in the figure below, the
percentages being the estimates of conversion:

Figure 2.4: Anaerobic degradation phases of organic matter (Sari Luostarinen, 2005, M.
Henze, D. Brdjanovic et al., 2008)

Examples of produced acids during the AD processes are given below:

12
Table 2.5: Common VFA intermediates and major mechanisms of methane formations (Perry
L. McCarty, 1964)

Chemical formula Major Mechanisms of

VFA Methane formation

Formic Acid HCOOH Acetic acid cleavage:

CH3COOH CH3COOH→ CH4+CO2
Acetic Acid
CH3CH2COOH
Propionic Acid
CH3CH2CH2COOH
Butyric Acid
CH3CH2CH2CH2COOH Carbon dioxide reduction:
Valeric Acid CO2+8H→CH4+2H2O
(CH3)2CHCH2COOH
Isovaleric Acid
CH3CH2CH2CH2CH2COOH
Caproic Acid

The methane production estimate per individual daily is given in the table below:

Table 2.6: Estimates of Methane Emission Rates from Septic Tank Liquid Surface
(Thammarat K. et al., 2011; Thammarat K. et al., 2011)

A well understanding of anaerobic processes kinetics helps for a good design, performance
optimization and control/operation of the treatment system; we can also predict the effluent
quality, system stability and waste stabilization.

2.3.2. Modeling and kinetics

2.3.2.1. Modeling theory

Modeling part is very important while it’s making easy the design, predictions and control of
wastewater treatment especially for AD.

Almost, for setting up a model the important steps to follow are shown in this section:

- Accuracy and model complexity (the latter is determined by the number of state
variables and parameters included). The meaning is that complex models don’t give
every time better results; a good choice of parameters is more than enough

13
 - The parameter selection for calibration. Principally, this selection should be based on
an evaluation of the identifiability of the specific parameters;
- The data collection, i.e. experimental measurements;
- Accuracy estimation; at this point many tests are carried ;
- Calibration and Validation is the last step before use of the model (J. Lauwers et al.
2013).

In recent years many mathematical models have been developed. Due to the high complexity
and non-linearity of processes in the anaerobic reactor, mathematical models enable the
representation of the main aspects of a biological system. They improve the understanding of
the system, the formulation and validation of some hypothesis, the prediction of the system’s
behavior under different conditions, reducing, consequently, the experimental information
requirements, costs, risk and time. The whole modeling process (selecting a model structure,
identifying the parameter values, and planning the experimental measurements) should be in
coherence with the objective pursued. In general, the three most common objectives of using
a model are: understanding the system’s behavior and interaction of components;
quantitatively expressing or verifying our hypothesis and predicting the behavior of the
system in the future or under other similar circumstances. (i) simplicity, the model should be
as simple as possible; (ii) causality, the model should represent the most relevant cause effect
relationships; (iii) identifiability, the values of the unknown parameters should be identifiable
from the available data; and (iv) predictive capability, the model should remain valid under
future or alternative reasonable conditions. Models contain unknown parameters, e.g., initial
conditions, and kinetic parameters which have to be estimated from experimental data.
Parameter identification is a delicate task due the potentially large number of parameters and
the scarcity of informative experimental data (J. Lauwers et al. 2013; A. Donoso-Bravo,
2011).

Figure 2.5: Schematic overview of the anaerobic dynamic modeling procedure (J. Lauwers et
al. 2013).

14
In general, there are two types of model classifications: dynamic or non-dynamic and white-
box, grey-box or black-box. The first refers to the time-frame of the model predictions.
Dynamic models are capable of making predictions continuous in time or at least at regular
discrete intervals, while the non-dynamic models only predict time-independent variables.
The distinction between white-box, grey-box and black-box models is based on the amount of
a priori information included. White box models are deductive, and use a priori information
to describe the biochemical reactions occurring during digestion. In contrast, black-box
models, or data-driven models inductively link the input directly to the output without
including any prior knowledge of the physical and chemical reactions occurring. Grey box or
mechanistically inspired models are those in which the parameters have a physical
interpretation but are adjustable, for instance by a parameter estimation procedure. This is
often the result of an approximation or simplification of the described process. Because
anaerobic digestion processes are of significant complexity most dynamic models are of this
type (J. Lauwers et al. 2013).

