APPROVAL SHEET

INDIVIDUAL ASSIGNMENT REPORT

TK 4090 INTERNSHIP
SEMESTER I 2014/2015

Annisa Mienda Chintyarani (13011071)

Note/comment :

Internship Location
Internship Period

: Map Tha Put Industrial Estate, Rayong, Thailand.

: May 22nd 2014 July 31st 2014

Has been examined and approved by:

Mentor

Supranee Kanokwajamrus
Senior Process Engineer
Date : _____________

Advisor

Dr. Dwiwahju Sasongko

Date :____________

PREFACE

The author would like to acknowledge her countless thanks to the Most Gracious and the Most
Merciful, Allah SWT who always gives their all the best of this life, so the author is able to
complete the internship and its report during May 22nd 2014 July 31st 2014 in PTT Global
Chemical Company Limited. Shalawat and Salaam to the Prophet Muhammad SAW and his
family. This script is presented to fulfill one of the requirements in accomplishing the Bachelor
Degree at Chemical Engineering Department, Faculty of Industrial Technology, Institut
Teknologi Bandung.
The authors would like to take their opportunity to express their deep and sincere gratitude to the
following:
1. Dr. Dwiwahju Sasongko, as the advisor who has guided the authors patiently during the
internship period
2. Dr. IGBN Makertihartha, as the coordinator of TK4090 Internship
3. Nittaya Boonyarit, as Process Engineer Manager in PTT Global Chemical
4. Supranee Kanokwajamrus, as Senior Process Engineer as well as authors mentor from
Process Engineer Division in PTT Global Chemical.
In addition, author would also thank others who give their full help and support during the
internship, they are:
1. Dilok Tuekla, as Vice President of Human Resources PTT Global Chemical Company
who gave an opportunity for us to get new experience throughout this internship program
2. Supat Arunlerktawin, as Manager of Training Center Management PTT Global Chemical
Company
3. Kammasit Wichitphan, as HR Officer at PTT Global Chemical Company
4. Jaratsri Rakkaew, as Senior HR Officer at PTT Global Chemical Company
5. Sirinun Sirisaard, as HR Officer PTT at Global Chemical Company
6. Kevin Wun, as Internship Manager at PTT Global Chemimal
7. All employees in PTT Global Chemical Company
8. All family in Bandung who always give support during internship program.
This report is not perfect and is open for corrections. Hope it will be useful for the readers.

Rayong, 31st July 2014

Author

TABLE OF CONTENTS
CHAPTER I .................................................................................................................................... 1
INTRODUCTION ........................................................................................................................... 1
1.1 Background ............................................................................................................................ 1
1.2 Objectives .............................................................................................................................. 1
1.3 Scopes of work ...................................................................................................................... 1
CHAPTER II ................................................................................................................................... 2
LITERATURE ................................................................................................................................ 2
2.1 The importance of wastewater treatment ............................................................................... 2
2.2 Wastewater treatment selection ............................................................................................. 2
2.3 Physical, biological, and chemical wastewater treatment ..................................................... 4
2.4 General PO/SM, polymer polyol, and polyether polyol plants wastewater characteristics . 5
CHAPTER III .................................................................................................................................. 6
METHODOLOGY .......................................................................................................................... 6
CHAPTER IV.................................................................................................................................. 7
RESULTS AND DISCUSSION ..................................................................................................... 7
4.1 Wastewater Characteristics .................................................................................................... 7
4.1.1 Wastewater sources ......................................................................................................... 7
4.1.2 Wastewater composition ................................................................................................. 7
4.1.3 Wastewater classification .............................................................................................. 10
4.2 Available Technology for Wastewater Treatment ............................................................... 11
4.2.1

Technology for high polluted and low polluted stream .......................................... 11

4.2.2

Technology for salt stream ...................................................................................... 29

4.3 Technology Selection .......................................................................................................... 37

CHAPTER V ................................................................................................................................. 41
CONCLUSIONS AND RECOMMENDATIONS ........................................................................ 41
5.1 Conclusions.......................................................................................................................... 41
5.2 Recommendations................................................................................................................ 41
APPENDIX A ............................................................................................................................... 42
REFERENCES .............................................................................................................................. 44

ii

TABLE OF FIGURES

Figure 2.1 Wastewater treatment method selection ........................................................................ 3

Figure 2.2 Inhibitory compounds for biological treatment ............................................................. 5
Figure 3.1 Workflow diagram of feasibility study .......................................................................... 6
Figure 4.1 Wet air oxidation process............................................................................................. 13
Figure 4.2 Scheme of ozone oxidation process ............................................................................. 14
Figure 4.3 Repsol PACT system unit ......................................................................................... 15
Figure 4.4 Comparison between external and internal membrane configuration ......................... 17
Figure 4.5 Process scheme of external membrane system in Commune De Monteux WWT ...... 18
Figure 4.6 Oxidation ditch system ................................................................................................ 20
Figure 4.7 Block diagram of TAR system .................................................................................... 25
Figure 4.8 Schematic figures of multiple hearth (left) and fluidized bed (right) .......................... 30
Figure 4.6 Block diagram of Ozone oxidation-MBR system ........................................................ 32
Figure 4.7 Block diagram of Fenton oxidation-oxidation ditch .................................................... 32
Figure 4.9. Schematic diagram of electrodialysis reversal system ................................................ 35

iii

TABLE OF TABLES

Table 4.1 Summary of wastewater characteristic from POSM, Polyether Polyol, and polymer
polyol unit........................................................................................................................................ 8
Table 4.1 Summary of wastewater characteristic from POSM, Polyether Polyol, and polymer
polyol unit (contd.) .......................................................................................................................... 9
Table 4.2 Wastewater classification .............................................................................................. 10
Table 4.2 Wastewater classification (contd.) ................................................................................ 11
Table 4.3 Required wastewater specification to discharge to Hemmaraj ..................................... 11
Table 4.4 Summary of single wastewater treatment method ........................................................ 20
Table 4.5 Reference plants and vendors of single methods .......................................................... 21
Table 4.5 Reference plants and vendors of single methods (contd.) ............................................. 22
Table 4.6 Summary of TAR system .............................................................................................. 24
Table 4.7 Summary of ozone oxidation MBR system ............................................................... 26
Table 4.8 Summary of ozone oxidation MBR system ............................................................... 27
Table 4.9 Summary of Fenton oxidation oxidation ditch system............................................... 29
Table 4.10. Comparison between fluidized bed and multiple hearth ............................................ 33
Table 4.11 Strengths and weaknesses of thermal oxidation system .............................................. 33
Table 4.12 Summary of technical and economic information about thermal oxidation system ... 34
Table 4.13 Summary of technical and economic information of EDR system ............................. 36
Table 4.14 Scoring of wastewater treatment method .................................................................... 39
Table 4.14 Scoring of wastewater treatment method (cotd.) ........................................................ 40
Table 4.15 Summary of HPW & LPW treatment methods ........................................................... 41
Table 4.15 Summary of HPW & LPW treatment methods (contd.) ............................................. 42
Table 4.16 Summary of salt treatment methods ............................................................................ 42
Table 4.16 Summary of salt treatment methods (contd.) .............................................................. 43
Table 4.17 Scoring result of HPW and LPW treatment methods ................................................. 44
Table 4.17 Scoring result of HPW and LPW treatment methods (contd.) .................................... 45
Table 4.18 Scoring result of salt stream treatment methods ......................................................... 46
Table 4.18 Scoring result of salt stream treatment methods (cotd.) .............................................. 47

iv

CHAPTER I
INTRODUCTION
1.1 Background
As environmental issue has been spread widely all over the world, people are now more concern
to the life of environment. One of the efforts that they do to save the environment is by reducing
waste that is dumped to the surroundings. This waste reducing effort is undertaken by various
parties, including industries which its activities are one of the largest waste producers in the
world.
PTT Global Chemical is an industry that has high concern to the life of environment. Though its
running production process definitely produces waste, PTTGC always strives to meet
specification of waste disposal. One of the projects that has been carried out recently by process
engineers in this company is about the propylene oxide, polyether polyol, and polymer polyol
plants, including its wastewater treatment system. Due to their concern on waste and
environment, they are striving to look for the best wastewater treatment method that could
reduce the wastewater contaminants and minimize its adverse impact on environment.
1.2 Objectives
The objectives of this feasibility study are:
1. To explore available methods for treating propylene oxide, polymer polyol, and polyether
polyol plants wastewater
2. To recommend commercially available technology for the selected method
3. To propose technology and vendor for treating the wastewater
4. To propose the most suitable method/technology for treating the wastewater
1.3 Scopes of work
The scopes of work of this feasibility study are:
1. Identify the PO, polyether polyol, and polymer polyol plants wastewater characteristics
2. Determine the general wastewater treatment process based on the wastewaters characteristics
3. Explore the information of the available wastewater treatment methods
4. Compare and select the most suitable wastewater treatment method based on specified criteria
5. Explore the information of the selected methods licenses
6. Compare and select the most suitable license for the selected method based on specified
criteria

CHAPTER II
LITERATURE
2.1 The importance of wastewater treatment
Across the world, there continues to be huge volumes of wastewater pumped directly into rivers,
streams and the ocean. The impact of this is severe, aside from the damage to the marine
environment and to fisheries it, it does little to preserve water at a time when many are predicting
that a global shortage is just around the corner.
As it stands this method of disposing of wastewater any form of water that has been
contaminated by a commercial or domestic process, including sewage and byproducts of
manufacturing and mining is largely an issue in developing nations. The regulation of waste
disposal in developing nations is seems not too firm, especially in monitoring the maximum
amount of wastewater contaminants that discharged by the industries. In the other hand, perhaps
the waste water treatment technology itself is still not capable to provide safe and
environmentally friendly treated water due to the high cost of installation and operation of
sophisticated wastewater treatment system. As an example, The World Bank estimated that
Vietnam will need an investment of $8.3 billion in order to provide the necessary wastewater
services (Wright, 2014). The underdeveloped wastewater treatment technologies and lack of
regulation regarding wastewater disposal are indeed threats to the environmental sustainability. If
such situation keep abandoned, we will probably no longer have water to use in everyday life.
When water is used by our society including industrial activities, the water becomes
contaminated with pollutants. If left untreated, these pollutants would negatively affect the water
and environment. For example, organic matter can cause oxygen depletion in lakes, rivers, and
streams. This biological decomposition of organics could result in fish kills and/or foul odors.
Nutrients in wastewater, such as phosphorus, can cause premature aging of the lakes, called
Eutrophication. Additionally, there are many pollutants that could exhibit toxic effects on aquatic
life and the public. Therefore, pollutants must be removed from the water to protect the
environment and public health.
2.2 Wastewater treatment selection
The applied wastewater treatment method actually depends on the characteristics of the
wastewater itself. Different characteristics of wastewater will result in different wastewater
treatment method. Therefore, it is important to determine the characteristics of the wastewater
before deciding which wastewater treatment is best to be applied.
Selecting wastewater treatment method based on wastewater characteristics is carried out
through the steps shown in Figure 2.1.

