Process Optimization of a Petroleum Refinery Wastewater Treatment Facility

Using Process Modeling and Site Specific Biokinetic Constants

Hank W. Andres1, David G. Kujawski2, Oliver J. Schraa1, Che-Jen Lin2 and Arthur D. Wong2
1
Hydromantis Environmental Software Solutions (ESS), Inc., 1 James Street S., Suite 1601,
Hamilton, ON, Canada L8P 4R5
2
Refinery Water Engineering & Associates (RWEA) Inc., 3312 Hwy. 365, Suite 213,
Nederland, TX, U.S.A. 77627
Correspondence email: andres@hydromantis-software.com
ABSTRACT

In this project, an old, out-of-service secondary clarifier was converted to a Complete Mix Batch
Reactor (CMBR) and was designed to provide maximum deployment flexibility so that it could
be operated in a number of modes. Simulation analysis with the MantisIW model in GPS-XTM
was used to determine the optimal number of batch runs to treat a high strength COD and
inhibitory waste stream to meet predefined effluent criteria for discharge to the Activated Sludge
Unit (ASU). The CMBR was also deployed in another instance as an isolated sidestream
chemostat reactor to treat a large quantity of floating free oil that was released to the wastewater
treatment plant. Simulation analysis of the chemostat reactor was used to determine the optimal
incubation period for the microbes to consume the free oil under aerobic conditions. A total of
four CMBR batches were required to consume the high levels of free oil. After 24 hours
immediately following the first CMBR effluent blend with the oxidation ditch influent, the
clarifier effluent oil and grease levels were consistently below 15 mg/L. After an MCRT process
control strategy had been effectively implemented at the WWTP, a full-scale Lawrence and
McCarty (1970) model field biokinetic study was executed to determine the site-specific
biokinetic constants of the existing wastewater treatment facility. The site-specific biokinetic
constants were determined by fitting the operating data as a function of the microbial growth rate
using statistical regression analysis. For the first time since it began operation, the true organic
loading capacity of the existing facility was conclusively quantified. The calibrated GPS-XTM
model utilizing the site-specific biokinetic constants is a fully predictive model that can be used
to analyze and optimize the wastewater treatment facility operations and accurately predict the
plant performance under hypothetical operating conditions.

KEYWORDS

Process, Modeling, Simulation, Biokinetic Constants, Activated Sludge, Petroleum Refinery,

Industrial Wastewater Treatment.

INTRODUCTION

Process modeling can be used to analyze and optimize industrial wastewater treatment plants
(WWTPs) (e.g. Bury et al., 2002; Goodfellow et al., 2004; Schraa et al., 2004; Stricker and
Racault, 2005; Takács et al., 1998), but model customization may be required to handle
pollutants not commonly found in domestic wastewater. In 2007, Hydromantis ESS, Inc.
developed the MantisIW activated sludge model which provides a general modeling framework
for industrial activated sludge plants and allows for flexibility in handling a wide variety of
industrial wastewaters including those found in the petroleum, petrochemical, organic chemical,
pulp and paper, pharmaceutical, and food and beverage industries (Schraa et al., 2007).

The objective of the current paper is to demonstrate how the MantisIW model, as implemented in
the GPS-XTM software package, can be used to evaluate the capacity of a petroleum refinery
wastewater treatment facility by presenting a successful case study. This case study involves
using the model to quantify the impact of deploying a sidestream Complete Mix Batch Reactor
(CMBR) to partially treat high-strength wastewater offline from the main wastewater treatment
facility. This paper will also discuss how site-specific biokinetic constants were determined for
the wastewater treatment facility from a full-scale field study that took place from October 1,
2010 to December 15, 2010.