2.3.2.2. Model examples

ADM1

The IWA Anaerobic Digestion Modeling Task Group was established in 1997 at the 8th
World Congress on Anaerobic Digestion (Sendai, Japan) with the goal of developing a
generalised anaerobic digestion model. ADM1 is a mathematical description of biochemical
as well as physico-chemical processes taking place within the reactor in anaerobic conditions.

Several benefits are expected from the development of this first generic model of anaerobic
digestion:

- increased model application for full-scale plant design, operation and optimization;
- further development work on process optimization and control, aimed at direct
implementation in full-scale plants;
- common basis for further model development and validation studies to make
outcomes more comparable and compatible;
- Assisting technology transfer from research to industry (D.J. Batstone et al, 2002).

An example of Application of ADM1 to the accumulation system: The model is based on

first-order and Monod kinetics for, respectively, hydrolysis of biodegradable particulate and
conversion of dissolved organic matter. The table below shows biochemical rate coefficients
and kinetic rate equations for particulate and soluble components. As the accumulation
system is characterized by having an influent flow, Q, but no effluent flow, the wastewater
volume (V) is variable. Accordingly, the mass balance for any wastewater component, C
(soluble or particulate) can be written according to the equation given below. By applying
numerical integration at small time interval of a minute, the solution is found.

(1)

15
Table 2.7: Biochemical rate coefficients and kinetic rate equations for particulate and
soluble components in the simplified mathematical model

Xb: biodegradable-particulate concentration (mgCOD/l), Xi: inert-particulate concentration

(mgCOD/l), Xm: biomass concentration (mgCOD/l), Sb: biodegradable soluble-substrate
concentration (mgCOD/l), SCH4: converted substrate to methane (mg CH4-COD/l), Si: soluble
inert concentration (mgCOD/l), Kh: first-order hydrolysis constant (1/d), Km: Monod
maximum specific uptake rate (mg COD_S/mg COD_X.d), Ks: half saturation concentration
(mgCOD/l), Y: yield of biomass on substrate ((mg COD_S/mg COD_X), Kd: First order
decay rate (1/d) (J. Lauwers et al., 2013; Elmitwalli T., 2006).

Monod’s model

For the previous models substrate of the digestion was assumed to consist of dissolved
organic substances, which were converted to methane by microbial acidogenesis and
acetoclastic methanogenesis. Because the latter is rate-limiting for solutes, several models
have been developed, that estimate biogas production using only the methanogenesis step.
After, these models have been extended by including acetogenesis for the conversion of
propionate into acetate. The kinetics of these steps is traditionally expressed by Monod type
kinetics, which considers a single growth-limiting substrate.

(2)

With µ (d-1) the specific growth rate, µmax (d-1) the maximum specific growth rate, [S] (g.L-1)
the substrate concentration, and KS (g.L-1) the substrate saturation constant (i.e. substrate
concentration at half µmax).
It was found, however, that the acetoclastic methanogenesis step exhibited inhibition at high
concentration of acetate. Accordingly, a kinetic equation was proposed, based on Haldane
kinetics (equation (3), as given in equation (4). The latter is sometimes referred to as
“Andrews’s kinetics”:

(3)

(4)

Where [VFA] in (g.L-1) is the unionized VFA concentration, and KI (g.L-1) the inhibition
constant.

16
As knowledge of anaerobic digestion has increased, it has been clear that a range of factors
can influence digestion efficiency, such as digester overloading or the occurrence of toxic
components such as sulphide, ammonia or heavy metals. Consequently, these inhibition
effects are included in more recent models. Because of the implicit pH dependence of these
models, the H+ concentration is calculated from the charge balance of the components
included in the model.

2.3.3. Important physical parameters

The environmental factors that are important in the process of AD include temperature, pH,
hydraulic and sludge retention time, composition of the substrate (especially carbonate, VFA
and ammonia), process configuration, solubility of gases, the availability of nutrients, and the
presence of toxic components in the process (W. Parawira, 2004).

