Topic for Co-operative Project Proposal

Department of Chemical Engineering

Faculty of Engineering Thammasat University

********************************************

1. Topic Design of wastewater treatment process for biodiesel

production: co-operative study at Global Green Chemicals Public Company
Limited (GGC Company)

2. Present by Ms. Anyamanee Siripojanakul ID. 5710758037

3. Advisor Asst. Prof. Dr. Phanida Saikhwan

4. Objectives
4.1 To design a wastewater treatment system for the plants in the same area of
Chonburi plant.
4.2 To verify, improve process efficiency and optimize the production process

5. Research Framework
5.1 Design the centralize water treatment system to treat all of wastewater
from all adjacent biodiesel projects in the plant.
5.2 The characteristics of water effluent discharging from the plant shall meet
the standard as indicated in the MOI Notification of Thailand.
5.3 Sourcing for vendor and discussing about the conceptual wastewater
treatment design system.

6. Keywords
Wastewater treatment design, Biodiesel production, Methyl ester

7. Introduction

7.1 Company profile

Global Green Chemicals Public Company limited or GGC Company, former

Thai Oleo Chemicals producers in Thailand under PTTGC Group. The company is
one of the leading procedures of methyl ester in Thailand.

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 At present, GGC Company holds a total nameplate capacity of 300,000 tons
per year for methyl ester or biodiesel “B100” and wants to enhance the production
capacity of methyl ester by establishing another plant or MEII plant with an installed
capacity of 200,000 tons per year.

Since the company has other two projects currently under the construction,
MEII and KN projects, which lead to consider the design of wastewater treatment that
are appropriate to the quality of incoming wastewater from different sources and
characteristics.

7.2 Supervisors of GGC Company

7.2.1 Mr.Danai Payaktanon (Project Engineer)

7.2.2 Mr.Jirawut Imrut (Procurement Analyst GGC Project)

8. Literature Review
The study of the related literature is divided into five main groups.

8.1 Overall Biodiesel Production Process

Biodiesel is an alternative diesel fuel that is produced from renewable

feedstock such as vegetable oils and animal fats. The most common way to produce
biodiesel is by transesterification, which refers to a catalyzed chemical reaction
involving vegetable oil or animal fat and an alcohol to yield fatty acid alkyl esters
(i.e., biodiesel) and glycerol. Transesterification is basically the transformation of
large, branched, triglyceride molecules of oils and fats into smaller, straight-chain
molecules, Phalakornkule et al. (2009).

As palm oil is the raw material for the biodiesel production, before crude palm
oil or CPO entering the transesterification section, the contaminants in feedstock such
as gum, apparent color and some odor still have to be removed, Young et al. (2015).

The first stage or pretreatment section was applied to reduce the apparent
color, some odor and gum in the CPO before entering the next section by degumming
and bleaching techniques. In the degumming section, hot water and phosphoric acid

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 will react with the CPO to make the gum agglomerate and precipitate, MO
ZHENGBO (2016).

The bleaching techniques using bleaching clay to help get rid of color to be
faded color, trace metal, oxidation matters or peroxide, smells better and can increase
stability of the feedstock, Gonçalves et al. (2017).

Pretreatment Process Biodiesel Process

200 KTA of Crude Palm Oil Refined Palm Oil
with FFA 10% with FFA 0.1%

Methanol
Hot Water Degumming Unit Reaction Unit Palm Stearin
Catalyst

Bleaching Earth Bleaching Unit Separation Unit

Glycerine Layer Esterification Unit Glycerin Methyl Ester

Distillation Unit Distillation Unit
Steam Deodorization Unit
25 KTA of Crude Glycerin 200 KTA of Methyl Ester
80-85% (B100)
Figure 8.1 a block diagram for the biodiesel production

Deodorization section is the last section in the pretreatment process and the
effluent oil from this section will be called as refined palm oil or RPO which will be
sent to the biodiesel process in the next step. Low and high pressure team (lps and
hps) can be used to get rid of the odor of the oil. Moreover, free fatty acid and trace of
oxidant matters can be eliminated as well, Marchetti et al. (2007).