MantisIW MODEL DESCRIPTION

The MantisIW industrial activated sludge model provides sufficient detail in terms of the
wastewater characterization and the biological and physical processes modeled to allow for
application of the model in a wide variety of industries. The model utilizes aspects of the ASM1
(Henze et al., 2000), ASM2d (Henze et al., 2000), Mantis (Hydromantis, 2010), and Baker
(1994) biological models along with a revised categorization of the influent chemical oxygen
demand (COD) and added biological and physical transformations. The user has flexibility in
choosing which aspects of the model to apply in a given situation by using the appropriate
influent categorization and the available model components. The inclusion of multiple model
components allows for tracking of a variety of industrial pollutants.

The main features of the MantisIW model include the following:

 Industrial-specific classification of organic influent COD

 Multiple transformation processes for COD components: volatilization, adsorption, and
biological growth. Certain COD components can undergo volatilization and biological
oxidation simultaneously.
 Description of volatilization: current activated sludge models do not separately account
for contributions from surface volatilization and air stripping due to aeration.
 Impact of nutrient and alkalinity requirements on all biological growth processes in
model: all processes can be limited if nutrient or alkalinity concentrations are low. The
impact of sulfur oxidation on alkalinity is included.

The model also includes the following features:

 Simultaneous nitrification/denitrification
 Inhibited biological oxidation of toxic compounds modeled using the Haldane equation
 Biological oxidation of reduced sulfur compounds
 Modeling the fate of colloidal material
In addition to the existing ASM1 influent COD state variables (i.e. readily biodegradable
substrate, slowly biodegradable substrate, soluble inert organic material and particulate inert
organic material), the MantisIW industrial-specific COD model components or state variables
have been categorized by considering the physical, chemical and biological properties
(biodegradability, hydrophobicity and volatility) of the different organic compounds.
Consideration was also given to the classes of compounds that are normally tracked in industrial
WWTPs due to health, safety and environmental concerns. The MantisIW influent COD
variables are defined below in Table 1, with accompanying typical and representative
compounds in terms of biodegradability, hydrophobicity and volatility.

Table 1 – Definition of MantisIW Influent COD Variables

Influent COD variable Typical compounds Representative compound

Oxygenated organic solvents
Halogenated organic solvents
Short-chain aliphatic compounds
Long-chain aliphatic compounds
Monocyclic aromatic compounds
Polycyclic aromatic compounds
Halogenated aromatic compounds
Toxic or inhibitory compounds
Colloidal material
 Alcohols Methyl ethyl ketone
 Aldehydes and ketones
 Carboxylic acids
 Esters
 Ethers
 Alkyl halides Chloroform
 e.g. chloroform, carbon
tetrachloride, methyl
iodide
 Hydrocarbons with less Methyl cyclohexane
than 18 carbon atoms
including: alkanes,
alkenes, alkynes, fats and
oils
 Hydrocarbons with 18 or Eicosane (C20H42)
more carbon atoms
including: alkanes,
alkenes, alkynes, fats, oils
 Aromatic compounds with Ethyl benzene
single benzene ring
 e.g. benzene, toluene,
styrene, xylene
 Aromatic compounds with Fluoranthene
multiple benzene rings
 e.g. naphthalene,
phenanthrene,
benzo[a]pyrene
 Aryl halides 1,2,4-Trichlorobenzene
 e.g. bromobenzene,
chlorobenzene)
 Phenolic compounds Phenol
 Lignins Lignins
The MantisIW model includes the following transformation processes:

 Aerobic and anoxic growth of heterotrophs on biodegradable substrate

 Inhibited aerobic and anoxic growth of heterotrophs on toxic compounds
 Adsorption and subsequent aerobic/anoxic heterotrophic growth on adsorbed substrate
 Volatilization due to surface evaporation and air stripping
 Hydrolysis of slowly biodegradable substrate and particulate organic nitrogen
 Decay of heterotrophs
 Ammonification of soluble organic nitrogen to ammonia
 Aerobic growth and decay of nitrifiers
 Aerobic growth and decay of sulfur oxidizing organisms

The influent COD components can undergo one or more transformation processes depending on
their individual characteristics. The possible transformations for each influent COD component
in the model are described in Table 2.