Aliran
air limbah
Wastewater
stream

Inorganik
Inorganic

Requires
Perlunya
pretreatment
for
Pretreatment
neutralization
untuk
netralisasi

ya

Off-gas treatment

ya

Koagulasi,
Coagulation,
flocculation,
flokulasi,
dan
sedimentation
sedimentasi

Mengandung
Contains
contaminantsyang
that
kontaminan
can be
filtered atau
or
dapat
disaring
adsorbed
diadsorb
No
tidak
Limbah dapat
Waste can be reused
dimanfaatkan
or its volume can be
kembali atau
reduced
direduksi
volumenya
No
tidak
Limbah harus
Destroy the waste
dihancurkan

Large land area is

Tersedia ruang
available
lahan yang luas
Limbah
Padat
Solid waste

No
tidak

ya

Filtrasi atau
Filtration/activated
Adsorpsi
karbon
carbon adsorption
aktif

ya

Pemisahan
Oil waterminyak
separation
/ air

ya

Requires aeration

Evaporasi
atau
Evaporation
or
ekstraksi
extraction

tidak

Trickling
Tricking
filterfilter
/ fixed
atau
Fixed-film
film biotreatment
Biotreatment

ya

Perlunya aerasi
Filter atau
Filter /
regenerasi media
adsorption
adsorpsi

ya

Lumpur
aktif
atau
Activated
sludge
/
aerated lagoon
aerated
lagoon

Air / Steam
Stripping

Contains
Mengandung
contaminantsyang
that
kontaminan
can be
filtered atau
or
dapat
disaring
adsorbed
diadsorb

ya

Filtrasi atau
Filtration/activated
Adsorpsi
karbon
carbon adsorption
aktif
Filter atau
Filter /
regenerasi media
adsorption
adsorpsi

No
tidak

Contains
Mengandung
contaminants
that
kontaminan yang
can be chemically
dapat dioksidasi
reduced or
atau direduksi
oxidized

ya

Chemical / reduksi
Oksidasi
oxidation/reduction
kimia

ya

Evaporasi
atau
Evaporation
/
ekstraksi
extraction

secara kimia

tidak
No
No
tidak

Limbah dapat

Requires solids
Perlunya
solids
recovery

recovery

ya

Anaerobic
treatment

Solid / Concentrated Phase

Waste can be reused

dimanfaatkan
or its volume can be
kembali atau
reduced

direduksi
volumenya

tidak
No

No
tidak

Insinerasi
atau wet
Incineration
air oxidation

ya

No
tidak

No
tidak

ya

Contains
Mengandung
contaminants that
kontaminan yang
can di-stripping
be stripped
dapat

Oil
minyak

ya
Perlunya
Needs
pretreatment to
pretreatment
remove oil &
penghilangan
minyakgrease
dan lemak

Air / Steam
Stripping

No
tidak

Contains
Mengandung
contaminants that
kontaminan
can be yang
dapatprecipitated
dipresipitasi

No
tidak

Dapat
Biodegradable
terbiodegradasi

Pretreatment

No
tidak

Mengandung
Contains
contaminantsyang
that
kontaminan
can di-stripping
be stripped
dapat
mis. amonia

Off-gas treatment

Organik
Organic

Equalization
tank
Kolam
ekualisasi

Figure 2.1 Wastewater treatment method selection

(Source: Setiadi, 2014)

Limbah harus
dihancurkan

Destroy the waste

Solid / Concentrated Phase

Insinerasi
atau wet
Incineration
air oxidation

2.3 Physical, biological, and chemical wastewater treatment

Physical wastewater treatment methods include processes where no gross chemical or
biological changes are carried out and physical phenomena are used to treat the
wastewater. Physical methods are usually carried out in order to remove large entrained
object in the wastewater such as solids. Examples of physical wastewater treatment
method are screening, sedimentation, clarification, filtration, and many others. Physical
treatment is usually carried out at the preliminary step of wastewater treatment before the
wastewater is routed to the next treatment steps.
Biological wastewater treatment is a method to treat wastewater by biological activity,
mostly microorganisms. Biological treatment is an important part of any wastewater
treatment plant that treats wastewater from either municipality or industry having soluble
organic impurities or a mix of two types of wastewater sources. Compared to chemical
treatment, biological treatment has more obvious economic advantage, both in terms of
capital investment and operating cost.
Although biological treatment seems economically promising, there are stringent
requirements for wastewater that will be treated biologically. The main requirement is that
the wastewater has to meet a certain amount of biological oxygen demand and chemical
oxygen demand ratio (BOD/COD). Wastewater with BOD/COD ratio is less than 0.1
shows that the wastewater is hard to be treated biologically. Therefore, the wastewater
should be treated by other method first before sent to biological treatment in order to
increase its BOD/COD ratio. A BOD/COD ratio of 0.4 0.6 shows that the wastewater
should be treated by aerobic biological treatment, which involves contacting wastewater
with microbes and oxygen to optimize the growth and efficiency of biomass. Wastewater
with BOD/COD ratio >0.6 shows that it should be treated by anaerobic biological
treatment which does not require addition of oxygen.
In biological treatment, the performance of the treatment is dependent upon the activity of
microorganisms and their metabolism which can be dramatically affected by toxic
compounds in the wastewater. Many materials such as organic and inorganic solvents,
heavy metals, and biocides can inhibit the biological activity in the treatment plant. Figure
2.2 lists inhibitory levels reported for some metals, inorganic, and organic substances
which affect the effectiveness of biological treatment.
If wastewater has low BOD/COD level and/or contains inhibitory compound which makes
it infeasible to be treated by biological treatment, then other options of wastewater
treatment needs to be carried out. One promising option is by chemical treatment, which
consists of using chemical reactions to improve the wastewater quality. Chemicals used in
chemical treatment are usually strong oxidizers such as chlorine, hydrogen peroxide,
ozone, and many others. Such oxidizers can remove nearly all contaminants in the
wastewater, including materials that are recalcitrant or even refractory to biological
treatment.
4

Contrary to biological treatment, influent requirements to enter chemical treatment are not
as stringent as biological treatment. However, the cost of chemical treatment is usually
higher, especially to treat highly contaminated wastewater.

Figure 2.2 Inhibitory compounds for biological treatment

(Source: Wastewater Treatment Manuals, 1997)

2.4 General PO/SM, polymer polyol, and polyether polyol plants wastewater
characteristics
In general, one of major wastewater sources in PO/SM, polymer polyol, and polyether
polyol plant is the alkaline washing unit. This alkaline washing produces an aqueous
stream, also called alkaline purge, highly loaded in organic compounds and sodium which
can be taken integrally to water treatment, without any prior pre-treatment, which permits
the recovery of organic matter. The typical composition of the alkaline purge is included
between values of 4 and 8% of compounds of alcoholic nature, largely monopropylene
glycol and methylbenzyl alcohol, between values of 3 and 6% of organic salts, largely
sodium benzoate and phenolate and a content greater than 2% of sodium hydroxide.
The purification treatment of waste water arising in the process of PO/SM, polyether
polyol, and polymer polyol is very expensive, mainly due to three aspects: its high content
in organic matter which is translated into a high value of the chemical oxygen demand
(COD greater than 40% by weight), the high flow of said stream and, finally, the fact that
it contains organic compounds which are not easily degradable.

CHAPTER III
METHODOLOGY
The main objective of this feasibility study is to determine the most suitable commercial
wastewater treatment method to treat wastewater from PO/SM, polyether polyol, and
polymer polyol plant. The objectives can be achieved through the following steps:
1. Studying wastewater characteristics
The aim of wastewater characteristics study is to determine the characteristics of the
wastewater. The wastewater characteristic is determined through studying data of
wastewaters contaminants.
2. Studying commercially available technology for the wastewater treatment
After determining characteristic of the wastewater, study about commercially available
technologies that are possible to treat the wastewater is carried out. These technologies
are further selected based on specified criteria to determine which technologies are the
best to be applied in the wastewater treatment system.
3. Technology selection
Selecting wastewater treatment technology is carried out through scoring. Before
scoring, criteria for selecting the wastewater treatment methods are determined. Those
criteria are then being scored based on the wastewater treatment data from the study.
Each criteria will contribute a certain percentage to the overall score. Method that has the
highest score will be considered as the most suitable wastewater treatment method. A
workflow diagram of this feasibility study is shown below.
Start
Studying wastewater
characteristic

Studying commercially
available technology

Wastewater
characteristic

Commercially
available
technologies

Technology selection
The most suitable
wastewater treatment
method
Finish
Figure 3.1 Workflow diagram of feasibility study

CHAPTER IV
RESULTS AND DISCUSSION
4.1 Wastewater Characteristics
4.1.1 Wastewater sources
The wastewater given in this case comes from three main units. These units are Propylene
Oxide/Styrene Monomer (POSM) Unit, Polyether Polyol (PoP) Unit, and Polymer Polyol
(PoP) Unit. More detailed information about the wastewater coming from each unit is
described below:
1. Propylene Oxide/Styrene Monomer (POSM) Unit
The POSM Unit generates five streams of wastewater. These streams are Highly Polluted
Water (HPW), Acid Purge (AP) Stream, Low Polluted Water (LPW), rain water, and
laboratory residual stream. The HPW is a caustic wastewater generated from washing
section and dehydration reaction in POSM unit, while the AP stream is generated in the
oxidation section. The LPW comes from final emptying of equipment that could not be
pumped out.
2. Polyether Polyol (PeP) Unit
The Polyol Unit consists of two subunits: Flexible and Rigid & CASE Unit. Each subunit
generates five streams of wastewater namely HPW, LPW, rain water, laboratory residual
stream, and by-product (high salt) stream. However, though the types and composition of
the stream from both subunits are identical, the flow rate is different between one and
another.
3. Polymer Polyol (PoP) Unit
The polymer polyol unit generates two types of wastewater: highly polluted water (HPW)
and low polluted water (LPW). The HPW comes from monomers recovery system and
condensate vacuum system. The LPW consists of liquid from final emptying of equipment,
rain water collected from process area, effluent from gas abatement device, and laboratory
residual stream.
4.1.2 Wastewater composition
The composition of wastewater that is generated in each unit is summarized in Table 4.1.

Table 4.1 Summary of wastewater characteristic from POSM, Polyether Polyol, and polymer polyol unit
(Source: OSBL Basis Design Data for Repsol, 2014)
3

Flow rate (m /h)

Unit

Type

Highly Polluted Water

(LPW)
Propylene
OxideStyrene
Monomer
(POSM)

Acid Purge (AP) Stream

Normal

Max

Contaminants (mg/l)

Temperature (oC)

pH

COD

BOD

Depends on the waste

water stream (usually
30-40C from the
washing sections).
The storage tank for
this streams usually
operates between 1520C

13-14

75

1.8-2

75,000

0.07

12-14

46%

21%

4.38

7.5-8.5 (vacuum
system), 0.5
(abatement
device)

1.1% (vacuum
system), 5%
(abatement
device)

0.1-0.6%
(vacuum
system), 3%
(abatement
device)

27-32

5.7 6.7

32

6.7

180,000 200,000

SS

Oil

TDS

Note

4-5
Using either
biological waste
water
treatments and
incinerator

Low Polluted Water

(LPW)
Rainwater
Laboratory residual
stream
Highly Polluted Water
(LPW)
Low Polluted Water
(LPW)

Polyether
Polyol
(Flexible)

Rainwater
Laboratory residual
stream
By-product stream (high
salt)

0.225

Potassium
content >14%
Polyol content
<5%

Table 4.1 Summary of wastewater characteristic from POSM, Polyether Polyol, and polymer polyol unit (contd.)
(Source: OSBL Basis Design Data for Repsol, 2014)
3

Flowrate (m /h)
Unit

Type
Normal
Highly Polluted Water
(LPW)
Low Polluted Water
(LPW)

Polyether
Polyol
(RIGID &
CASE)

Contaminants (mg/l)

Temperature (oC)

Note

Max

pH

COD

BOD

0.078

12-14

46%

21%

7.5-8.5 (vacuum
system), 0.5
(abatement
device)