Transesterification reaction catalyzed by alkali homogeneous catalyst such as

sodium and potassium hydroxides yields higher conversion of vegetable oil to methyl
esters in short time, the reaction has several drawbacks: energy intensive; recovery of
glycerol is difficult; the catalyst has to be removed from the product; alkaline

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wastewater requires treatment and free fatty acid (FFA) and water interfere with the
reaction, Atadashi et al. (2011).

The reason why there is a great interest in the alkali process is it is more
efficient and less corrosive than the acid process, making this a preferred catalyst to
be used in the field, Marchetti et al. (2007).

8.2 Wastewater from Biodiesel Production and Characteristics

During the biodiesel production process, a large amount of water is used for
product rinsing in order to remove undesirable substances such as residue remaining
oil or Oil & Grease, soaps, organic compounds (methanol and glycerol), free fatty
acids and remaining catalyst.

The characteristics of biodiesel wastewater is normally found with high

contents of COD, SS, highly stable emulsion oil and grease (O&G) with various pH
level depending on the type of process being used. Biodiesel wastewater is a viscous
liquid with an opaque white color, contains water, glycerol, soap, methanol, FFAs,
catalysts, and a portion of methyl ester. These contaminants contribute to the high
contents of COD and O&G, Jaruwat et al. (2010).

The biodiesel wastewater is mainly generated from the washing process which
can remove excess contaminants and impurities to ensure only the high quality
biodiesel that meets the specifications is produced, Daud Nurull Muna et al. (2015).

Water washing is most often used for purifying crude biodiesel after being
separated from the glycerol phase. This method includes the addition of hot distilled
water, precipitation of saturated biodiesel is eliminated and the emulsion formation is
prevented. After settling and separating the aqueous phase, fresh water is added to the
washed biodiesel.

The washing is usually repeated several times (2-5 times) until colorless spent
washing water is obtained and meaning that the impurities are completely removed
from biodiesel product. Some of disadvantages of this process are long separation

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time and loss of yield in the rinsing water contributes to the generation of polluted
liquid effluent, Veljković et al. (2014).

8.3 Design of Wastewater Treatment Process (full-scale)

To ensure proper design of oil/water separation systems, engineers must

understand the nature and characteristics of the oil to be removed. Removal of oils
from wastewater is typically the first step in wastewater treatment and the most
important step. Poor oil removal from raw wastewater can also have significant
detrimental impact on subsequent treatment technologies such as biological treatment,
T. E. Schultz (2006).

Some production plants are more likely to deliver the wastewater to a

treatment facility of a water agency due to their inability to treat this wastewater with
high organic content, Daud Nurull Muna et al. (2015).

In most cases of their own treatment system within the plant, an upstream
chemical-physical pretreatment is required to achieve a good efficiency and efficient
operation of the biological treatment. Moreover, the reuse of all process wastewaters
in the production of biodiesel is an interesting option for the factory management. A
typical treatment process for reusing the wastewater should include the use of a
physico-chemical process as primary treatment followed by sedimentation or
floatation, a biological treatment or secondary treatment and a reverse osmosis
system, Veljković et al. (2014).

Several treatment processes have been developed for the wastewater generated
by the biodiesel production via alkali catalyzed transesterification. However, the
optimum design based on the conclusion from many researchers can be concluded in
the following lists below;

8.3.1 Preliminary treatment

To enhance the operation and maintenance of subsequent units, the

preliminary treatment is necessary. The first level of wastewater treatment process
actually is preliminary treatment which involves the removal of wastewater

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constituents which may cause maintenance or operational problems in downstream
treatment, Puchongkawarin (2015).
Since the design is required to support and receive the wastewater from
different sources, equalization tank can be used to eliminate or minimize the problems
associated with such fluctuations in wastewater flow and characteristics, Ebrahimi et
al. (2016).

WW1

WW2 Equalization Tank Equalized

WW
WW3

Figure 8.2 Equalization tank in preliminary treatment

The equalization tank is just an empty tank which the tank design of volume
can be received by wastewater from different sources that should be enough for all
plants. This tank can minimize fluctuations in flowrate to wastewater treatment
process, reduce fluctuation in organic load or concentration of pollutants to prevent
shock loading of biological treatment system, reduce fluctuation in wastewater pH
value and minimize fluctuation in the amount of chemicals to be added to chemical
treatment downstream plant, T. E. Schultz (2006).