Table 2 – Possible Transformations for Influent COD Components in MantisIW Model

Type of Organic COD Components Included Possible Transformations

Compound
Readily biodegradable,  Readily biodegradable
soluble, non-volatile substrate
Slowly biodegradable,  Slowly biodegradable
particulate substrate
Readily biodegradable,  Oxygenated solvents
soluble, volatile  Halogenated solvents
 Short-chain aliphatic
compounds
 Mono-cyclic aromatic
compounds
Biodegradable toxic or  Phenol
inhibitory compounds
Partially miscible, non-  Long-chain aliphatic
volatile compounds
 Poly-cyclic aromatic
compounds
 Colloidal material
Partially miscible,  Halogenated aromatic
volatile compounds
 Aerobic/anoxic heterotrophic
growth
 Hydrolysis to readily
biodegradable substrate
 Aerobic/anoxic heterotrophic
growth
 Volatilization
 Inhibited aerobic/anoxic
heterotrophic growth
 Volatilization
 Adsorption
 Aerobic/anoxic heterotrophic
growth on adsorbed material
 Adsorption
 Aerobic/anoxic heterotrophic
growth on adsorbed material
 Volatilization

The COD transformation processes in MantisIW are presented in Figure 1 (overview of COD
transformations) and Figure 2 (overview of biological growth processes). The transformations
are shown along with the required electron acceptors and nutrients.
 Legend
Soluble COD
Long-chain Particulate COD
aliphatic
Transformation Processes
Electron Acceptors
Poly-cyclic Adsorbed
aromatic Adsorption compounds Nutrients/Alkalinity

Colloidal
Oxygen
or nitrate
Halogenated
aromatic

Oxygenated Soluble
solvents
Volatilization Ammonium
phosphorus
Alkalinity

Halogenated
solvents

Oxygen Inert Decay

Mono-cyclic Products
or nitrate
aromatic

Short-chain
aliphatic Oxygen
or nitrate
Heterotrophic
Biomass Growth biomass Decay
Phenolic

Readily bio-
degradable
Slowly bio-
Hydrolysis degradable

Figure 1 – Overview of COD Transformation Processes in MantisIW (Adsorption,

Volatilization, and Heterotrophic Growth/Decay; Schraa et al., 2007)
Legend
Soluble Substrate
Particulate Substrate
Transformation Processes
Electron Acceptors
Oxygen
Nutrients Alkalinity Nutrients/Alkalinity
or nitrate

Substrate Heterotrophic
COD Biomass Growth biomass
Inert Decay
Products

Sulfate
Oxygen Nutrients Soluble
& alkalinity phosphorus

Reduced Sulfur oxidizer

Sulfur Biomass Growth biomass Decay

Nutrients Nitrate
Oxygen
& alkalinity
Particulate Slowly bio-
organic N degradable
Nitrifier
Ammonium
Biomass Growth biomass

Soluble
Ammonification organic N Hydrolysis

Figure 2 – Overview of Biological Growth Processes in MantisIW (Schraa et al., 2007)

PROCESS OPTIMIZATION CASE STUDY – PETROLEUM REFINERY
WASTEWATER TREATMENT FACILITY

The MantisIW model was used to optimize a petroleum refinery WWTP located in the
Midwestern United States with an overall mandate to evaluate the wastewater treatment plant
capacity and improve compliance reliability by using innovative process control strategies.
Another goal of this study was to establish site-specific biokinetic constants and quantify the true
operational capacity of the existing wastewater treatment facility. Several opportunities for
improved WWTP performance were identified and evaluated using the MantisIW model as
implemented in the GPS-XTM software package, which is considered one of the most advanced
dynamic modeling software packages available (Lee et al., 2010).