1.1% (vacuum
system), 5%
(abatement
device)

0.1-0.6%
(vacuum
system), 3%
(abatement
device)

Oil

TDS

Rainwater
Laboratory residual
stream

0.15

By-product stream (high

salt)

Polymer
Polyol

SS

Highly Polluted Water

(HPW)

5% (max. 9%)

BOD/COD
ratio: 0.04

Low Polluted Water

(LPW)

0.3% (max.
1%)

BOD/COD
ratio: 0.05

Potassium
content >14%
Polyol content
<5%
Nitrogen
content: 4,500
ppm

According to wastewater compositions and characteristics in Table 4.1, it is shown that

contaminants in the wastewater are mostly organic compounds, which is represented by
chemical oxygen demand (COD) level. The range of COD level in the wastewater streams
varies greatly, from 3,000 ppm to 180,000 ppm. Some of the streams also have very low
ratio of BOD/COD (< 0.1) which indicates that those streams are hard to be degraded
biologically. In addition, by-product streams from polyether polyol plant consist of polyol,
a chemical compound which is recalcitrant to biological treatment.
Although some streams are seem to be hardly biodegradable, some of the remaining
streams are likely possible to be sent to biological treatment due to its low level of COD.
Those streams are the LPW of polyether polyol (flexible) unit which has BOD/COD level
of 0.47, LPW from PO/SM plant, and also LPW from polyether polyol plant.Beside
organic contaminants, some streams in the wastewater also have nitrogen, salt
components, and even a small amount of oil.
4.1.3 Wastewater classification
The variety of contaminants in the wastewater makes the streams should be classified
based on the type and level of contaminants. This is done because some types of
contaminants may inhibit treatment process to remove the other contaminants type. For
example, the presence of salt in the wastewater may inhibit chemical process to remove
organic contaminants. Thus, salt and organic-containing wastewater should be separated
and treated by different method.
Based on the types and contaminants level, the wastewater is separated into three main
streams. The first and the second streams are streams without salt content while the third
streams are streams that contain salt, namely salt stream. The major contaminants in the
first and second streams are organics and nitrogen. The first streams are those that contain
high COD level (>10,000 ppm) as well as low BOD/COD ratio (<0.1). These streams are
indeed hard to be degraded biologically. The second streams are those that contain
medium to low COD (<10,000 ppm) level and medium to high BOD/COD ratio. We now
call the first streams as high polluted water (HPW) and the second streams as low polluted
water (LPW). Classification of streams along with their calculated compositions after
being combined is shown in Table 4.2. Calculation of combined streams composition is
given in Appendix A.

Classification
High Polluted Stream (HPW)

Low Polluted Stream (LPW)

Table 4.2 Wastewater classification

Streams
HPW from PO/SM
Acid purge from PO/SM
LPW from polymer polyol
HPW from polymer polyol
LPW
from
polyether
polyol
(flexible) unit
LPW from polyether polyol (rigid &
CASE) unit
LPW from PO/SM

Final characteristics
Flow rate: 45.7 m3/h
COD: 145,219 ppm
N:295 ppm
BOD/COD: <0.1
Flow rate: 10.38 m3/h
pH < 1
BOD: 10,088 ppm
COD: 19,373 ppm
BOD/COD: 0.52

10

Classification
Salt stream

Table 4.2 Wastewater classification (contd.)

Streams
Final characteristics
By-product from polyether polyol Flow rate: 0.5 m3/h
(rigid & CASE) unit
Potassium content: 100,382
By-product from polyether polyol ppm
Polyol content: 35,581 ppm
(flexible) unit
62,160
ppm
HPW from polyether polyol BOD:
COD: 136,160 ppm
(rigid & CASE) unit
HPW from polyether polyol
(flexible) unit

All of the streams will be discharged to Hemmaraj Industrial Wastewater Treatment. The
required wastewater specification to be discarged to Hemmaraj is shown in Table 4.3.
Table 4.3 Required wastewater specification to discharge to Hemmaraj
(Source: Hemmarajs wastewater discharge specification, 2014)

Contaminant

Maximum level

BOD

< 500 mg/l

COD

750 mg/l

Suspended solid

200 mg/l

TDS

3000 mg/l

TKN

100 mg/l

pH

5.5 9.0

Temperature

45oC

Oil and fat

10 g/l

4.2 Available Technology for Wastewater Treatment

As we separate the wastewater into three main streams, the treatment method for each
stream should be different. Available technologies that may be possible to treat the
wastewater streams are described below.
4.2.1 Technology for high polluted and low polluted stream
4.2.1.1 Single method
In order to reduce the contaminant as well as to meet the wastewater discharge
requirement to Hemmaraj, the wastewater needs to be treated by several means of
technology. The technology could be chemical, biological, or even combination of
chemical and biological treatment. If the contaminant in the wastewater is not too high, the
wastewater can be treated by only one technology to meet the Hemmarajs discharge
specification. The technology is referred as a single method. The following explanation
11

will describe available single methods that could be applied to reduce the wastewater
contaminant. All of the following single methods have been applied commercially, either
as industrial or municipal wastewater treatment method.
1. Wet Air Oxidation (WAO)
The wet air oxidation process is a type of chemical treatment. It is an oxidation reaction
that occurs in the liquid phase. The chemistry of wet oxidation is such large molecules
which are difficult to treat biologically are oxidized by dissolved oxygen at an elevated
pressure and temperature. The elevated pressure in wet air oxidation process is required to
maintain the water in the liquid phase.
Wet oxidation reaction kinetics has been the subject of numerous studies. It is then
indicated that the oxidation proceeds by a free-radical reaction mechanism. In the absence
of initiators, free radicals are formed by reaction of oxygen with the weakest C-H bond of
the oxidized organic compound. The free radicals which has large electron affinity then
oxidizes organics and other compounds, such as sulfur, halides, nitrogen, and phosphor.
The formation of free radicals is shown in reaction (1) (4), while oxidation of wastewater
contaminants is shown in reaction (5) (10).
RH + O2 Ro + HO20
RH + HO2o Ro + H2O2
H2O2 + M 2OHo
H2O2 H2O + O2
Organics + O2 CO2 + H2O + RCOOH*
Sulfur species + O2 SO42-/other inorganic sulfates
Halides species + O2 inorganic halides
Organic Cl + O2 Cl- + CO2 + RCOOH*
Organic N + O2 NH3/NO3/elemental nitrogen + CO2 + RCOOH
Phosphorus + O2 PO43*
Major fraction of residual organic compound

(1)
(2)
(3)
(4)
(5)
(6)
(7)
(8)
(9)
(10)

Since the liquid phase in wet air oxidation is not vaporized, this process requires less
energy for auto thermal operation rather than incineration. The nitrogen and sulfur
compound that may present in the waste water stream are not released as gaseous NOx and
SOx, but remain in the solution as acceptable nitrate and sulfate, meanwhile the
hydrocarbon compounds are converted to CO2 and water. The complete oxidation is rarely
happens, so a portion of organic COD will remain and ready to be treated biologically. The
wet oxidized effluent usually exhibits BOD: COD ratio of 0.6-0.7
The oxidation reaction is usually carried out at temperatures of 150oC to 320oC and
pressure from 150 to 3200 psig. Oxygen as the oxidizing agent can be introduced from
compressed air or even pure compressed oxygen. However, the use of air as oxygen source
could lead to larger compressor cost, higher pressure rated equipment, and heat loss to

12

nitrogen component in the air. Therefore, the use of pure oxygen as the oxidizing agent is
such an attractive option.
During the operation, the feed of wet air oxidation system is pumped through heat
exchangers by a high pressure pump combined with a small amount of compressed air.
Introducing the feed stream along with small amount of compressed air is carried out in
order to prevent fouling in the heat exchangers, which are used to heat the cold feed. For
starting up, an external source of heat is needed to heat the cold feed. Heating the cold feed
for starting up can be carried out in trim heater using steam or hot oil as the external
sources of heat. The hot feed is then introduced from the bottom of the WAO reactor and
the oxygen is introduced from another bottom part of the reactor.
The outlet stream leaving the WAO reactor contains of two phase; hot gas and hot liquid.
The outlet stream is then sent through heat exchanger to be cooled forthwith heating the
incoming feed. The stream then goes through process cooler to be cooled by cooling water
prior to pressure let-down across the pressure control valve. The cooled two-phase stream
is sent to pressure control valve to be flashed before entering the separator. The separator
receives the flashed two-phase stream, resulting separation of liquid effluent and noncondensable gas. The off-gas exits at the top of the separator and sent to the final treatment
unit or being used for other process heating, such as in PO/SM boilers
An application of wet air oxidation as wastewater treatment method can be seen at POSM
plant of Repsol YPF in Tarragona, Spain. In its wastewater treatment plant, the oxidation
of waste water occurs in bubble reactor at 295oC at 95 bar and 1.5 hour of reaction time
using pure compressed oxygen as the oxidant.. The nominal COD reduction of waste water
being treated by wet air oxidation is approximately 61%, resulting liquid effluent with
COD range of 20,000-30,000 mg/L which is further treated by PACT. The scheme of wet
oxidation process in POSM Plant of Repsol Tarragona is shown in Figure 3.

Figure 4.1 Wet air oxidation process

(Source: The Use of WAO and PACT for the Treatment of PO/SM Industrial Wastewater, 2002)

13

2. Ozone Oxidation
Ozone (O3) is one of the strongest commercially available oxidizing agents. This molecule
consists of three oxygen atoms which is unstable and very reactive under normal nearearth condition. When decomposes in water, ozone creates hydroxyl radicals which react
quickly with a number of organic and inorganic compounds containing accessible amino
groups, double bonds, or aromatic systems. A complex chain of reaction that occurs and
results formation of OH* and superoxide* radicals is shown by reaction (1) (4) (Karat,
2013).
O3 + OH- O2*- + HO2*
(1)
**O3 + O2 O3 + O2
(2)
**O3 HO3
(3)
**
HO3 OH + O2
(4)
Ozone reaction with inorganic or inorganic compounds is shown by reaction (5) and (6).
CN- + O3 CNO- + O2
(5)
RCH2OH + 2O3 RCOOH + 2O2 + H2O
(6)
Oxidation by ozone can be performed in ozonation reactor at a large range of pH. The OH*
radical formation is dominant at high pH (>10), while the oxidative reaction with O3 is
more selective at low pH (<4) but occurs relatively slow. Oxidative reaction in neutral pH
is also preferable to minimize the need of pre and post pH adjustments. The temperature to
carry out the oxidative reaction is usually at ambient temperature (~25oC). Higher
temperature will generally increase the reaction rate, yet reducing the solubility of O3 in
water.
The general ozonation unit is shown in Figure 4.2. The unit consists of O2 tube that
provides pure O2 which is used as feed for producing O3, O3 regenerator, ozonation tank,
and residual ozone destructor. Air can also be used as feed to produce O3 by replacing the
O2 tube by air compressor to introduce the air to the O3 generator. O3 is synthesized in tube
or plate generators, yielding air-ozone or oxygen-ozone mixtures with concentrations of
ozone less than 20% (by mass) which is totally safe (Rein Munter in Industrial
Wastewater Treatment). O3 which is not dissolved during contacting is converted back to
oxygen before being discharged to atmosphere or reuse application. The conversion of
ozone into oxygen may be accomplished using thermal or thermal-catalytic system.