8.3.2 Primary treatment

A portion of the organic matter and suspended solids are removed in primary
treatment. The liquid effluent from primary treatment may still have a high BOD and
contain large amounts of suspended organic matter. The separated organic solids from
this stage are sometimes stabilized by anaerobic digestion or incinerated for energy
recovery; the remains from sludge stabilization are used either for landfill or fertilizer.
The removal is achieved by sedimentation and some chemicals such as polymers may
be added to enhance solid removal, Puchongkawarin (2015).

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1) Primary physico-chemical treatment
The physico-chemical treatment of the biodiesel wastewater involves
adsorption, acidification (pH adjustment) and flocculation/coagulation
processes or their combination, eventually followed by a physical treatment
such as sedimentation, filtration or floatation, Veljković et al. (2014).
Coagulation-flocculation is effective for removing high concentration
organic pollutants and heavy metal in water and wastewater. As such,
biological treatment or secondary treatment of the biodiesel wastewater is
expected to be very difficult. For this reason supportive physico-chemical
methods are often used and the most frequently employed method is
coagulant, Madaeni and Eslamifard (2010).
The biodiesel wastewater was dark yellowish cream in color, highly
turbid, smell, has high organic load as seeds are used as a chief raw material in
the production, with high levels of COD, BOD, oil, high suspended and
dissolved solids.

Figure 8.3 Coagulation-flocculation processes

Dosage of coagulant was one of the most important parameters to

determine the optimum condition and performance. Basically, insufficient
dosage or overdosing would results in the poor performance in the
flocculation, De Gisi et al. (2013).
Many researchers stated that PAC or polyaluminum chloride provides
removal efficiency more effective than others (alum, ferric chloride and ferric
sulfate). The better efficiency of coagulation enhance the better performance
of flocculation process for removing suspended solid (SS), color, COD and
O&G in the wastewater, Costa et al. (2017).

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 However, the pretreatment of biodiesel wastewater treatment by
acidification (phosphoric acid) and coagulation can enhance the efficiency of
DAF and more economical treatment system. The efficiency of O&G, COD
and SS removal by the DAF with alum would be the best condition for the
biodiesel wastewater, Daud Nurull Muna et al. (2015).

2) Dissolved air floatation

Flotation is an accelerated gravitational separation technique in which
fine gas bubbles are injected into a water phase containing immiscible liquid
droplets (oil) or oily solid particles so that the gas bubbles attach themselves to
the droplets. Since flotation device owns a big processing capacity and
produces less sludge, oily wastewater treatment has great potentiality.
Currently the most commonly used method is dissolved air flotation, MING et
al. (2016).
Dissolved air floatation or DAF has been widely used treatment
method for oil in water emulsions (O/W). Gravity settling is not usually a
feasible treatment method due to the fine droplets which have a very low
settling rate, Karhu et al. (2014).
The DAF is reliable separation method and also simple. In addition,
the DAF has been used for treating wastewater to separate oil from aqueous
dispersion, chemically treated wastewater, and oil refinery wastewater,
Rattanapan et al. (2011).

3) Primary sedimentation; more dense than secondary

Primary sedimentation unit is a single-packed bed which is used to
prepare wastewater to be ready for biological or secondary treatment, De Gisi
et al. (2013).
For medium and large scale WWTPs, wastewater influent typically
undergoes primary settling to remove 50-70% of the particulate matter.
Primary settling has effects on both wastewater and sludge treatment, which
turns out to be lower oxygen demand and higher energy recovery.

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 Primary sedimentation increases the solid fraction of COD sent to
anaerobic digestion, and this leads to an increase in biogas production, and
energy recovery of up to 130%. It could also reduce energy consumption by
up to 13.5% compared to a scenario without primary sedimentation,
Puchongkawarin (2015).