The petroleum refinery WWTP treats the wastewater from a refinery which produces 85,000
barrels per day (BPD) of sour crude oil. The refinery has the typical challenges of profitable
operations while meeting permit levels for wastewater discharge and sludge disposal. The
wastewater treatment facility operates under a National Pollutant Discharge Elimination System
(NPDES) permit and treats an average wastewater flow of approximately 0.8 MGD. The WWTP
process design consists of a single train API separator, equalization tank, storm water tank,
diversion tank, an activated sludge unit (ASU) with an oxidation ditch configuration and brush
aerator oxygen supply system, a secondary clarifier, and 3 non-aerated polishing lagoons in
series. The ASU dissolved oxygen (DO) levels are typically the limiting factor for plant loading
capacity, and the plant has often been forced to operate with low DO residuals. Since there is no
Dissolved Air Flotation unit (DAF) between the API Separator and the ASU, there is little
buffering capacity when high levels of free oil enter the process sewer.

Refinery Water Engineering and Associates, Inc. (RWEA) partnered with Hydromantis
Environmental Software Solutions, Inc. (HESSI) with the goal of creating a calibrated process
model of the petroleum refinery WWTP to provide process insight and assist with maximizing
the available plant capacity. A schematic of the plant, as represented in GPS-XTM, is shown in
Figure 3.

Figure 3 – Petroleum Refinery WWTP GPS-XTM Process Model

The main scope of work for the petroleum refinery WWTP optimization is outlined below:

1. Maximize the capacity of the existing wastewater treatment facility and infrastructure.
2. Determine the maximum plant loading capacity and establish site-specific biokinetic
constants for the existing wastewater treatment facility.
3. Implement operational changes and process control strategies to improve oxygen transfer
efficiency and oxygen utilization rates.

Complete Mix Batch Reactor Implementation

In May 2010, to maximize the wastewater treatment capacity while utilizing existing
infrastructure, a project was completed to convert an old, out-of-service secondary clarifier into a
Complete Mix Batch Reactor (CMBR), equipped with a new fine bubble diffused air system.
The CMBR was designed to provide maximum deployment flexibility so that it could be
operated in a number of modes, including:

1. In batch or continuous mode of operation.

2. As an isolated reactor in series or parallel configuration with the ASU.
3. As a continuous feed reactor for an increased capacity extension of the ASU.
4. For isolated treatment of stored high-strength influent wastewater. Some of this
wastewater was formerly deemed untreatable at full strength, and was slowly blended
with influent to the ASU.
5. As an isolated sidestream chemostat reactor for the treatment of intermittently generated
liquid waste streams which were formerly shipped offsite for disposal, such as amine
solutions, phenolic caustics, sulfidic caustics, undesirable slop oils etc.
6. For onsite microbial population incubation or controlled adaptation of the ASU microbes
for specific types of influent contaminant treatment.

The CMBR effluent can be discharged to multiple locations in the plug-flow ASU (i.e. step feed)
or directly to the polishing lagoons.

A GPS-XTM model of the CMBR, shown in Figure 4, was created to evaluate the performance of
different CMBR operating modes under different influent loading conditions.

Figure 4 – Complete Mix Batch Reactor (CMBR) GPS-XTM Process Model

The first mode of operation that was evaluated using the model was operating the CMBR as a
sidestream chemostat reactor for the treatment of intermittently generated high-strength COD
and inhibitory waste streams which also contain significant amounts of amine solutions, phenolic
caustics, sulfidic caustics, undesirable slop oils, hydrogen sulfide, and spent catalysts which are
known to be inhibitory. The model was calibrated with available operating data from previous
batch reactor runs in this mode of operation.