2.3.3.1.Temperature effect

Temperature is one the most important parameters for the bacterial growth as the anaerobic
processes are very susceptible to its change. High temperatures (mesophilic and thermophilic
conditions) allow high growth rates and then high removal efficiency. Depending on the
optimum temperature conditions for bacteria growth, we have different classes of MO:

Figure 2.6: Relative growth rates of psychrophilic, mesophilic and thermophilic

methanogens after Wiegel (Gatze Lettinga et al., 2001)

On the figure above we can add another category active above 70 0C up to around 1100C: the
hyperthermophile microorganisms (M. Henze, D. Brdjanovic et al., 2008).

The optimum range for mesophilic digestion is between 30 and 40 0C, and for temperatures
below the optimum range the digestion rate decreases by about 11% for each 1 0C temperature
decrease. According to the Arrhenius expression, the reaction rate coefficient kT at
temperature T (0C) is given by this equation:

(5)

17
Where k20=first-order rate constant at 20°C (1/mg.day); θ=temperature-activation coefficient
varying from 1.02 to 1.25; and T=temperature (°C) (T. Viraraghavan et al., 1996; Metcalf &
Eddy, 2004).

The decrease of temperature for the reactor implicates the low activity of microorganisms in
the system. As shown using Arrhenius equation, the highest temperature coefficient were
observed higher for the suspended solids indicating that suspended solids degradation was the
most sensitive process to temperature (Lew et al., 2009).

Temperature doesn’t affect only the rate of process, but also the final degradation extent. At
low temperatures, more organic matter will remain undegraded at a given HRT due to slow
hydrolysis of volatile solids. However, as long as the solids can be retained in the anaerobic
reactor, they are removed from the liquid phase (Seghezzo, L., 2004). Many other authors
found the range between 25-350 as the optimum, but 18-250 is also good enough, reason why
the anaerobic treatment technologies are more suitable for tropical and subtropical zones (L.
Sasse, 1998).

Temperature does not influence only the metabolic activities of microbial population, but has
also a profound effect on such factors as gas-transfer rates and the settling characteristics of
the biological solids. The effect of temperature may be different for the various physical,
chemical, and biological processes taking place in the reactor, and this fact must be taken into
consideration when modeling the system (Seghezzo, L., 2004).

Micro-organisms are classified into different temperature classes according to their

temperature optima. Psychrophilic bacteria are abundant at 0-200C, mesophilic at
approximately 30-400C, and thermophilic at over 550C. Methanogens are also temperature
sensitive and depending on the temperature of an anaerobic digestion process, different
methanogens prevail. Most of the anaerobic digestion systems are mesophilic, while
psychrophilic operation has been considered difficult due to the slower degradation rates and
long HRT and SRT (Sari Luostarinen, 2005). Thermophilic condition allows more hydrolysis
in the reactor (Huoqing Ge, Paul D. Jensen, Damien J. Batstone, 2010).

The acetogenesis stage is carried out by fewer specialized species of microorganisms and is
thus more likely to be sensitive to temperature. Low temperatures or psychrophilic
applications are of interest for wastewater produced in the bottling, malting and brewery
industries, which produce cold effluents with organic concentrations below 1 kg COD /m3.
However, some attempts to treat such dilute wastewater under psychrophilic conditions have
not been successful (W .Parawira, 2004).

Among the thermophilic, mesophilic and psychrophilic treatment, thermophilic anaerobic

treatment has many unique advantages. Because reaction rates increase with temperature,
significantly higher loading potential and considerably shorter retention times can be
expected if anaerobic treatment is applied under thermophilic condition. Therefore,
thermophilic anaerobic process could be an attractive alternative treatment (Do Hee Kim et
al., 2004), but some contradictory conclusions can be sort out in the table 9 below:

18
Table 2.8: Comparison of the performance of mesophilic and thermophilic anaerobic
digestion (W. Parawira, 2004)

2.3.3.2. PH effect and other inhibition factors

Very low PH (below 5: acidic) or high (above 9: alkaline) is not adequate for the optimum
anaerobic treatment performance.