8.3.3 Secondary treatment or biological treatment

Biological treatment of oily wastewater can be cost-effective, environmental

friendly, and more compatible with existing plant facilities compared to the other
techniques. However, excess sludge production is a by-product of this process, raises
a serious issue during the wastewater treatment. Treatment and disposal of
considerably high produced sludge may even account for almost 60% of total
associated costs and energy demand of the treatment plant. Thus, the optimal design is
essential to reduce the cost, Ebrahimi et al. (2016).
After primary treatment, wastewater is sent to secondary treatment to remove
organic matter and any remaining SS by means of biological treatment, either under
aerobic or anaerobic conditions, Puchongkawarin (2015).
This treatment process focuses on the ability of MIC or microorganisms to
convert organic wastes into stabilized compound, Masters and Ela (2014).

1) Secondary physico-chemical treatment

A chemical–physical upstream or in the primary treatment is useful in
removing lipophilic compounds (biodiesel, fatty acids, unreacted glycerides), which
inhibit the subsequent biological treatment. Due to the high organic load in the
biological treatment, it is worth using pure oxygen instead of a traditional aeration
system. A secondary chemical–physical treatment can be used to prevent activated
sludge de-flocculation as well as increase the concentration in the mixture, De Gisi et
al. (2013).

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 2) Combined trickling filter (TF) and activated sludge (AS) system
The effluent of primary sedimentation was divided between the TF and AS
systems. Half of the inlet flow is sent to the TF system, while the two outlet streams
are sent to the AS system. The combination of trickling filter (TF) and activated
sludge (AS) treatment processes is an attractive option for the treatment of high-
strength industrial wastewater. The results obtained for the AS system. Similarly to
the TF system, a better performance of the AS system was registered for the high
organic load or COD removal, De Gisi et al. (2013).
A greater demand of dissolved oxygen or DO of organic matter corresponds to
a greater value of the organic loading ratio, with a consequent reduction in the
dissolved oxygen concentration in the AS-reactor system. Activated Sludge process
with complex mixing with recycle and excess sludge is wasted from recycle line.
Separate sludge to disposal and send clear water out from the secondary clarifier.

3) Aeration/Oxidation tank
Supplying air to the wastewater unit operation and the MIC will use air, BOD
and organic compound to produce CO2 and water. This unit will be effectively used
when the BOD value is not higher than 1,000 mg/L in case of aerobic treatment. If the
BOD value is higher than 1,000 mg/L, the unit must be operated under anaerobic
condition, Masters and Ela (2014).

4) Secondary sedimentation
Using of Ecofloc CHA233, a mixture of natural polymer and aluminum salts
in small percentages, assisted to increase the sedimentation of the light sludge. The
sludge from primary sedimentation is heavier or more dense than secondary
sedimentation, De Gisi et al. (2013).

5) Filtration
Clear water is carried out from the secondary clarifier will be filtrated again to
filter backwash effluent out. The remaining clear water will be sent to the last unit of

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secondary treatment or disinfection unit in RO system. Mostly use sand filters before
sending the water to reverse osmosis or RO unit, De Gisi et al. (2013).

6) Storage tank
The effluent was subsequently sent to storage tanks in order to complete the
treatment on filtration and RO which will be effectively in the batch condition since
from the upstream process is operated in continuous condition, De Gisi et al. (2013).

7) Reverse Osmosis or disinfection unit

There are 2 objectives for the disinfection unit: the first is to kill any
microorganism in water and to prevent microorganism regrowth during the period
before being used or when transported along the pipe.
The removal of COD and salts can be obtained with a membrane system in
order to reuse permeate of the RO system. The percentage of permeate can be
measured as the ratio between the flow rate of permeate at the end of the test and the
feed flow rate of the RO unit, De Gisi et al. (2013).
However, the RO process continues to have the limitations. For example, RO
membranes are more sensitive than thermal desalination processes to scaling, fouling,
oxidant attach and pH effects, Ghazi Al-Enezi (2002).
Treatment by reverse osmosis effectively decreases the turbidity, COD, BOD,
TDS and SS of the wastewater up to 98%. Treatment by RO effectively decreases the
pollutant loads of the wastewater up to 98% and Ro treated wastewater may be used
as make-up water for cooling towers or feed water for water demineralization unit,
Madaeni and Eslamifard (2010)

8) Up-flow anaerobic sludge blanket (UASB) bioreactor

UASB bioreactor is one of the most popular anaerobic wastewater treatment
systems and has been the most widely used high-rate anaerobic reactor for wastewater
treatment throughout the world since the 1980s. The UASB bioreactor was found to
be a successful biological treatment system, achieving a high COD removal efficiency
for the treatment of petroleum refinery effluent, Rastegar et al. (2011).