Influent concentrations of the high-strength waste included influent COD concentrations ranging
from 2,500 mg/L to 4,000 mg/L, influent NH3-N concentrations ranging from 275 mg/L to 350
mg/L, and influent phenol concentrations ranging from 250 mg/L to 400 mg/L. Effluent criteria
for discharge to the ASU was an effluent COD concentration below 400 mg/L, an effluent NH3-
N concentration below 100 mg/L, and an effluent phenol concentration below 40 mg/L. The
CMBR reactor was initially seeded with 75% mixed liquor from the ASU and 25% was filled
with the high-strength wastewater. The results from the simulation analysis, shown in Figure 5,
indicated that with each subsequent batch, the contaminant removal efficiencies decreased and
the effluent concentrations increased due to biomass growth inhibition from the high-strength
influent wastewater. The analysis indicated that after four six-hour batch runs, the CMBR would
need to be dumped and reseeded to meet the effluent criteria. Without this valuable insight from
the simulation analysis, a “trial and error” approach would have been applied in the field and the
effluent concentrations from the CMBR would have been significantly higher.

800
COD Concentration (mg/L)

700
600
Effluent COD Limit
500
400
300
200
100
0
0 5 10 15 20 25 30 35 40
Time (h)

160
NH3-N Concentration (mg/L)

140
Effluent NH3-N Limit
120
100
80
60
40
20
0
0 5 10 15 20 25 30 35 40
Time (h)

Figure 5 –CMBR Chemostat Effluent for High-Strength Wastewater Treatment

A second modeling application was executed during a wastewater plant upset which occurred on
July 15, 2010. A combination of inadvertent sewer dumps, malfunctioning WWTP equipment,
and rain resulted in an extremely difficult to treat influent stream with greatly reduced diversion
tank availability. The API separator and equalization tank were overloaded and functioning at a
rate well below their design capacity. The ASU (i.e. the oxidation ditch and secondary clarifier)
and the first lagoon became coated with 1.5 inches of floating free oil. NPDES permit
compliance became threatened for a number of contaminants. The oxidation ditch oxygen uptake
rates (OUR) decreased below 15 mg/(L.h) during the plant upset.

The CMBR was deployed as an isolated sidestream chemostat reactor to treat the floating free oil
that was released to the wastewater treatment plant. Floating free oil was collected and removed
from the oxidation ditch, secondary clarifier and lagoon surfaces by a vacuum truck for input to
the chemostat reactor. Simulation analysis of the chemostat reactor was used to determine the
optimal batch run length for the microbes to consume the free oil under aerobic conditions. The
OUR in the CMBR was plotted to track the microbial activity and is shown in Figure 6. The
results showed that after a four hour period, the microbial activity under aerobic conditions was
minimal, hence a four hour batch run length was chosen for the chemostat reactor so that the free
oil could be treated as efficiently as possible.

140
Oxygen Uptake Rate (mg/(L.h)

120
100
80
60
40
20
0
0 1 2 3 4 5 6
Time (h)

Figure 6 – CMBR Chemostat Oxygen Uptake Rate of Microbes for Free Oil Treatment

The CMBR was initially seeded with 75% mixed liquor from the ASU, while the remaining 25%
of the tank was filled with the floating free oil from the vacuum truck discharge. After the first
four hour batch, 50% of CMBR batch was blended into the oxidation ditch influent. The CMBR
was then refilled with more vacuum truck discharge. This batching procedure was repeated a
total of four times. There were two main benefits to the batch procedure, the first was that the
microbes were able to consume the high levels of free oil and the second was that biomass in the
main treatment system was augmented with CMBR biomass that was conditioned to consume
the free oil in the ASU.

After four hours of CMBR operation in a chemostat mode (i.e. after the first batch and during
batches #2 to #4), there were no free oil observed in the CMBR. After 14 hours of oxidation
ditch operation immediately following the first CMBR effluent blend with the ASU influent,
there were no remains of free oil on the surface of the oxidation ditch or the secondary clarifier.
During the peak periods of the floating free oil upset, the oxidation ditch bulk water oil and
grease levels near the influent point of the ASU ranged from 1,000 mg/L to 5,000 mg/L. The
oxidation ditch float oil and grease levels near the influent point of the ASU ranged from 10,000
mg/L to 100,000 mg/L. However, after 24 hours immediately following the first CMBR effluent
blend with the oxidation ditch influent, the clarifier effluent oil and grease levels were
consistently below 15 mg/L.