The value and stability of the pH in an anaerobic reactor is extremely important because
methanogenesis only proceeds at a high rate when the pH is maintained in neutral range (6.3
to 7.8) (Seghezzo, L. 2004).

The pH affects microbial conversions directly through the micro-organisms, which all have
their specific pH optima (e.g. around 6.0 with hydrolytic bacteria, 6.0-8.0 with methanogenic
bacteria). Some authors point out that the growth rate of methanogenic microbes decreases
sharply below pH=6.6 (W. Parawira, 2004). Effects may also be indirect with changes in
chemical equilibrium of the system related to, for example, toxicity of ammonia and VFA,
availability of nutrients and substrate ingredients (e.g. proteins), and availability of carbon
dioxide. When the alkalinity in the influent is in a good range, the pH is maintained in
optimum ranges. With high enough alkalinity, high concentrations of VFA can be tolerated
without acidification of the anaerobic system. Note that oxygen is toxic to methanogens as
well as nitrate and sulphate (Sari Luostarinen, 2005).

In a one-step anaerobic treatment process, the pH is typically maintained at conditions more

optimal for methanogens to prevent the predominance of acid-forming bacteria, which may
cause the accumulation of VFAs. Acidogenesis can occur at pH values approaching neutrality

VFA: The concentration of VFAs is one of the most important parameters in the monitoring
of the anaerobic digestion process. It is commonly agreed that VFA build-up is the result of
unbalanced digestion conditions. The decrease in pH accompanying accumulation of VFAs is
the main cause of toxicity and reactor failure in the anaerobic digestion process. The
concentrations of acetic, propionic and butyric acids are considered the best indicators of the
metabolic state of the most sensitive microbial groups in the anaerobic system. Several
studies confirmed the suitability of monitoring VFAs to detect imbalances in the anaerobic
digestion processes investigated (W. Parawira, 2004).

19
Nutrients: such as nitrogen and phosphorus, and trace elements (sulphur, potassium, calcium,
magnesium, iron, nickel, cobalt, zinc, manganese and copper) are required for efficient
anaerobic degradation and these are usually present in sufficient amounts in most wastes
from households that are treated in anaerobic digesters

For complete inactivation of pathogens, AD at thermophilic condition has proven to be

efficient for sewage sludge by many researchers. Watanabe et al. (1997) found on several
wastewater treatment plants 1 CFU/g TS faecal coliforms and enterococcus and 1.8 CFU/4 g
TS salmonella in the effluent of the thermophilic digester. But due to the high concentration
of organics in the effluent, the bacteria are however easily reactive and re-grow again
(Iranpour et al., 2005).

2.3.3.3. HRT and organic loading rate OLR

The Hydraulic retention time (HRT in unit time) is a term used for determination of tank
volume.
HRT= V/Q Where V is the volume of the tank while Q represents the flow to the tank in [m3]
and [m3/s] respectively.

In the literature and from the field experience, some authors suggest minimum retention times
from 6 to 24 hours for adequate suspended solids removal. Residential hydraulic retentions
based on average daily flows are usually adequate. The critical hydraulic retention time is
determined just as the sludge and scum layers approach their minimum respective clear space
limits. When a tank’s hydraulic retention time is sufficient for settlement, the clear zone
contains liquid waste fairly free of solids. Generally, HRT of at least 1 day minimum may be
considered. Long HRT and SRT are needed for the process (Bounds T.R, 1997). The HRT is
an economic parameter as a shorter HRT means low investments but effluent quality is
generally affected.

The OLR is the quantity of organic matter fed per unit volume of the digester per unit time,
(in gVS/l/day)

20
 CHAPTER 3

3. METHODOLOGY

To achieve my objectives, the following methodology will be used. Many lab experiments
and measurements will be carried out to develop the model as shown in this chapter.