Figure 4.2 Scheme of ozone oxidation process

(Source:)

14

3. Powdered Activated Carbon (PACT)

PACT unit combines activated carbon adsorption and biological degradation to remove
organic components in the wastewater. The biological activity is combined with carbon
adsorption due to the wastewater components characteristic, which mostly contains
aromatic and polyol compound that are hard to be degraded by microorganisms. The
addition of activated carbon helps to adsorb organic components that can hardly be
degraded by microorganisms, so they could cling to their food source more efficiently.
An ordinary PACT unit consists of an aeration basin followed by a clarifier. The aeration
basin is used for treating the wastewater by activated carbon absorption forthwith
biological treatment. The effluent stream exiting the PACT unit is then sent to the clarifier
to separate the liquid effluent and the sludge that contains microorganisms as well as
activated carbon. Due to the presence of both biological growth and adsorption of organic
components occurring in the PACT system, wasting of spent carbon is required. This
wasted carbon is regenerated and returned to the PACT system.
In order to optimize the removal of organic compound, PACT system is usually combined
in series. Such system is applied in the waste water treatment of Repsol YPFs POSM
plant. The PACT unit consists of two aeration basins, each followed by a clarifier. The
first and the second set of PACT unit are called PACT-1 and PACT-2. The PACT-1
consists of 65 m diameter concrete aeration basin and a 17 m diameter clarifier while
PACT-2 consists of 30 m diameter aeration basin and a 17 m diameter clarifier. The flow
rate of wastewater that enters this system is 90 m3/h and average COD level of 26,000
ppm. The total COD reduction of both PACT tank is 97.6%. The scheme of the PACT unit
is shown in Figure 4.3.

Figure 4.3 Repsol PACT system unit

(Source: The Use of WAO and PACT for the Treatment of PO/SM Industrial Wastewater, 2002)

15

In some plants, the presence of PACT system is followed by wet air regeneration (WAR).
This system is used to recover the spent carbon from the PACT system. The recovered
activated carbon is then sent back to PACT unit to adsorb organic contaminant in the
wastewater.
The process for wet air generation is actually similar to the wet air oxidation process but
compressed air is used instead of oxygen. Before entering the wet air regeneration process,
the PACT sludge is thickened to ~5% solids content to obtain sufficient COD content for
auto thermal operation. The sludge is then pumped using hydraulic exchange pump and
compressed air is added to the sludge before passing the heat exchanger to be heated to
210oC. The hot stream sludge is then injected to the bottom of stainless steel bubble
reactor which operates at 243oC and 63 bar. The effluent leaving the reactor passes through
heat exchanger and cooled, resulting cooled fluid which sent to two phase separator. The
two phase separator successfully results two separated phases: gas and slurry. The gas
phase is sent to POSM plant boilers and the regenerated activated carbon slurry returns to
PACT aeration tank. The inert ash from in the bottom of the reactor is collected and
purged periodically to the storage drum, from where it is sent to filter press to be
dewatered before disposal.
4. Fenton Oxidation
Fenton oxidation is a process of oxidizing contaminants in the wastewater by using a
mixture of hydrogen peroxide (H2O2) and ferrous ion (Fe2+). The process is based on
formation of reactive oxidizing species by two reaction pathways: a radical pathway,
which considers an OH radical formation (reaction 1) and a non-radical pathway
considering ferryl ion production (reaction 2). Each reaction is shown as the following:
Fe2+ + H2O2 Fe3+ + OH- + OH*
Fe2+ + H2O2 FeO2+ + H2O

(1)
(2)

The Fenton reagent destroys a wide variety of organic compounds without formation of
toxic by-products (Barbusinski, 2009). Fenton oxidation process is characterized by its
cost effectiveness, simplicity, and suitability to treat aqueous wastes with variable
compositions. Comprehensive investigations show that Fenton oxidation is effective in
treating various industrial wastewater contaminants including aromatics, dyes, pesticides,
surfactans, explosives, and many other substances. Fenton reagent can also be effectively
used to for destruction of toxic waste and non-biodegradable compounds to render them
more suitable for a secondary biological treatment.
An application of Fenton oxidation in wastewater treatment plant was shown by its
effectiveness to treat a highly contaminated wastewater from a pharmaceutical plant. The
wastewater has COD level of 300,000 ppm, BOD level of 2900 ppm, and total suspended
solid (TSS) of 45,950 ppm. The Fenton oxidation process could reduce approximately
90% COD level in the wastewater.

16

5. Membrane Bioreactor (MBR)

The MBR process is a suspended growth activated sludge that utilizes microporous
membrane for solid-liquid separation. In this system, contaminants in the wastewater are
degraded by biological activity within the bioreactor. Treated wastewater and solids that
include biomass are then separated by ultrafiltration or nanofiltration membrane.
The typical arrangement of MBR system includes an aerated portion of the bioreactor,
anoxic zone, and the membrane filter. Based on the membrane location, there are two
configurations of MBR system: external and internal/submerged MBR sytem. Comparison
between the two MBR systems configurations is provided in Figure 4.4.

Figure 4.4 Comparison between external and internal membrane configuration

(Source: MBR for Municipal Wastewater Treatment)

17

Based on the fact that our wastewater has quite high flow rate, external membrane
configuration seems to be preferred due to its ability to handle higher flux. The external
MBR system has been widely applied either in industrial or municipal wastewater
treatment. One of the applied external MBR configuration is at municipal wastewater
treatment of Commune De Monteux, where its MBR can handle maximum flow rate of
400m3/h and has COD removal up to 96%. This MBR system is provided by Siemens
Water. The process scheme of external MBR system is shown in Figure 4.5.

Figure 4.5 Process scheme of external membrane system in Commune De Monteux WWT
(Source: Siemens Water Technology, 2010).

MBR system operates at ambient pressure and temperature and has transmembrane
pressure (TMP) up to 150 kPa. Standard flux rate for external MBR system ranges
between 50 to 200 L/m3/hr. Typical sludge retention time within the bioreactor is 5 30
days.
6. Thermophilic Membrane Bioreactor
The principle of thermophilic MBR is actually similar to MBR; a bioreactor equipped with
membrane filter which facilitates separation of solids and liquid effluent from the
bioreactor. A major different between them is that the bioreactor in thermophilic MBR
operates at temperature over 50oC, usually 75oC. The elevated temperature can be
achieved by autoheating due to the heat produced by aerobic metabolism of the
microorganisms that consume abundant organic material present in the wastewater.
However, a minimal quantity of organic material is needed to sustain self-heating. Juteau
(2006) stated that a theoretical minimum of 24 g/l COD, oxygen consumption of 1.42
kg/kg organic matter oxidized, and BOD/COD ratio of 0.5 can produce heat of 20,000
kJ/kg volatile solid destroyed (assumed specific heat: 4.2 kJ/kgoC).
18

Thermophilic bioreactor performs well at higher organic loading rates and operates at
higher biodegradation rates compared to mesophilic (ambient temperature and pressure)
bioreactor. This is due to the enhancement of contaminants solubility, such as organics,
oil, and grease at higher temperatures. The effectiveness of thermophilic MBR in
degrading contaminants results a smaller size of bioreactor which also means smaller
footprint. On the contrary to these advantages, thermophilic conditions cause poor
settleability of sludge due to deterioration of sludge settling properties (Abeynayaka &
Visvanathan, 2010).
Another characteristic revealed in the investigation of aerobic thermophilic bioreactor is
the absence of nitrification (NH4+ NO3-) over 40oC. As a result, various hypothesis
arise, such as there is only ammonification occurs at thermophilic bioreactor, there is direct
aerobic deammonification, or there is actually nitrification of ammonia but quickly
denitrified. What is clear is the fact that an important part of the nitrogen is in the form of
ammonia. Due to the high temperature, ammonia can be completely volatilized and cause a
very bad smells (Abeynayaka & Visvanathan, 2010). This problem can be avoided by
recuperating ammonia vapors with scrubber or lower the ammonia volatilization by using
highly efficient aerator with oxygen transfer rate (OTE) of >90%.
The application of thermophilic MBR in wastewater treatment plant has recently been
spread widely. This technology has been applied in specialty chemical plant, food industry,
pharmaceuticals, and many others. An applied thermophilic MBR system in a specialty
chemical plant could handle wastewater with COD loading up to 180,000 ppm and has an
average COD removal of 90%.
7. Oxidation Ditch
Oxidation ditch is a modified activated sludge biological treatment that utilizes long solid
retention time to remove biodegradable organics. Typical oxidation ditch consists of a
single or multichannel configuration within ring, oval, or horseshoe-shaped basin. The
wastewater within the basin is circulated by the work of surface aerators. The circulating
wastewater helps to mix the oxygen with the wastewater which could foster microbial
growth and ensures contact of microorganisms with the incoming wastewater. A scheme of
oxidation ditch system is shown in Figure 4.6.
Oxidation ditch system operates at ambient temperature and pressure. The wastewater that
enters the ditch is aerated and circulated at about 0.25 0.35 m/s to maintain the solids in
suspension. The RAS recycle ratio is from 75 150% and the OTE ranges from 2.5 3.5
lb/Hp-hour. Required BOD loading that enters the system rates vary, from less than 160
ppm to more than 40,000 ppm (US Environmental Protection Agency, 2000).

19

Figure 4.6 Oxidation ditch system

(Source: US Environmental Protection Agency, 2000)

The main advantage of oxidation ditch is the ability to achieve removal performance with
low operational requirements as well as operating and maintenance costs. There is also
added measure of reliability and performance over other biological processes owing to a
constant water level and continuous discharge which lowers the overflow rate. Oxidation
ditch system also has long hydraulic retention time and complete mixing, which minimize
the impact of shock load or hydraulic surge. In addition, it produces less sludge than other
biological treatment processes due to the extended biological activity during the activated
sludge process. The last, the operation of oxidation ditch is more energy efficient and
result in reduced energy cost compared to other biological treatment processes.
Contrary to the advantages, oxidation ditch system has disadvantages such as is high
suspended solids concentration in the effluent and requirement of larger land area than
other biological treatment processes. This can prove costly, limiting the feasibility of
oxidation ditch in urban, suburban, or other areas where land acquisition costs are
relatively high.
In summary, information about commercially available single method is given in Table 4.4

Method
WAO
Ozone Oxidation
Fenton Oxidation
PACT
MBR
Thermophilic MBR
Oxidation ditch

Table 4.4 Summary of single wastewater treatment method

Organic loading
Operating condition
COD removal
Up to 150,000 ppm
T: 150320oC
55 75%
COD
P: 11 217 atm
>100,000 ppm COD T&P: ambient
60 92%
Up to 300,000 ppm
COD

T: 20 80oC ; P: atm
pH: 3.5

90%

BOD/COD: 0.4
0.6

T & P: ambient

98.5 99%
89 97%
Up to 98.5%
Up to 97%

T: 40 75oC

Scale

Industry

20

Reference plants of each method along with the vendors are listed in Table 4.5.
Table 4.5 Reference plants and vendors of single methods
Method
Reference plants
Vendors
WAO
1. Atofina Italias methyl methacrylate plant,
Siemens (1 4)
Rhoo, Italy
Kenox (5)
2. BASF ethylene facility, Port Arthur, Texas
3. Tosco refinery
4. Municipal treatment plant of The Passaic
Valley, New Jersey
5. Ontario Hydros Bruce Spent Solvent
Ozone Oxidation 1. Wastewater treatment plant city of Kalundborg, ITT (1)
Denmark (20% municipal and 80%
Xylem (2 3)
pharmaceuticalsinsulin production plant,
1200 m3/h) (ITT)
2. Municipal wastewater treatment plant in
Regensdorf, Switzerland (900 m3/h) (Xylem)
3. Hospital Waldbrohi wastewater treatment,
Germany (648 m3/h) (Xylem)
Fenton Oxidation 1. Specialty chemical maufacturer, Louisiana (40
US Peroxide
GPM wastewater with 400 - 600 mg/l phenol
compound and 4000 - 5000 mg/L COD)
2. Refinery Plant, Southeast US (15 GPM
scrubber blowndown system containing COD,
phenols, and organic compounds)
3. Emergency treatment of phenol contaminated
wastewater at chemical plant, Alabama
4. Aircraft Painting Stripping and Maintenace
Facility, Midwest US (wastewater containing
toxic compounds e.g. methylene chloride,
pentachlorophenol, nitrophenols)
5. Wood treating facility (wastewater containing
phenols, naphtols, and cresols)
MBR
1. Syral, Groupe Tereos, Nestle, France (250 v/h)
Degremont industry
(Degremont Industry)
(1 3)
2. Groupe SCA, Laakirchen, Austria (2,500 m3/h) Xylem (4 5)
(Degremont Industry)
3. PetroChina Company Ltd. (1600 m3/h )
(Degremont Industry)
4. Gebt Lang Papier GmbH Ettringen paper mill
(396 m3/h) (Xylem)
5. SCA Graphic Laakirchen AG, Austria paper
mill (826.5 m3/h) (Xylem)
Thermophilic
1. Sartomer Specialty Chemicals
BioConversion
MBR
2. Alpharma Pharmaceuticals
Solutions
3. Glaxo Pharmaceuticals
4. K&K Foods
5. Specialty Food Chemicals
6. Ferro Specialty Chemicals
7. Groundwater remediation
8. Sartomer Specialty Chemicals
9. Wolverhampton Chemicals

21

Table 4.5 Reference plants and vendors of single methods (contd.)