Mean Cell Retention Time (MCRT) Process Control Implementation

In an effort to further maximize the treatment capacity of the existing wastewater treatment
facility, the plant operational control approach was switched from a Food-to-Mass Ratio (F:M)
strategy to a Mean Cell Retention Time (MCRT) strategy. This modification to the process
control strategy began in July 2010.

In some wastewater applications, the use of the F:M strategy for control of the activated sludge
process is sufficient. However, in many types of industrial wastewater treatment applications,
this strategy is deficient due to:

1. Wide ranges of variability in the influent.

2. Wide ranges of relative biodegradability of the substrate in the influent.
3. The intermittent presence of biologically toxic and inhibitory compounds in the influent.

Inherently, the actual calculation of F:M has several pitfalls, including:

1. In petroleum refinery wastewater, there is no efficient and representative test for the
substrate. A Biochemical Oxygen Demand (BOD5) test would be representative, but does
not have a quick enough turnaround time for the process information to be applicable. In
addition, it requires that the bacteria used in the test are acclimated to the wastewater of
interest. Conversely, the use of the MCRT strategy does not depend on measuring the
substrate.
2. Unlike the use of the MCRT strategy, an F:M strategy cannot be directly related
mathematically to the microbial growth rates and site-specific biokinetic constants.
3. Unlike the MCRT strategy, the process for determination of the optimum target control
ranges for F:M is not practical under the operating conditions of a petroleum refinery
activated sludge process. As such, the optimum target F:M ranges are typically based on
another plant’s design specifications, which may not match the specific plant’s process
considerations.
4. Adjustment of the waste activated sludge (WAS) flow rate to control the F:M ratio is a
“trial and error” process. With the use of the MCRT strategy, the WAS flow rate is
calculated directly and administered to hit the target control range.

Since an MCRT process control strategy has been implemented at the WWTP, increased ASU
contaminant removal efficiencies and process stability have been observed.
Determination of the Maximum Plant Capacity and Site-Specific Biokinetic Constants

Process control and operation of a petroleum refinery WWTP is not always straightforward due
to the high number of process variables involved in biological wastewater treatment. Also, there
are many other non-biological chemical mechanisms occurring simultaneously in a bioreactor,
which may appear to be the result of biological treatment, but may in fact be facilitated by
enzymatic reactions, chemical oxidation, precipitation, adsorption, ligand complex formation
reactions, sludge entrapment and air stripping. To quantitatively define the true performance of
the specific microbiological population functioning in a given plant, the site-specific biokinetic
constants must be determined. Effective process control is dependent on being able to quantify
the actual kinetic and metabolic reactions of microbial growth in the system. This knowledge
culminates in maximizing the true operational plant capacity, starting with maximization at the
individual microbial cell level.

Once the MCRT process control strategy had been effectively implemented at the WWTP, a full-
scale Lawrence and McCarty model field biokinetic study (Lawrence and McCarty, 1970) was
executed from October 1, 2010 to December 15, 2010 to determine the site specific biokinetic
constants of the existing wastewater treatment facility. The Lawrence and McCarty model,
which can incorporate the Monod equation for relatively non-inhibitory activated biological
systems and the Haldane equation for severely inhibitory biological systems, is the most flexible
and accepted model for the field determination of biokinetic constants for industrial wastewater
facilities. The 3 MCRT’s that were targeted during the study, which is the minimum
requirement for curve fitting, were 15 days, 21 days and 7 days respectively. During the
biokinetic study, the CMBR was operated in continuous mode in parallel with the main ASU and
the CMBR was not operated in a sidestream chemostat mode for the entire duration of the study.