3.1.Framework for the methodology

Review and hypothesis setup

EXPERIMENTS
BW sludge from
households

Batch experiments in closed vessels/septum Lab Scale ST behaviour in gas production.

bottles at mesophilic conditions (400C) Different parameters to be measured
periodically: BOD5, COD, SS, VSS, TKN,
VFA, CH4, pH (APHA 2005)

Bio-Methane Potential (BMP) to determine

total gas production and then methane from
BW

Kinetics as relationship between heating Results from thermal application to the Lab
period, and CH4 production scale ST (heat at 400C)

Mathematical model, calibration and

validation
Figure 3.1: Framework of the methodology

21
 3.2.Collection, Sampling and experimentation

The black water to be utilized as complex substrate for anaerobic digestion is coming from
households and communities surrounding AIT in Pathumthani Province. This matter is
immediately brought to the experimental setup for preparation and homogenisation.

The inoculum used is a black water sludge coming from the laboratory scale septic tank
already operating at 400C where different types of bacteria are expected to be.

a) Batch experiments (BMP)

o Sampling:

The sampling will be made carefully using closed vessels and filled at 60% of BW and faecal
sludge as inoculum. The closing material is rubber lid pinned by aluminium ring to keep
anaerobic condition inside by isolating the sample to the outside environment. The recipients
should be put in dark place to prevent any disturbance from light.

The replicates number of the vessel will be at least three due to the complexity of the
substrate, reproducibility of the tests, and statistical significance (average value); this option
will reduce errors and the analysis will be based on the right inputs/outputs. In 1 litre vessels
(recommended volume: 100ml to 1000ml), the sampling should be done independently for
the 3 replicates per single test.

Freshly collected sludge will be stored at 35-40°C for one week to remove any remaining
biodegradable fraction before using it as inoculum for the batch test when necessary.

The head space of all the reactors will be purged with CO 2/ nitrogen gas for one minute to
create anaerobic conditions before the reactors will be tightly closed with rubber cover.

Three blank reactors containing only inoculum diluted with tap water were will be also set up
to monitor the biogas produced from the inoculum for the correction of biogas produced from
BW.

The BW/inoculums ratio will be in the range of 0.5–2.3 g VS/g VS, to prevent acidification.
The pH approaching the neutrality 6.5-7.8 is recommended for the batch test (M.M. Alves et
al., 2003).

To avoid drops in pH, chemicals will be added to the substrate to supply a buffer capacity.
Sodium bicarbonate, sodium hydroxide, sodium carbonate and sodium sulphide; one of them
will be used when necessary.

22
 Gas collection

Closed vessel
containing
BW+inoculum

Heated water
bath

Figure 3.2: Batch setup for BMP test/Vessels immerged in heated water bath (adapted from
T. Gibson & M. Smyth, 2007)

o Heating the samples:

Heat affects the bio-methanation rate and usually higher temperatures imply greater methane
yields in a shorter digestion time. However, sharp increases of temperature should be avoided
because they can cause a decrease in bio-methane production due to the death of specific
bacteria strains, particularly sensitive to temperature changes. To keep constant the
temperature during BMP tests it will be needed to submerge the reactors in a water bath kept
at the selected temperature or to incubate them in a thermostatically controlled room for
around one month. This time for the incubation will depend on the bio-degradability of the
organic matter.

The vessels containing samples have to be heated at 400C. The Lab scale ST will be operated
at different temperatures from ambient and then 40 0C. Temperature and pH will be controlled
daily to prevent the failure of the test as the methanogenesis process is totally dependent on
those two parameters.

Before heating the vessels, the initial conditions are determined (BOD, COD, etc)
representing the characteristics of the influent substrate.

o Methanogenic activity estimate

The biomethane potential (BMP) will be used to determine the ultimate production of CH 4
under anaerobic conditions in the vessels.

23
For not underestimating the BMP for CH4 estimate, dilution will be considered where
necessary to prevent the overload in the vessel. This will enhance digestion of the present
organic matter. Gas will be measured by means of volumetric methods (typically liquid
displacement) if not available by manometric (determination of pressure variation by
transducers), gas-chromatographic methods with flame ionization (FID) or thermal
conductivity (TCD) detectors. For the liquid displacement, an alkaline solution will be used
at concentration ranging from 1 to 2% to dissolve the CO2 produced.