Method
Reference plants
Vendors
PACT

Siemens

Oxidation ditch

1. Central water reclamation facility, Florida

(capacity of 22.4 MGD)
2. Municipal wastewater treatment of Santa Rosa
Country, Florida (capacity of 3 MGD)

Westech
Engineering
Xylem
S & N Airoflo

4.2.1.2 Combined method

Although there are many commercial single wastewater treatment methods, it is known
that none of the said single methods is able to treat the wastewater to meet the discharge
requirement to Hemmaraj. All of the contaminants are still over the limit of Hemarajs
wastewater discharge requirement. Moreover, some of the streams are not feasible to be
combined and treated in a single method because contaminants in a certain stream can
inhibit the treatment. Therefore, a combination of single method is needed in order to meet
the discharge requirement.
The idea of single method combination is to combine the chemical and biological
treatment. The highly polluted water (HPW) will be treated by both methods: chemical
treatment first and followed by biological treatment. The chemical treatment is needed to
reduce BOD/COD ratio of HPW, so that the ratio meets the requirement to enter biological
treatment. The low polluted water (LPW) is directly sent to biological treatment due to its
BOD/COD ratio that has met the requirement of biological treatment. Below are detailed
22

descriptions of wastewater treatment method combination that could possibly treat the
HPW and LPW.
1. Wet Air Oxidation Powdered Activated Carbon Wet Air Regeneration
Combination of wet air oxidation, powdered activated carbon, and wet air regeneration is
called TAR. In this method, the wet air oxidation system acts as a chemical treatment
which treats the highly polluted water at the beginning. The effluent leaving the WAO
system is then enters the PACT to be treated by biological means and activated carbon
along with the LPW. The mixture of WAOs effluent and LPW that has been treated will
leave the PACT system and enter the sand filter for final treatment before being discharged
to Hemaraj.
In our case, the HPW wastewater with flow rate of 45.7m3/h will first enter the wet air
oxidation system. Here, the organic contaminant which is represented by COD will be
oxidized and converted into carbon dioxide, water, and organic acid. In the other hand, the
organic nitrogen contaminant will be converted into ammoniac, nitrate, or elemental
nitrogen, carbon dioxide, and organic acid.
If we consider a 65% removal of organic contaminant by the WAO, (similar to WAO
performance in POSM Plant of Repsol Tarragona, Spain) the HPWs COD concentration
will be reduced to 50,827 ppm. Along with the LPW, this WAO effluent is sent to the
PACT. However, due to the acidic pH of LPW, the LPW stream needs to be neutralized
first until reach a certain pH. The neutralized LPW which flow rate is 10.38m3/h and COD
concentration of 19,373 ppm is then combined with the WAOs effluent and routed to the
PACT system.
If we consider the PACTs maximum performance of COD and organic nitrogen
contaminant removal are 83%, the COD concentration in the PACT effluent will be 360
ppm and TKN concentration will be 36 ppm. This concentration has actually met the
discharge specification of Hemmaraj. However, to ensure that the amount of suspended
solid has already met the discharge requirement as well, this PACT effluent is routed to the
sand filter to reduce the remaining suspended solid. After being treated by the sand filter,
the wastewater is ready to discharge to Hemmaraj.
As the fresh activated carbon cost that is used in PACT system has a large contribution in
the overall cost of the method, this activated carbon needs to be regenerated. Regeneration
of activated carbon is done by the WAR. The sludge containing activated carbon and
biomass leaving the PACT system will be separated from the liquid effluent and enter the
WAR to be burnt by air. After being treated in the WAR, the regenerated activated carbon
will be sent back to the PACT system. It is also important to note that the amount of
activated carbon is usually lost approximately 10% of the initial mass in the WAR system.
Therefore, a 10% addition of fresh activated carbon is needed to the PACT system.
Summarized information about the TAR system is listed in Table 4.6.
23

Table 4.6 Summary of TAR system

Operating condition
Pros & Cons
Performance
Estimated cost
Sufficient
energy COD removal:
Capital
cost:
WAO
3
o
o
due
to
the
liquid

WAO:
75

90%
$4,831,396/m
/h
T/P: 150 C 320 C/11
Oxidation
PACT: 83%
Operating cost: $
217 atm
Autothermal
TKN removal: up to 2.6/m3
Retention time: 15
operation
83%
120 min
oxides
of
Flow rate: 1 50 m3/h No
nitrogen or sulfur in
PACT
the off-gases
T/P: ambient
High
operating
Minimum dissolved
condition
O2 : 2 ppm
special
Flow rate: 0.1 378.5 Needs
material for the
m3/h
WAO reactor
WAR
o

Needs
VOCs
T/P: up to 260 C/up to
treatment
75 atm
Flow rate: > 0.5 m3/h Large footprint

2. Ozone Oxidation Membrane Bioreactor (MBR)

The combination of ozone oxidation and membrane bioreactor utilizes ozone oxidation as
the chemical treatment followed by membrane bioreactor as the biological treatment. As it
has been mentioned before, ozone is a strong oxidizing agent which can destroy a wide
range of contaminants. The treated wastewater from ozone oxidation is routed to the
membrane bioreactor to be treated by biological activity.
In the given case, if we consider the maximum performance of COD removal in ozone
oxidation system is 90% (Stacy, 2007), the treated effluent will have COD level of 1452.2
ppm. The treated effluent from ozone oxidation system will be combined with LPW which
has been neutralized to a certain level of pH. The combined stream is then routed to the
MBR system which consists of de-nitrification tank, nitrification tank, and ultrafiltration
membrane.
The combined effluent from ozone oxidation system and neutralized LPW will enter the
MBR system. If we take the maximum COD and TKN removal of MBR system is 97%
and 98% each (Stacy, 2007), the COD level in the treated effluent of MBR system will be
333.84 ppm and the TKN level will be 5.9 ppm. Such levels of COD and TKN have
already met the requirement discharge to Hemmaraj. Therefore, the treated effluent leaving
ozone oxidation-MBR system can be directly discharge to Hemmaraj. A simple flow
diagram of this system is shown in Figure 4.7. Summarized information about the
combination of ozone oxidation and MBR system is listed in Table 4.7.

24

Neutralization
HPW
Fresh activated carbon 10%

45.7 m /h
COD: 145,219 ppm
N: 295 ppm

O2
HPW
COD: 50,827 ppm

Wet Air Oxidation (WAO)

Org. + O2 CO2 + H2O + RCOOH

LPW
pH: 6 - 9

Powdered Activated Carbon

(PACT)

LPW
3

10.38 m /h
COD: 19,373 ppm
pH < 1

HPW + LPW

Sand filter
Discharge to Hemmaraj

Regenerated act.
carbon

Org. N + O2 NH3/NO3/elemental N + CO2 + RCOOH

Air

Sludge

56 m /h
COD: 360 ppm
TKN: 36 ppm

Wet Air Regeneration

(WAR)
Ash

Filter press

Dewatered ash to
disposal

Figure 4.7 Block diagram of TAR system

25

Table 4.7 Summary of ozone oxidation MBR system

Operating condition
Pros & Cons
Performance
Estimated cost
Very powerful
COD removal:
Capital
cost:
Ozone oxidation
oxidizing agent
Ozone oxidation: 60
$136,017.6/m3/h
T/P: ambient
Remove wide range
99%
Operating cost: $
Flow rate: 1 10,000
3
of pollutant
MBR: 89 - 97%
7.62/m3
m /hr
Environmentally
TKN removal: up to
O3 dosage: 0.7 1.1 g
friendly
96 - 98%
/ g COD eliminated
Ozone minimizes
T in Catalytic Ozone
sludge production
destructor : 30 70oC

Small footprint (10

Catalyst in catalytic
40 % to
destructor: palladium,
conventional)
manganese, nickel
High operating cost
oxides)
Low energy
MBR
efficiency
T/P: ambient

Requires corrosionTMP: up to 150 kPa

resistant material
Standard flux rate: 50
2
due to ozones
200 L/m .hr
corrosivity
SRT: 5 30 days

3. Thermophilic Membrane Bioreactor Chemical Treatment

The combination of thermophilic MBR and chemical treatment has been recently used in
industrial waste water treatment. The utilization of thermophilic MBR may be relatively
new and is believed to have better performance than the existing biological treatment. One
of hundreds vendor that has been widely trusted to provide this combination of technology
is BioConversion solution, which gives a commercial name of this wastewater treatment
combination as Advanced Fluidized Composting.
Chemical treatment that used in this method is usually utilization of oxidizing agent such
as hydrogen peroxide (H2O2). The oxidizing agent will oxidize and destroy contaminant in
the wastewater. The amount of oxidizing agent used depends on the amount of
contaminant in the wastewater itself.
Contrary to the previous methods, the applied combination of thermophilic MBR-chemical
treatment has reversed order between the chemical and biological treatment. The
wastewater will be routed to the MBR first (biological treatment) and then to the chemical
treatment. The vendor claimed that this treatment order can be used in almost all kinds of
wastewater stream, even in wastewater with high COD content. They also claimed that this
treatment order is done to reduce the operating cost, because routing the HPW alone
directly to the chemical treatment will consume high amount of chemical.
If we follow the applied order of thermophilic MBR-chemical treatment, we need to
combine the HPW and LPW together in the beginning and send them to the thermophilic
bioreactor system. The combination of HPW and LPW will result wastewater flow rate of
56 m3/h, COD content of 121,926 ppm, and TKN content of 240 ppm. The treated effluent
leaving the thermophilic bioreactor is sent to the ultrafiltration membrane to separate