Once the operating data from the biokinetic study was collected, a rigorous data screening
process was completed using information recorded in the operator logs, supplemental lab data
and statistical analysis to remove outliers from the data set. After the data set had been screened
and the outliers removed, the biological kinetic expressions were obtained by fitting the
operating data as a function of the microbial growth rate using statistical regression analysis.
The determination of site-specific biokinetic constants, shown in Table 3, conclusively
quantified the true organic loading capacity of the existing facility for the first time since it began
operation.

Table 3 – Site-Specific Biokinetic Constants for the Existing Wastewater Treatment Facility

Biokinetic Constant Value

k – Maximum Substrate Utilization Rate 0.274 mg COD mg VSS-1 d-1

Ks – Half Saturation Constant 165.8 mg COD L-1

K – Specific Substrate Utilization Coefficient 0.0017 L mg COD-1 d-1

Y – Cell Yield 0.424 mg VSS mg COD-1

Kd – Decay Rate Coefficient 0.01 d-1

Once the site-specific biokinetic constants were determined, they were integrated into the GPS-
XTM model of the wastewater treatment facility and the model was calibrated using operating
data from the field biokinetic study period. Calibration of biological wastewater treatment
process models involves characterizing the influent waste streams, specifying operational
variables, and adjusting certain key model parameters to minimize the error between the
measured and predicted data. The model calibration results using the site-specific biokinetic
constants are shown in Figure 7, Figure 8 and Figure 9.

30000
Suspended Solids (mg/L)

25000

20000

15000

10000

5000

0
10/01/10 10/11/10 10/21/10 10/31/10 11/10/10 11/20/10 11/30/10 12/10/10

MLSS - Measured MLVSS - Measured

MLSS - Simulated MLVSS - Simulated

Figure 7 – GPS-XTM Model Calibration Results – Oxidation Ditch Activated Sludge Unit

250

200
Concentration (mg/L)

150

100

50

0
10/01/10 10/11/10 10/21/10 10/31/10 11/10/10 11/20/10 11/30/10 12/10/10

COD - Measured TSS - Measured COD - Simulated TSS - Simulated

Figure 8 – GPS-XTM Model Calibration Results – Secondary Clarifier Effluent TSS and COD
 25 10

20 8
Oil & Grease (mg/L)

NH3-N (mg/L)
15 6

10 4

5 2

0 0
10/01/10 10/11/10 10/21/10 10/31/10 11/10/10 11/20/10 11/30/10 12/10/10

O&G - Measured O&G - Simulated

NH3-N - Measured NH3-N - Simulated

Figure 9 – GPS-XTM Model Calibration Results – Clarifier Effluent Oil & Grease and NH3-N

Each plot shows the simulated results (solid lines) and the measured data (data points) over time.
When reviewing the calibration results, it should be noted that typical wastewater measurements
contain error due to analytical variability, sampling location, and normal random process
variability. Therefore it is not possible to match the data exactly. Overall the model is matching
the plant’s performance and response to influent variability reasonably well and the model is a
satisfactory representation of the process. The biomass (MLSS and MLVSS) and effluent
concentrations are consistent between the model and the sampling results.

The calibrated GPS-XTM model utilizing the site-specific biokinetic constants is a fully predictive
model that can be used to analyze and optimize the wastewater treatment facility operations and
accurately predict the plant performance under hypothetical operating conditions. Predictive
control of complex biological wastewater treatment systems is the next stage to achieve
maximum utilization of refinery treatment assets as well as maintaining effluent quality. Just as
chemical reaction kinetics are used in every upstream refinery unit operation to optimize the
process, biological kinetic modeling can be utilized to achieve a greater control over
environmental stewardship and provide a return on investment.