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 Basically, the RO unit is used to filter out the filtrate and recycle treated water
back in to the main process for drinking water factory. Since the treatment system in
MEI plant using RO unit as the separator between high and lower COD value. The
higher COD value will be sent to the anaerobic UASB bioreactor.

9) Water receiver
All of the effluent water from the treatment system will be treated by the
nearest industrial estate or the final treatment before discharging to the natural water
resource.

8.3.4 Alternative options for wastewater treatment system

Related to the 8.3.1 to 8.3.3, the alternative option for the wastewater
treatment design will be classified into four alternative options. The four options
below will start with the equalization tank to equalize the incoming wastewater from
different sources with different characteristics.

WW1

WW2 Equalized WW

WW3

Figure 8.4 Equalization tank

The 4 alternative options will start with the effluent from the equalization
tank.
1) Low to moderate BOD and COD value

Coagulation DAF Primary Activated Primary Secondary Secondary

Sludge Sedimentation Activated Sludge Sedimentation
Aeration

Figure 8.5 A treatment system for low to moderate BOD and COD value

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 Starting with the primary treatment, the coagulant will be added to the
equalized wastewater, separate the scum sludge by the DAF or dissolved air floatation
unit, remove suspended solid and some COD removal in the primary activated sludge,
separates sludge from the wastewater in the primary sedimentation unit. The effluent
will be fed to the secondary treatment.
Air will be supplied to the effluent water in the secondary activated sludge
aeration tank to reduce the COD value by MIC or microorganism then the wastewater
will be separated from the secondary sludge in the secondary sedimentation unit.
The treated water will be sent to the last unit or disinfection unit to kill any
pathogen or MIC in the water and prevent MIC growth during the period before used
of the water such as chlorine disinfection unit and UV-radiation and oxidation. The
chlorine disinfection unit is the most commonly used method due to the lower cost,
reliability and easy to operate.

2) Low to moderate COD and high BOD value

If the BOD value is higher than 1,000 mg/L, the aeration or aerobic treatment
will not be efficient anymore. Anaerobic treatment will be used to deal with the
higher BOD value of the wastewater. The secondary treatment will be operated in the
anaerobic condition.
Recalling the treatment system from low to moderate BOD and COD value,
the secondary activated sludge aeration will be changed into the activated sludge unit
as in the primary treatment.

Coagulation DAF Primary Activated Primary Secondary Secondary

Sludge Sedimentation Activated Sludge Sedimentation

Figure 8.6 A treatment system for low to moderate COD with high BOD value

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 3) Low to moderate BOD value with high COD value
The higher COD value will not be treated efficiently by the activated sludge
unit. The effluent water from the DAF unit will be sent to the UASB or up-flow
anaerobic sludge blanket bioreactor before going to the primary activated sludge
an in the first option.

Coagulation DAF Primary Activated Primary

UASB
Sludge Sedimentation

Figure 8.7 A treatment system for low to moderate BOD with high COD value

4) High BOD and COD value

In this option, the secondary activated sludge aeration in the third option will
be changed into the secondary activated sludge since the BOD value is high.

8.3.5 The wastewater treatment system of the plant Methyl Ester I

The system receives the wastewater from 3 different processes with different
flowrate and wastewater characteristics. The 3 processes consist of biodiesel or
methyl ester process, fatty alcohol process and fatty acid. Every effluent from the
process will be equalized in the equalization tank and go through the system as shown
in the figure below.