26

liquid effluent and sludge containing biomass and hardly biodegradable compounds. The
sludge is routed to the chemical treatment tank. Here, the oxidizing agent (usually H2O2)
will oxidize the remaining contaminants in the wastewater which are hard to degrade
biologically. The treated effluent from chemical treatment tank will be routed back to the
MBR system to reduce more levels of contaminant. Take the maximum performance of
COD and TKN removals are 99.8% and 75% (similar to the commercial scale of this
technology that treats pharmaceuticals wastewater with COD level of 200,000 ppm). The
wastewater effluent leaving this method will have COD level of 244 ppm and TKN level
of 60 ppm and is ready to discharge to Hemmaraj. A simple block diagram of this method
is shown in Figure 4.6.
Due to the very high amount of COD level and low ratio of BOD/COD in our HPW, a
pilot test should be done before deciding whether the treatment order is reversed
(biological first followed by chemical treatment) or not. If the pilot scale tests result
shows that routing the wastewater directly to MBR system is inefficient (take a long time
to reach the mentioned percentage of performance), then separating entrance for HPW and
LPW is needed. The HPW is firstly sent to the chemical treatment to lower its COD level
as well as increasing the BOD/COD ratio. The effluent of chemical treatment is then
combined with the neutralized LPW and treated in the MBR system. The effluents
contaminant will have accepted levels to be discharged to Hemmaraj.
Summarized information about the combination of thermophilic MBR and chemical
treatment system is listed in Table 4.8.
Table 4.8 Summary of ozone oxidation MBR system
Operating condition
Pros & Cons
Performance
Estimated cost
Lower even zero
COD removal: Up t0 Capital
cost:
Thermophilic
waste sludge
99.8%
$56,574/m3/h
bioreactor
production
TKN removal: up to
Operating cost: $
T: 45oC 75oC

High
loading
rate
75%
4.5/m3
Retention time: 20
capability
30 min for readily
Smaller footprint
biodegradable
(10 - 40% smaller
compounds
than conventional
Flow rate: up to 158
technology)
m3/h

Autothermal
Minimum OTE: 10
operation
15%
Achieve equivalent
Minimum dissolved
result to WAO
O2 : 1 ppm
for most waste
Ultrafiltration
stream
with less cost
membrane

Require
operation
T/P: ambient
and
maintenance
Flux range: 40 135
which is more
l/m2 . h
complicated than
TMP: up to 210 kPa
disposal
Chemical treatment
tank
T/P: ambient

27

4. Fenton Oxidation Oxidation Ditch

Fenton oxidation has been widely used in wastewater treatment plant due to its powerful
and selective activity in reducing contaminants in the wastewater. Such high performance
of Fenton oxidation makes the requirement of biological treatment that follows the Fenton
oxidation is not too high. A simple yet effective biological treatment is enough to be
placed after Fenton oxidation system. The choice of biological treatment then falls on
oxidation ditch which is more energy intensive, produces less sludge, and many other
excellences than other biological treatments.
In the combination of Fenton oxidation and oxidation ditch, the HPW is first routed to the
chemical treatment tank where oxidation reaction of contaminant by Fenton regent occurs.
If we take the maximum COD removal in Fenton oxidation system is 90% (similar to the
applied Fenton oxidation system in paper mill wastewater with COD level of 300,000
ppm), the effluent leaving chemical treatment tank will have COD level of 14,522 ppm. It
is important to note that oxidation reaction by Fentons reagent is only effective at acidic
pH (approximately at pH 3.5). Therefore, an acidification of HPW stream is needed before
this stream is treated in the chemical treatment tank.
The chemical-treated effluent is then routed to the oxidation ditch to be treated by
biological treatment. Before entering the oxidation ditch system, this stream is combined
with the neutralized LPW which pH is around 6 9. The effluent leaving oxidation ditch
will pass through the clarifier to separate the sludge and the liquid effluent. The sludge
which contains biomass will be routed back to the oxidation ditch while the liquid effluent
will be sent to the disinfection system to remove the remaining biomass. The disinfection
system usually uses chlorine to kill the remaining microbes in the wastewater before being
discharge to environment. If we take the maximum COD and TKN removal in oxidation
ditch each is 98.5% and 94%, the final COD and TKN level in the effluent will be 501 and
17.7 ppm. This level of contaminant in the wastewater is accepted to be discharged at
Hemmaraj.
A simple block diagram of Fenton oxidation-oxidation ditch is shown in Figure 4.7.
Summarized information about the combination of Fenton oxidation and oxidation ditch
system is listed in Table 4.9.

28

Table 4.9 Summary of Fenton oxidation oxidation ditch system

Operating condition
Pros & Cons
Performance
Estimated cost
Very selective
COD removal:
Capital
cost:
Fenton oxidation
oxidizing agent
Fenton: 90%
$55,713.4/m3/h
(H2O2/Fe2+)
Does not require
Oxidation ditch: 95 Operating cost: $
T/P: 20oC 80oC /
special material
98.5%
4.4/m3
atmosphere
for the reactor
TKN removal: up to
pH around 3.5

Autothermal
90 94%
Retention time: 5 10
operation
min
Can save energy
Flow rate: 15.75
saving up to 40%
1800 m3/h
compared to
Amount of H2O2: 35
conventional
50% (w/w)
biological treatment
Catalyst: Fe salt:

Requires
high
Fe(NO3)3,
concentration of
FeSO4.7H2O,
H2O2 which cost is
FeCl2.4H2O
higher than air
H2O2 : Fe = 10 : 1

Requires larger land

Oxidation ditch
area than
T/P: ambient
conventional
pH: 6 9
biological treatment
Minimum dissolved
TSS in effluent is
O2 : 2 4 ppm
relatively higher
Circulated wastewater
than other biological
velocity: 0.25 0.35
treatment process
m/s
HRT: 6 30 hours
SRT: 15 30 days

4.2.2 Technology for salt stream

As the salt content in the salt stream may disturb the chemical and biological treatment, the
salt stream needs to be treated by special treatment. Technologies that have been
commercially used to treat salt-contained wastewater and become consideration in our
method selection are described as the following.
1. Thermal Oxidizer
Thermal oxidizer is a unit where combustion of contaminants, especially organic content
in the waste occurs. The combusted organic content will be converted to carbon dioxide,
water, and ash. The phase of waste that can be combusted in thermal oxidizer could be
either liquid or solid. Thermal oxidizer has been widely used in industrial waste treatment
especially to treat high solid-content and highly contaminated waste. By thermal oxidizer,
almost all contaminants in the waste will be burnt and converted to ash and gases.
There are two types of thermal oxidizer that have been commercially available. The first
one is the fluidized bed technology which consists of windbox section where combustion

29

air is introduced, a bed section where the waste is fluidized along the sand, and a freeboard
section where combustion is completed. In fluidized bed, waste and auxiliary fuel are
injected co-currently to the unit. The exhaust gases and ash that are produced from the
combustion will pass through energy recovery facilities before it is treated in air pollution
control system. The ash is usually removed in a slurry form by wet scrubbing system and
some of thermal oxidizer units have a dry ash removal system upstream of the scrubbers.
The residence time in fluidized bed thermal oxidizer is 5 60 seconds.
The second type of thermal oxidizer is multiple hearth technology. It is a vertical
refractory-lined cylinder with a series of horizontal refractory brick hearths and rotating
center shaft. The multiple hearth is separated into three zones; the top hearth or drying
zone where water is evaporated, the middle hearth or the combustion zone where volatile
contaminants are oxidized, and the cooling zone where the ash is cooled by incoming
combustion air. In multiple hearth, the waste and auxiliary fuel are injected counter
currently to the system. The residence time in multiple hearth system is 40 60 minutes.
Schematic figures of fluidized bed and multiple hearth thermal oxidizers are shown in
Figure 4.8.

Figure 4.8 Schematic figures of multiple hearth (left) and fluidized bed (right)
Source:

The operation of thermal oxidizers can be run autothermally. In general, about 70% of heat
required by waste incineration come from the waste itself (Dangtran, dkk,200x). The
remaining 30% of the heat are obtained from auxiliary fuel and/or from the combustion air.

30

The supplementary heat can also be recuperated from the flue gas to preheat the
combustion air up to 1250oF to achieve autogenous combustion.
Although fluidized bed and multiple hearth function are similar, the different in their basic
design leads to some advantages for the fluidized bed system. Some plants even replaced
multiple hearth with fluidized bed Manchester Water Pollution Control Facility,
Manchester, NH, Wyoming Valley in Wilkes Barre, PA, and T.Z. Osborne in Greensboro,
NC and claimed that the replacement results a better performance. Some of the
excellences of fluidized bed compared to multiple hearth are lower NOx formation, lower
CO formation, lower THC formation, easier for control and automation, wider rang in feed
variability, lower fuel usage, lower maintenance cost, lower power requirement, etc.
Summarized comparison between fluidized bed and multiple hearth is shown in Table 4.10

31

O2

10.38 m /h
COD: 19,373 ppm
pH < 1

LPW
HPW
COD: 1452,2 ppm
pH: 6 - 9
N: 260 ppm
De-nitrification tank

Ozone oxidation

O3

Neutralization

O3 destructor
Unreacted O3

Discharged to
Hemmaraj

LPW

Nitrification tank
+

Ultrafiltration
membrane

Organic N NH4 NO2 + NO3

NO3 NO2 NO N2O N2

HPW

56 m /h
COD: 333.84 ppm
N: 5.9 ppm

45.7 m /h
COD: 145,219 ppm
N: 295 ppm

Concentrate containing biomass & untreated compounds

Figure 4.6 Block diagram of Ozone oxidation-MBR system

HPW

LPW
3

45.7 m /h
COD: 145,219 ppm
N: 295 ppm

10.38 m /h
COD: 19,373 ppm
pH < 1

Discharge
3

Neutralization

Acidification

56 m /h
COD: 501 ppm
TKN: 17.7 ppm

LPW
pH: 6 - 9
Fenton
2+

H2O2/Fe

HPW
COD: 14,522 ppm

Oxidation ditch

Clarifier

Disinfection

Sludge

Figure 4.7 Block diagram of Fenton oxidation-oxidation ditch

32

Table 4.10. Comparison between fluidized bed and multiple hearth

Parameters

Multiple hearth

Fluidized bed

Flow

Counter current

Intense back mixing

Heat transfer

Poor

High

Waste detention time

- 3 hours

1 5 minutes

Gas detention time at high

temperature

1 - 2 seconds

6 8 seconds

Combustion temperature

1500 1800 oF

1400 1500 oF

Gas exit temperature

800 1000 oF

1500 1600 oF

Excess air

75 100%

40%

Thermal oxidation system can handle a large range of feed flowrate and contaminants as
well as remove nearly all contaminants in the wastewater. Even so, the application of
thermal oxidizer also raises cons. This is due to the pollutant gas released which make this
process is considered as not green process. A summary of strengths and weaknesses of
thermal oxidation system is shown in Table 4.11.
Table 4.11 Strengths and weaknesses of thermal oxidation system
Weakness
Strength
Complete stabilization process destroying all volatile solids
and pathogens
Large volume and mass reduction lowers truck traffic as
compared with other biosolids handling alternatives
Low life cycle cost for medium and large facilities
Low potential for onsite or offsite odors
Requires small land area and can operate continuously in all
weather conditions
Lower auxiliary fuel requirements than other biosolids
handling alternatives
Strictest monitoring and reporting requirement ensure public
of proper operation
Produces recoverable energy that can be used to produce
heated air, gas, water, and oil that can be used for heating and
electricity
Pre-stabilization process not required

High initial capital cost

Poor public image and acceptance due to
misinformation and perceptions
May not be appropriate for non-continuous
operation
Permitting is more complex than for other
biosolids alternatives
Not perceived as green process
Ash reuse programs have not been well
developed
Emits pollutant gases such as CO, NOx, SOx, and
THC (total hydrocarbon, usually exhibits as CH4)

In the end, technical and economic information of thermal oxidizer system is provided in
Table 4.12.