FUTURE WORK

Now that the maximum plant loading capacity has been determined and site-specific biokinetic
constants for the wastewater treatment facility have been established and incorporated into the
process model, the calibrated GPS-XTM model could be used the evaluate various operational and
process control strategies to improve the oxygen transfer efficiency and the oxygen utilization
rates of the existing WWTP. Algorithms could also be added to the model to quantify the
operating costs that are related to process control modifications and compare plant performance
and predicted effluent quality with the associated costs.
CONCLUSIONS

The MantisIW activated sludge model provides a general modeling framework for industrial
activated sludge plants and allows for flexibility in handling a wide variety of industrial
wastewaters including those found in the petroleum refinery industry. The model utilizes aspects
of several published biological models along with a revised categorization of the industrial-
specific influent COD state variables and biological and physical process transformations. The
model can be used to optimize and evaluate process operation alternatives of industrial
wastewater treatment facilities.

An old, out-of-service secondary clarifier was converted into a Complete Mix Batch Reactor
(CMBR) to maximize the WWTP capacity while utilizing existing infrastructure. The CMBR
was designed to provide maximum deployment flexibility so that it could be operated in a
number of modes. In a case where an intermittently generated high-strength COD and inhibitory
waste stream required in the CMBR, simulation analysis indicated that with each subsequent
batch, the contaminant removal efficiencies decreased and the effluent concentrations increased
due to biomass growth inhibition from the high-strength influent wastewater. The analysis
indicated that after four six-hour batch runs, the CMBR would need to be dumped and reseeded
to meet the effluent criteria. Without this valuable insight from the simulation analysis, a “trial
and error” approach would have been applied in the field and the effluent concentrations from
the CMBR would have been significantly higher.

The CMBR was also deployed as an isolated sidestream chemostat reactor to treat a large
quantity of floating free oil that was released to the wastewater treatment plant. Simulation
analysis of the chemostat reactor was used to determine the optimal batch run length for the
microbes to consume the free oil under aerobic conditions. The results showed that after a four
hour period, the microbial activity under aerobic conditions was minimal, hence a four hour
batch run length was chosen for the chemostat reactor so that the free oil could be treated as
efficiently as possible. A total of four CMBR batches were required to consume the high levels
of free oil. During the peak periods of the floating free oil upset, the oxidation ditch bulk water
oil and grease levels near the influent point of the ASU ranged from 1,000 mg/L to 5,000 mg/L.
However, after 24 hours immediately following the first CMBR effluent blend with the oxidation
ditch influent, the clarifier effluent oil and grease levels were consistently below 15 mg/L.

In an effort to further maximize the treatment capacity of the existing wastewater treatment
facility, the plant operational control approach was switched from a Food-to-Mass Ratio (F:M)
strategy to a Mean Cell Retention Time (MCRT) strategy. Since an MCRT process control
strategy has been implemented at the WWTP, increased ASU contaminant removal efficiencies
and process stability have been observed.

Once the MCRT process control strategy had been effectively implemented at the WWTP, a full-
scale Lawrence and McCarty model field biokinetic study was executed to determine the site-
specific biokinetic constants of the existing wastewater treatment facility. Once the operating
data from the biokinetic study was collected and the outliers were removed from the data set, the
biological kinetic expressions were obtained by fitting the operating data as a function of the
microbial growth rate using statistical regression analysis methods. The determination of site-
specific biokinetic constants conclusively quantified the true organic loading capacity of the
existing facility for the first time since it began operation.
Once the site-specific biokinetic constants were determined, they were integrated into the GPS-
XTM model of the wastewater treatment. The calibrated GPS-XTM model utilizing the site-
specific biokinetic constants is a fully predictive model that can be used to analyze and optimize
the wastewater treatment facility operations and accurately predict the plant performance under
hypothetical operating conditions. Process models with site-specific biokinetic constants are a
tool that can be accepted by regulatory agencies to quantify the maximum plant capacity of a
wastewater treatment facility and determine if the existing facility is adequate to treat the
anticipated wastewater load or if capital improvements must be made to the wastewater
treatment facility to provide an adequate level of treatment.

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