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 Figure 8.8 A treatment system in the plant methyl ester I (MEI)

The RO-unit or reverse osmosis is normally used to separate solids and water
to recycle the water back in the main process but in this treatment system the unit is
used to separate wastewater into two groups, high COD and low COD value.
The low COD value will be treated by primary activated sludge aeration tank,
primary sedimentation, secondary activated sludge aeration tank, secondary
sedimentation and to the effluent water receiver before sending to Hemaraj Industrial
Estate to be treated in the final treatment.
The high COD value will be sent to UASB or up-flow anaerobic sludge
blanket bioreactor which will treat the wastewater by using anaerobic treatment.

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8.4 Laws and Regulations of Industrial Wastewater in Thailand

Under the Factory Act B.E. 2535 of Ministry of Industry or MOI Notification
(Clause 14) specifying that: “Discharge of wastewater effluent from a factory shall be
prohibited unless there is any treatment, other than dilution, applied to such
wastewater so that its characteristics meets what prescribed by the Minister of
Industry”

The Notification of Ministry of Industry (No. 2) B.E. 2539 issued under the
Factory Act B.E. 2535 regarding Industrial Effluent Standards dated June 14, 1996
shall be revoked and The Notification of MOI regarding Industrial Effluent Standard
B.E. 2560 shall take into effect from June 7, 2017 onward.

The Minister of Industry has prescribed the Notification hereof;

8.4.1 The characteristics of effluent discharging from a factory

Item Unit Standard Value

1 pH value
2 Total Dissolved Solid (TDS)
3 Suspended Solid (SS)
- 5.5 – 9.0
mg/L 2.1) Not more than 3,000 mg/L depending on
receiving water or type of industry under
consideration of Pollution Control
Committee (PCC) but not exceeding
5,000 mg/L
2.2) Not exceeding TDS of receiving water having
salinity of more than 2,000 mg/L or TDS of
sea water if discharging to sea by not more
than 5,000 mg/L
mg/L Not more than 50 mg/L depending on receiving
water or type of industry or type of wastewater
treatment system under consideration of PCC but
not exceeding 150 mg/L

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Item Unit Standard Value
4 Temperature °C Not more than 40
5 Color and Odor ADMI Color not exceeding 300
6 Sulfide (as H2S) mg/L Not more than 1.0
7 Cyanide (as HCN) mg/L Not more than 0.2
8 Heavy Metals
8.1 Zinc (Zn) mg/L Maximum permitted value is 5.0
8.2 Chromium (Hexavalent) mg/L Maximum permitted value is 0.25
8.3 Chromium (Trivalent) mg/L Maximum permitted value is 0.75
8.4 Arsenic (As) mg/L Maximum permitted value is 0.25
8.5 Copper (Cu) mg/L Maximum permitted value is 2.0
8.6 Mercury (Hg) mg/L Maximum permitted value is 0.005
8.7 Cadmium (Cd) mg/L Maximum permitted value is 0.03
8.8 Barium (Ba) mg/L Maximum permitted value is 1.0
8.9 Selenium (Se) mg/L Maximum permitted value is 0.02
8.10 Lead (Pb) mg/L Maximum permitted value is 0.2
8.11 Nickel (Ni) mg/L Maximum permitted value is 1.0
8.12 Manganese (Mn) mg/L Maximum permitted value is 5.0
9 Fat, Oil and Grease (FOG) mg/L Not more than 5 mg/L depending on receiving
water or type of industry under consideration of
PCC but not exceeding 15 mg/L
10 Formaldehyde mg/L Not more than 1
11 Phenols mg/L Not more than 1
12 Free Chlorine mg/L Not more than 1
13 Pesticide mg/L None
14 Biochemical Oxygen Demand mg/L Not more than 20 mg/L unless the specific type of
(BOD5)* industry, or different capacity level of receiving
water can be permitted to be more than 20 mg/L
by PCC but the maximum allowable value shall
not be more than 60 mg/L
15 Total Kjedahl Nitrogen (TKN)** mg/L Not more than 100 mg/L unless the specific type
of industry, or different capacity level of receiving
water can be permitted to be more than 100 mg/L
by PCC consideration but the maximum allowable
value shall not more than 200 mg/L

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Item Unit Standard Value
16 Chemical Oxygen Demand mg/L Not more than 120 mg/L depending on receiving
(COD)*** water or type of industry under consideration of
PCC but not exceeding 400 mg/L