33

Table 4.12 Summary of technical and economic information about thermal oxidation system
Allowable inlet flow rate

Main equipment

Operating condition

Additional equipment
Operating mode

Operation & Maintenance

Cost

Fluidized bed:
Windbox section where combustion air is introduced
Refractory arch where hot air distributed homogenously through the bed
Combustion zone where biosolids and fuel is introduced
Freeboard which acts a s afterburner to complete combustion of volatile
hydrocarbon
Multiple hearth:
Upper hearth where biosolids water and organic compounds evaporated
Middle hearth/combustion zone
Lower hearth/cooling zone
Fluidized bed:
Bed area/combustion zone: 1350 1500oF
Freeboard: 50 1000F higher than combustion zone
Biosolids detention time: - 3 hours
Multiple hearth:
Upper hearth: 800 1000oF
Middle hearth: 1500 1700oF
Lower hearth: 350 400oF
Biosolids detention time: 1 5 min
Heat exchangers
Air pollution control system which includes venturi/nozzle scrubber, cooling
tray, and electrostatic precipitator
Continuous (24 hours, 4 5 days per week)
70% of the heat required by biosolids come from the biosolids: 25% of the flue
gas can preheat the combustion ait up to 1250oF to achieve autogenous
combustion
The remaining 30% of the heat are from auxiliary fuel
Autogenous combustion condition: combustion air temperature: 1200oF and
solid content 25 28%

Capital cost

$175,000 - $250,000

Operating
cost (per dry
ton organics)

$155 - $260 (fluidized bed)

$172 - $313 (multiple hearth)

Applied scale
Available vendors

Reference Plants

Industry
Degremont Technology
Hitachi Zosen
Industrial Furnace Company
Cockerill Maintenance & Ingenierie
Municipal wastewater treatment of Waldwick, New Jersey
Pharmaceutical waste
Chemical and paper mill waste
Petrochemical waste

34

2. Electrodialysis Reversal
Electrodialysis is a membrane process for recycling water from electrolyte, including salt
solution. The electrodialysis system consists of cation and anion exchange membrane,
dilution and concentration chamber, and also cathode and anode.
The principle of electrodialysis system is that the dissolved salts which have positive and
negative charge will migrate through ion-selective semipermeable membranes. This
phenomenon happens as a result of their attraction to two electrically charged electrodes.
The anions will pass through the anion-selective membrane but are not able to pass by the
cation selective membrane, which blocks the anion in the brine stream. Similarly, cations
move in the opposite direction through cation selective membrane under the negative
charge and are trapped by anion-selective membrane.
EDR system is a variation of ED process. EDR uses electrode polarity reversal to
automatically clean the membrane surface. EDR works the same way as ED, except the
polarity of the power is reversed two to four times per hour. When the polarity is reversed,
the source water will dilute and concentrate compartments are also reversed and so are the
chemical reactions at the electrodes. This polarity reversal will prevent the formation of
scale on the membrane. A schematic diagram of EDR system and a summary of its
technical and economic information are shown in Figure 4.9 and Table 4.13.

Figure 4.9. Schematic diagram of electrodialysis reversal system

(Source: U.S. Department of the Interion Bureau Reclamation, 2010)

35

Table 4.13 Summary of technical and economic information of EDR system

Allowable inlet flow rate
Main equipment

Operating condition

Additional equipment

Operating mode
Operation & Maintenance
Energy consumption
Capital cost
Cost

Operating
cost

Applied scale

Available vendors

10 25 gallons/day/ft2 membrane area

Cation-exchange membrane
Anion-exchange membrane
Dilution and concentration chamber
Cathode and anode
pH: 2 11
Pressure: atmosphere
Ratio of permeate and feed water flow rate: 85 95%
Raw water pumps
Debris screen
Slow mix flocculator
Clarifier
Gravity filters
Chlorine disinfection
Clearwell storage
Continuous
Reversal frequency: 15 30 minutes
Cleaning using 5% hydrochloric acid solution
Average membrane life: 12 15 years
2.4 kWh/m3 with electricity cost of $0.03/kWh
$3,400,000 for EDR capacity of 165.6 m3/h (United Nations Environment Program,
Division of Technology, Industry, and Economics)
$248/ton TDS removed
$0.21/m3 (for EDR capacity of 165.6 m3/h) (United Nations Environment
Program, Division of Technology, Industry, and Economics)
Industry
Asahi Chemical Industry Co.
Asahi Glass Col. Ltd
DuPont Co.
FuMa-Tech GmbH
GE Water and Process
LanXess Sybron Chemicals
MEGA a.s.
PCA GmbH
Tianwei Membrane Co.Ltd.
Tokuyama Co-Astom

The EDR system can handle TDS loading up to 12,000 ppm and able to remove 50 94%
of TDS in the feed water. Even so, EDR system has stringent limitations for the feed water
that enters this system. Those limitations are:
pH: 2 11
total organic carbon (TOC): up to 15 mg/l
free chlorine up to 0.5 ppm
turbidity: up to 2 NTU
iron: 0.3 ppm
Mn2+: 0.1 ppm
H2S: up to 1 ppm

36

The stringent limitations of EDR system make feed water needs to be routed to a complex
pretreatment system before entering the EDR. Moreover, our salt stream wastewater has
high amount of organic contaminant which makes it impossible to be treated directly in the
EDR system. One solution that can be taken is to treat the salt stream in the same treatment
system as the HPW and LPW in order to remove its organic contaminants before entering
the EDR. However, as it has been mentioned before, the high concentration of salt in the
salt stream makes the biologic and chemical treatment become inefficient. Such condition
is indeed a dilemma because the salt stream cannot either be treated directly in the EDR or
pretreated by the chemical and biological treatment. Thus, EDR is likely not an option for
treating the PO/SM, polymer polyol, and polyether polyol salt stream.
4.3 Technology Selection
The goal of technology selection is to decide which wastewater treatment method is the
most suitable to treat the wastewater from PO/SM, polymer polyol, and polyether polyol
units. Both HPW & LPW and salt stream commercial treatment method are selected based
on specified criteria which consist of technical and economic aspects. Parameters for
selecting HPW & LPW and salt stream treatment methods are shown in Figure 4.10.
Capacity
COD loading

TDS loading

Severity of operating
condition
Performance
Technical

Footprint
Commercial plant

Criteria

Maintenance
Commercial scale
Sludge production

Pretreatment

Proprietary equipment
(2%)
Environmental issue
Safety in operation
Capital cost
Economic
: Exception for salt
stream methods

Operating cost

Figure 4.10 Wastewater treatment methods selection parameters

37

Each parameter has percentage for scoring. The more the parameter takes effect in the
technical or economic aspect, the higher the percentage is. Selection of wastewater
treatment method is done by giving score to each parameter. The scores for each parameter
are shown in Table 4.14
Scoring of the commercially available wastewater treatment methods is done based on the
summarized information that is shown in Table 4.15 and 4.16. The scoring result for HPW
& LPW and salt stream treatment method are shown in Table 4.17 and Table 4.18
respectively.

38

Table 4.14 Scoring of wastewater treatment method

Criteria
HPW & LPW
1. Capacity
2. COD (HPW&LPW) / TDS
loading (Salt stream)
3. Severity of operating
condition

4. Method's performance

Technical issue 5. Footprint

(60%)
6. Commercial plant

7. Maintenance

a. Periodic maintenance

b. Easiness of maintenance

c. Turnaround period

Score

Percentage
HPW&LPW/salt stream

Salt Stream

Chem>45m3/hr,Bio>57m3/hr
Chem<45 m3/hr, Bio<57m3/hr

Flowrate > 0.5 m3/h

Flowrate < 0.5 m3/h

3
1

5%

>145,000 ppm
<145,000 ppm
Ambient T & P
25 < T < 200oC, 1< P < 10 bar
T > 200oC, P > 10 bar
Good(>90%)
Average (50 - 89%)
Poor (<50%)
Small
Medium
Large

>100,000 ppm
<100,000 ppm
Ambient T&P
25 < T < 200oC
T > 200oC
Good (>90%)
Average (50 - 89%)
Poor (<50%)
Small
Medium
Large

3
1
3
2
1
3
2
1
3
2
1

5% / 8%

>4
2-4
<2
No periodic maintenance
6 months - 1 year
less than 6 months
Easy
Medium
Hard

>4
2-4
<2
No periodic maintenance
6 months - 1 year
less than 6 months
Easy
Medium
Hard

3
2
1
3
2
1
3
2
1

5%

> 4 years
3 - 4 years
0 - 3 years

> 4 years
3 - 4 years
0 - 3 years

3
2
1

3%

10% / 7%

5% / 8%

5%

1%

2%

39

Table 4.14 Scoring of wastewater treatment method (cotd.)

Criteria
HPW & LPW
8. Sludge production
(HPW&LPW) / Complexity of
pretreatment (Salt)
9. Proprietary equipment
Technical issue 10. Environmental issue
(60%)

a.Hazardous waste

b. Release of pollutant gases

11. Safety in operation

1. Capital cost
Economic issue
(40%)

2. Operating & maintenance

cost

Score
Salt Stream

Percentage
HPW&LPW/salt stream

Small
Medium
High
No proprietary
Have proprietary
No use
Use

Not required
1-3
>3
No proprietary
Have proprietary
Not required
Required

3
2
1
3
1
3
1

5%

No release
Release gas, non-toxic
Release gas, toxic
High
Medium
Less
$1,000,000 - 5,000,000
$5,000,001 - 10,000,000
> $10,000,000
< $3/m3
$3 - 6/m3
> $6/m3

No release
Release gas, non-toxic
Release gas, toxic
High
Medium
Less
< = $1,000,000
$1,000,001 - 5,000,000
> $5,000,000
<$260 / ton TDS
$260 - $320/ton TDS
>$320/ton TDS

3
2
1
3
2
1
3
2
1
3
2
1

4%

2%
3%

5%

15%

25%

40

Table 4.15 Summary of HPW & LPW treatment methods

TAR

Ozone-MBR

Thermophilic MBR-Chem.
Fenton-oxidation ditch
treatment

Capacity

50 m3/h (WAO)
378.5 m3/h(PACT)

1 - 10,000 m3/h

157.7 m3/hr

15.75 - 1800 m3/h

COD loading

150,000 ppm

> 100,000 ppm

183,174 ppm

300,000 ppm

Severity of operating
condition

P: up to 221 bar
T: up to 320oC

P & T: ambient

T: 45 - 75oC

T: 20 - 80oC

Performance

Up to > 90%

Up to > 90%

Up to > 90%

Up to > 90%

Footprint

Larger than conventional

method

Can reduce 10 40% of

conventional treatments
footprint

Can reduce 10 40% of

conventional treatments
footprint

Larger than conventional

method

Commercial plant

>4

>4

>4

>4

a. Periodic
maintenance

No periodic maintenane

6 - 12 months

6 - 12 months

No periodic maintenance

b. Easiness of
maintenance

Easy

Hard

Medium

Easy

Maintenance

c. Turnaround period > 4 years

Sludge production

1.7 year for ozone generator 5 - 7 years for membrane

replacement
replacement

Very slow amount of blowdown MBR produces less sludge

ash, WAR cen reduce sludge up than biological treatment
to 90%
no sludge produced from
ozone oxidation

Little amount to zero sludge

production

> 4 years

Fenton oxidation produces

sludge, oxidation ditch
produces less sludge than
conventional bio. treatment

41

Table 4.15 Summary of HPW & LPW treatment methods (contd.)