The biogas production is recorded daily by the displacement of alkaline water as the volume
of methane produced. The methane content is recorded as percentage of methane:

b) Lab scale ST experiments

Figure 3.3: Lab scale ST for experiments

The temperature of the reactor has to be kept at 400C and ensure the equal distribution of heat
into the tank using the control setup available (external surface of ST heated by hot water
recirculation). The heat transfer is achieved while the surfaces are made of plastic. The
effluent from the Lab scale setup will be collected in bigger ST for more digestion before
discharge to the environment.

o Sampling and experimentation

The samples are taken within the tank from the clear zone and the bottom (accumulated
solids) daily. The tests to be made are: COD, TSS, VSS, TKN, and VFA for the accumulated
sludge samples, while for the clear zone the COD is determined.

With a gas meter, the amount of biogas is recorded at fixed intervals of 24hours. The specific
CH4 production is reported as volume of CH 4/gVS, or CH4/gCOD, or CH4/g of sample.

24
 c) Mathematical model

The maximum methane production rate can be considered as the slope of the initial linear
part of methane production versus time. Hydrolysis constant rates are the most sensitive
parameters even by using BMP estimation.

The calibration will be done by comparing model results with experimental measurements of
methane production and adjusting the unknown parameters until the model results adequately
fit the experimental observations. The calibrated model has to be cross-validated with
continuous digesters data sets from laboratory scale septic tanks.

From the batch results, the kinetics governing the methanogenesis process in digestion of
black water (BW) are determined by assuming the first order principle.

BMP results will give us the information on the hydrolysis rate as it is considered as limiting
the anaerobic conversion process. Assuming the first order hydrolysis model:

Or after integration:

With B the value of the ultimate methane production and B the methane produced at time t.

The value of the first order hydrolysis constant Kh is determined from the linear curve slope.

3.3.Analysis

In all experiments, the following data are determined: biogas content, pH, Total Solids (TS),
VS, COD and alkalinity. All analytical procedures are performed in accordance with APHA
(2005).

25
 CHAPTER 4

4. EXPECTED RESULTS

After a careful work in the laboratory and a good analysis, the results presented in this
paragraph will be achieved.

By representing the results graphically, the higher the biodegradability of substrate, the
higher the bio-methanation rate is, by keeping equal all operational conditions. This aspect
affects the bio-methane curve which will be close to the Y-axis during the initial phase (CH4
in Y-axis and time in X-axis). The bigger or more complex the organic solid particles are, the
lower the bio-methanation rate is during the initial phase since the first step of the anaerobic
digestion, i.e. disintegration and hydrolysis, takes a long time to be complete, revealing this
step as the limiting step of the whole process. One of these two scenarios will be observed
depending on the characteristics on BW to be utilized. BMP will give us an idea on
disintegration apparent kinetic rate constant k of the BW.

Moreover, with the BMP test, we will have a calibrated mathematical model suitable to
simulate the digestion process of BW and predict the performances of full-scale anaerobic
digesters. After validation, good model performance has to be attained.

The expected values for the methane production should be in the range reported by many
authors (55 to 80%).

26
Time table

Aug- Sep- Oct- Nov- Dec-13 Jan- Feb- Mar- Apr- May-
13 13 13 13 14 14 14 14 14

Week 1 2 3 4 1 2 3 4 1 2 3 4 1 2 3 41 2 3 4 1 2 3 4 1 2 3 4 1 2 3 4 1 2 3 4 1 2 3 4

Activity

Proposal Preparation

Defence of thesis proposal

Literature review

Laboratory scale septic tank

operation

Sample Analysis

Report preparation

Submission of draft thesis report

Mentor and Supervisor meeting

Final Examination

27
Budget
The following table shows a budget estimate to be used during the period of the research:

Parameters Estimated quantity Estimate cost

(Baht)
Laboratory experiments 100 12,500
(BOD, COD, TKN, VSS, TS,
TN)
BMP tests 10 4,000
Transport 1 3,500
Total 20,000

28
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