Remarks:

*10 types of industries which has been accepted by PCC to discharge the effluent of
which BOD5 is up to 60 mg/L as follows:

1) Animal furnishing factories 2) Starch factories

3) Food from starch factories 4) Animal feed factories

5) Textile factories 6) Tanning and grinding factories

7) Pulp and paper factories 8) Chemical factories

9) Pharmaceutical factories 10) Frozen room factories

**Effective after 1 year of announcement by Ministry of science, technology and

Environment for factories type 2 and 3, but after 2 years for factories type 13(2) and
15(1). There are discharge the effluent of which TKN is up to 100 mg/L.

***5 types of industries which are permitted by PCC to discharge the effluent of COD
up to 400 mg/L as follows:

1) Food from starch factories 2) Animal feed factories

3) Textile factories 4) Tanning and grinding factories

5) Pulp and paper factories

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 8.4.2 Analytical methods of effluent according to Notification of MOSTE
NO.3

Analysis of parameters prescribed in the industrial effluent standard shall be

conducted as in the table below:

Parameter Analytical Methods

1 pH value pH meter
2 Total Dissolved Solids (TDS) Evaporation (Temperature 103 -105 °C, 1 hour)
3 Suspended Solids (SS) Glass fiber filter disk
4 Temperature Thermometer
5 Sulfide as H2S Titration
6 Cyanide as HCN Distillation following Pyridine-Barbituric Acid
7 Heavy Metals
7.1 Zinc (Zn) Atomic Absorption Spectrophotometry-Direct Aspiration or
7.2 Chromium (Cr) Plasma Emission Spectroscopy-Inductively Coupled Plasma
7.3 Copper (Cu) : ICP
7.4 Cadmium (Cd)
7.5 Barium (Ba)
7.6 Lead (Pb)
7.7 Nickel (Ni)
7.8 Manganese (Mn)
7.9 Arsenic (As) Atomic Absorption Spectrophotometry-Hydride Generation
7.10 Selenium (Se) or Plasma Emission Spectroscopy-Inductively Coupled
Plasma : ICP
7.11 Mercury (Hg) Atomic Absorption Cold Vapor Technique
8 Fat, Oil and Grease Extraction by organic solvent
9 Formaldehyde Spectrophotometry
10 Phenols Distillation, 4-Aminoantipyrine
11 Free chlorine Iodometric Method
12 Pesticides Gas Chromatography
13 Biochemical Oxygen Demand Azide Modification at 20 °C, 5 days or other methods
(BOD5) approved by PCC
14 Total Kjedahl Nitrogen (TKN) Kjedahl Method
15 Chemical Oxygen Demand Potassium Dichromate Digestion
(COD)

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 Remarks:

1) Analytical methods of effluent from industrial plants and industrial estates

should follow Manual of Water and Wastewater Analysis by Thai
Environmental Engineer Association or Standard Methods for the
Examination of Water and Wastewater by American Public Health
Association (APHA), American Water Work Association and Water
Environment Federation.
2) The sampling methods, frequency and sampling duration of effluent will be
specified by Pollution Control Department in the Royal Gazette.
3) MOSTE: Ministry of Science, Technology and Environment.
4) Wastewater means waste in liquid state including pollutants or contaminants
in such liquid.
5) Discharge means wastewater generated from an industrial process or industrial
estate which is discharged into public water resources or the environment,
including wastewater generated from workers and other activities in the
factory or in industrial estate. All discharges have to meet the standard.

8.5 Environmental Sustainability of Biodiesel in Thailand

Since the objective of the cooperative study is to optimize process to minimize
waste. The sustainability section will be conducted to see the possible options to
satisfy the objectives.
The utilization of the biodiesel wastewater as a potential source of energy is a
convenient way of reducing the biodiesel costs and making more competitive when
compared to petroleum diesel. The combination of a cleaner technology and
environmental engineering including the appropriate waste treatment is a good
approach to improve the environmental performance of the biodiesel production and
to make more sustainability, Veljković et al. (2014).