TAR

Ozone-MBR

Thermophilic MBR-Chem.
Fenton-oxidation ditch
treatment

No

Ozone injector

No

No

Hazardous waste

No

No

No

No

Pollutant gases

Off-gas:VOCs, CO2

No

Safety in operation

No special PPE

Needs special PPE

No special PPE

Needs special PPE

Capital cost

$4,831,396/m3/h

$136,017.6/m3/h

$56,574/m3/h

$55,7134/m3/h

O & M cost

$2.6/m3

$7.62/m3

$4.5/m3

$4.46/m3

Proprietary equipment
Environmental issue

Off-gas: CO2,NH3,VOCs

No

Table 4.16 Summary of salt treatment methods

Thermal oxidizer

Electoridialysis Reversal

Capacity

Up to 12,000 m3/h

Up to 9,100 m3/h

TDS loading

Varies greatly

Up to 12,000 ppm

Severity of operating condition

Up to 816oF

P & T: ambient

Performance

Remove nearly all contaminants and convert it into CO2, water, ash, and gases 50 99% of TDS removal

Footprint

Smaller than conventional treatment and thermal oxidizer

Smaller than conventional treatment and thermal

oxidizer

Commercial plant

>4

>4

42

Table 4.16 Summary of salt treatment methods (contd.)

Thermal oxidizer

Electoridialysis Reversal

a. Periodic maintenance

Annual maintenance (2 4 days/year)

19 23 days for membrane cleaning in place

b. Easiness of
maintenance

Can be done manually

Can be done manually and automatically

c. Turnaround period

5 10 years

12 15 years

Complexity of pretreatment

No pretreatment needed

Wastewater needs to be pretrated

Proprietary equipment

No

Membrane

Hazardous waste

No

No

Pollutant gases

CO, NOx, SOx, and THC

Maintenance

Environmental issue

No pollutant gases

Safety in operation

Needs special PPE

No special PPE

Capital cost

$1517.65/m3/h

$20,531.4/m3/h

O & M cost

$242.5/dry ton organics

$248/dry ton organics

43

Table 4.17 Scoring result of HPW and LPW treatment methods

Technical
issue

Capacity

5%

COD loading

5%

Severity of operating condition

10%

Performance

5%

Footprint

5%

Commercial plant

5%

Periodic maintenance

1%

Easiness of maintenance

2%

Turnaround period

3%

Sludge production

5%

Proprietary equipment

2%

Produce hazardous waste

3%

Release of pollutant gases

4%

5%

1.4

1.45

1.65

1.5

Maintenance

60%

Environmental issue

Safety in operation
Total technical score/1.8

44

Table 4.17 Scoring result of HPW and LPW treatment methods (contd.)

Economic
issue
40%

Capital cost

15%

Operating & maintenance cost

25%

Total Economic score/1.2

0.9

0.55

0.95

0.95

Total score / 3

2.34

2.6

2.45

Total score / 100

78

66.7

86.7

81.7

Note:
A: Wet air oxidation PACT Wet air regeneration / B: Ozone oxidation membrane bioreactor
C: Thermophilic membrane bioreactor chemical treatment / D: Fenton oxidation oxidation ditch

45

Table 4.18 Scoring result of salt stream treatment methods

Technical issue
(60%)

Capacity

5%

TDS loading

8%

Severity of operating condition

7%

Method's performance

8%

Footprint

5%

Commercial plant

5%

Periodic maintenance

1%

Easiness of maintenance

2%

Turnaround period

3%

Complexity of pretreatment

5%

Proprietary equipment

2%

Use of hazardous chemical

3%

Release of pollutant gases

3%

3%

1.51

1.45

Maintenance

Environmental issue

Safety in operation
Total technical score / 1.8

46

Table 4.18 Scoring result of salt stream treatment methods (cotd.)

Economic issue
(40%)

Capital cost

15%

Operating & maintenance cost

25%

Total economic score/1.2

1.2

1.05

Total score/3

2.71

2.5

Total score/100

90.3

83.3

Note:
E: Thermal oxidizer; F: Electrodialysis reversal

47

According to Table 4.17, it is clearly shown that the MBR-chemical treatment method
(technology C) excels in technical aspect compared to other three combination of
technologies. Combination of MBR-chemical treatment has technical score of 1.65 out of
1.8, the highest score among HPW & LPW treatment methods. If it is viewed from
economic aspect, the highest economic score is 0.95 out of 1.2. Identical highest scores are
achieved by combination of MBR-chemical treatment and fenton oxidation-oxidation ditch
(technology D). According to the overall score, combination of MBR and chemical
treatment has the highest overall score among others, which is 2.6 oout of 3 or 86.7%.
For the salt treatment method scoring result that is shown in Table 4.18, it is clearly shown
that the thermal oxidizer method excels both in technical and economic aspects. The total
technical score of this technology is 1.51 out of 1.8 while the total economic score is 1.2
out of 1.2. Both technical and economic scores of the thermal oxidizer technology are the
highest among another salt stream treatment technology.
From the scoring result, it can be finally concluded that the most suitable method to treat
the HPW and LPW is combination of MBR and chemical treatment. The most suitable
technology to treat the salt stream method is the thermal oxidizer.

48

CHAPTER V
CONCLUSIONS AND RECOMMENDATIONS
5.1 Conclusions
The conclusions that can be taken from feasibility study of wastewater treatment in
propylene oxide, polymer polyol, and polyether polyol plants are mentioned as the
followings:
1. Thermophilic membrane bioreactor chemical treatment is the most suitable
wastewater treatment method for high polluted and low polluted wastewater
2. Thermal oxidizer is the most suitable wastewater treatment method for the salt
stream
3. Bioconversion Solutions is the recommended vendor for thermophilic membrane
bioreactor chemical treatment method
4. Degremont Industry is the recommended vendor for thermal oxidizer treatment
method
5.2 Recommendations
1. Pilot scale test of the wastewater treatment method needs to be carried out before
being applied in the real plant
2. More reliable data about the capital and operating cost should be used, e.g. from
the vendor

41

APPENDIX A
CALCULATION OF HPW, LPW, AND SALT STREAM COMPOSITION

HPW composition
HPW from PO/SM
3

32 m /h
Oil: 4 5 ppm
pH: 13 14
COD: 182,000 ppm
COD:
182,000
ppm
AP
from
PO/SM
3

6.7 m /h
pH: 1.8 2
COD: 75,000 ppm

LPW from polymer polyol

3

4 m /h
COD: 10,000 ppm
BOD/COD: 0.05
HPW from polymer polyol
3

3 m /h
COD: 90,000 ppm
N: 4,500 ppm
BOD/COD: 0.04

Total flow rate: 32 + 6.7 + 4 + 3 = 45.7 m3/h

Final COD concentration:
= ((182,000 x 3) + (75,000 x 6.7) + (10,000 x 4) + (90,000 x 3)) / (32 + 6.7 + 4 + 3)
= 145,219 ppm
Final N concentration:
= (4,500 x 3) / (32 + 6.7 + 4 + 3) = 295 ppm
LPW composition
LPW from polyether polyol
(flexible) unit
4.38 m3/h
BOD:/COD: 0.47

LPW from PO/SM

Final emptying of
equipment, rainwater,
laboratory residual stream

LPW from polyether

polyol (rigid & CASE)
unit
m3/h
66 m3/h
COD: 182,000 ppm
LPW from polyether polyol (flexible unit)
Assumption: wastewater flow rate from vacuum system = abatement device = 2.19 m3/h
Final COD concentration: ((11,000 x 2.19) + (50,000 x 2.19)) / 4.38 = 30,500 ppm
42

Final BOD concentration: ((6000 x 2,19) + (30,000 x 2.19)) / 4.38 = 18,000 ppm
LPW from polyether polyol (Rigid & CASE unit)
Assumption: wastewater flow rate from vacuum system = abatement device = 3 m3/h
Final COD concentration: ((15,000 x 3) + (100,000 x 3)) / 6 = 57,500 ppm
Final BOD concentration: ((2000 x 3) + (28,000 x 3)) / 6 = 15,000 ppm
Final COD concentration of LPW
COD = ((4.38 x 30,500) + (57,500 x 6)) / 10.38 = 19,373 ppm
Final BOD concentration of LPW
BOD = ((4.38 x 18,000) + (15,000 x 6)) / 10.38 = 10,088 ppm
BOD/COD ratio = 10,088 / 19,373 = 0.52
Salt stream composition
By-product from polyether
polyol (rigid&CASE) unit
0.15 m3/h

By-product from polyether

polyol (flexible) unit
0.225 m3/h

Potassium content >14% & Polyol content < 5%

HPW from polyether polyol HPW from polyether polyol
(rigid&CASE) unit
(flexible) unit
0.078 m3/h
0.07 m3/h
COD: 460,000 ppm; BOD: 210,000 ppm; pH: 12 - 14
Final COD content
((460,000 x 0.078) + (460,000 x 0.07)) / (0.078 + 0.07) = 136,160 ppm
Final BOD content
((210,000 x 0.078) + (210,000 x 0.07)) / (0.078 + 0.07) = 62,160 ppm
Final potassium content
((0.225 x 140,000) + (0.15 x 140,000)) / (0.225 + 0.15) = 100,382 ppm
Final polyol content
((0.225 x 50,000) + (0.15 x 50,000)) / (0.225 + 0.15) = 35,851 ppm

43

REFERENCES
Abeynayaka, 2009. Thermophilic Aerobic Membrane Bioreactor for Industrial Wastewater
Treatment. Thailand: Asian Institute of Technology.
Abeynayaka and Visvanathan. 2010. Performance comparison of mesophilic and
thermophilic aerobic sidestream membrane bioreactors treating high strength wastewater.
Elsevier.
BioConversion Solutions. Case Study: Food Processing Solution: AFC Thermophilic
Membrane Bioreactor.
BioConversion Solutions. Case Study: K&K Foods, Inc. Solution: AFC Thermophilic
Membrane Bioreactor.
BioConversion Solutions. Case Study: Pharmaceutical.
BioConversion Solutions. Case Study: Pharmaceuticals Solution: Treatment of HighStrength Contaminated Groundwater.
Jegatheesan, dkk. 2011. Advances in Biological Wastewater Treatment. Thailand: Asian
Institute of Technology
Juteau, P. 2006. Review of the use of aerobic thermophilic bioprocess for the treatment of
swine waste. Livestick Science 102 (2006) 187 196.
Kurian, R. and Nakhla, G., Performance of Aerobic MBR Treating High Strength Oily
Wastewater at Mesophilic Thermophilic Transitional Tempeartures. WEFTEC 06.
Mrowiec, dkk. Anoxic and Anaerobic Wastewater Treatment in Presence of Aromatic
Hydrocarbon. Poland: University of Bielsko Biala.
OSBL Basis Design Data for Repsol, 2014
PMCBioTec Company. High-Strength waste Treatment to Eliminate Sludge, Save
Money, and Improve Environmental Public Relations
Rozich, A.; Colvin, R.; Hahn, C. White Paper: Design and Operation of a High Strength
Organic Wastewater Treatment System to Approach Zero Net Sludge Production at a
Specialty Chemical Plant. BioConversion Solutions.
Setiadi, T. 2014. Air Limbah Industri. Bandung: Institut Teknologi Bandung
Siemens. Biological Treatments: Membrane Bio Reactor (MBR). Water Technologies.
Sutton, Paul M. 2006. Membrane Bioreactors for Industrial Wastewater Treatment:
Applicability and Selection of Optimal System Configuration. Enfield: P.M. Sutton &
Associates, Inc.
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