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 Figure 8.9 A proposed options of development for improvement of the Biodiesel
Industry in Thailand

The proposed option can be classified into clean technology and waste
exchange applications. Aiming to improve the environmental performance of the
biodiesel industry by minimizing wastes generated from the production processes as
well as increasing value of the wastes for sale. The outcome of these measures is also
expected to enhance the production efficiency of the biodiesel factories, Raghareutai
et al. (2010).

8.5.1 Clean technology measures

The clean technology measures consist of 4 methods: recovery of methanol

from methyl ester and glycerin; substitution of the sodium hydroxide (NaOH) catalyst
by sodium meth-oxide (NaCH3O); reuse of water at the ME washing step and
minimization of ME loss at the purification step.

1) Recovery of methanol from methyl ester and glycerin

After the separation unit, the remaining excess methanol can be
recovered and reused by the distillation column to save on purchasing cost of
the alcohol but also cost of treatment due to a reduced COD in the wastewater.

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 2) Substitution of the sodium hydroxide by sodium meth-oxide
To reduce use of washing water but the sodium meth-oxide is
relatively expensive and difficult to handle (highly caustic and volatile).

3) Reuse if water at the methyl ester washing step

The final washing water effluent could be reused as the first washing
water since the effluent contained less glycerin and methanol contaminants
and the industry could save approximately the water cost 3.6 baht/m3 of
biodiesel produced.

4) Minimization of methyl ester loss at the purification

Using controlled temperature water at 70 C and 5%H3PO4 aqueous
solution at 50 C, the ME can be readily separated from the washing water and
the COD content would be lower at the same time, which in turn reduces the
wastewater treatment costs.

8.5.2 Waste exchange measures

To minimize disposal of glycerin and spent bleaching earth, the two main
wastes from the production.
Glycerin can be reused as fuel (syngas), can be recycled as raw material for
other industries (pharmaceutical and cosmetic fields), and can be sold as high purity
glycerin. The same as spent bleaching earth can be reused in industrial and
agricultural section (fertilizer, soil improvement).

22
 8.5.3 Biogas recovery from biodiesel wastewater treatment
The wastewater had a significantly high COD and O&G because of
contamination with oil feedstock, soaps, methanol and glycerol. The biogas had
methane content up to 70%. The biogas can be used as fuel for electricity generation
and use of biogas as fuel also contributes to reduce the global warming potential
(GWP).

Figure 8.10 A schematic diagram for optimized waste management for the biodiesel
production industry using palm oil refinery.

The proposed options were developed with a clean technology approach and
industrial ecosystem strategy to minimize use of raw materials and waste generation.
Furthermore, the waste exchange approach aimed for the value-added conversion of
crude glycerin, which is the most common produced waste from the biodiesel
production process.
The wastewater should be treated not only for the purpose of contaminant
removal, but also for generation of beneficial by-products such as biogas.

9. Experiment and learning step (Research Methodology/proposal strategy)

9.1 Study the biodiesel production process and its wastewater characteristics
9.2 Study the wastewater treatment for biodiesel production
9.3 Optimize and design the proper treatment system

23
 9.4 Preparing TOR or term of reference
9.5 Sourcing vendor who can supply the package of wastewater treatment
system
9.6 Preparing and submitting the proposal project
9.7 Technical Bid Evaluation
9.8 Commercial Bid Evaluation
9.9 Negotiation among the team project
9.10 Final recommendation of the treatment package
9.11 Writing a report
9.12 Project action plan is shown in the table below:

2017 2018
PHASES OF THE PROJECT
Aug Sep Oct Nov Dec Jan Feb Mar Apr

1. Receive the project title

2. Study the related literatures

3. Preparing TOR

4. Bid survey

5. Issue official TOR

6. Submit proposal

7. TBE

8. CBE

9.Negotiation

10.Final/Award recommendation

11.Writing the report

24
10. The expected advantages
1) To obtain improved values of wastewater characteristics such as chemical
oxygen demand (COD), biochemical oxygen demand (BOD5), suspended solid
(SS), color, and pH value from biodiesel production.
2) To recover, reduce and verify process efficiency by optimizing the wastewater
design.

25
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