Chapter 7 Wastewater Treatment

381
CHAPER 7
WASTE TREATMENT
7.1 INTRODUCTION
Waste is a general problem in a chemical plant and it still remains a global problem
in developed countries. Normally, a plant takes the raw materials to produce,
through stages of processing steps, one or more products for sale with purpose to
generate income. However, it is seldom possible to convert 100% of the raw
materials into desired products, hence, there is almost always some waste or
residual. Based on Second Law of Thermodynamic, there is no process can achieve
100% efficiency, so, the wastes are always to be taken into consideration.
In the manufacturing and heavy industries, there have been rapid increases
in the generation of pollutants and industrial wastes, resulting in the deterioration of
environment. Waste treatment is an essential process in order to reduce and
minimize the environmental pollutions, especially for those contains toxic
components. It is a responsibility to treat the waste to an acceptable form or level
before discharge into the ecosystem. Waste treatment is an economic burden to a
process plant since it does not bring any economic advantage to the company
participated. However, the implication
implication of waste treatment plant becomes important
with regards to environmental pollution. Thus, waste treatment is important in order
to contribute to a safe environment.
In Malaysia, Department of Environment (DOE) is responsible to make sure

the all chemical plants design a waste treatment unit to treat the waste to an
acceptable form or level before discharge them into the environment. Direct
discharge of unwanted material into the natural ecosystem may pollute and destroy
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382
the balance of the ecosystem. Before the wastes are discharged to the environment,
some consideration must be done. Firstly, we have to consider the economic
aspect, whether the waste can be recover and sell as a by-product or not. There are
2 approaches to deal with waste produced from an industry:
1. Waste minimization
2. End-of-pipe Treatment
Waste minimization is to eliminate or reduce the waste generated at the

source or by not producing it in the first place. Therefore, it will eliminate any
problems in treating it and at the same time we can save more on capital cost.
On the other hand, end-of-pipe treatment means to transform the generated

waste into another kind of materials or components that is harmless so that it can be
released to the environment by using any physical, chemical, and biological or the
combination of three methods. However, the treated waste is still hazardous to the
environment; we can send it to waste treatment experts such as Kualiti Alam in Bukit
Nenas, Negeri Sembilan. In this chapter, we will deal with the liquid wastes
generated by Butyl Acetate production.
7.2 REGULATIONS
In Malaysia, the matters relating to the disposal of plant wastes regulated under
Environment Quality Act 1974. Department of Environment (DOE) is the parties that
responsible for managing matters that related to waste disposal. In order to ensure
that the premises or plant obey the regulation regarding the waste disposal, the
waste must be treated according to the parameter set as in (Appendix 7G:
Parameter of Environment Quality Act 1974). Basically waste treatment plants are
non-profitable. Hence, an optimum plant is needed to apply in order to minimize the
expenses occur from the waste treatment plant.
plant. It must be effective in order to
comply with the standard sets by the authorities.
The wastewater is essentially the water supply of the community after it has
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383
establishments, together with groundwater, surface water and other means may be
present. If untreated wastewater is allowed to accumulate, the decomposition of the
organic materials it contains can lead to the production of
of malodorous gases. In
addition, untreated wastewater usually contains numerous pathogenic micro-
organisms that dwells in human internal organs or may be present in industrial
wastes.
The selected method to treat these wastes must be suitable in order to

control the concentration of chemical compound before releasing to environment.
However, these wastes could be minimized while operation by considering several
units operations where waste minimization can be utilized.
7.3 AIR AND WATER STANDARDS
7.3.1 Ambient Air Quality Standards
Ambient air quality standard is a national target for an acceptable concentration

specific pollutant in air. Under the clean Air Act, EPA develops two standards
pollutant of concern.
1. A primary
primary standard is to protect public health. The clean
clean Air Act mandated
primary standards be based entirely on health-related information, without
considering the cost of attaining the standard.
2. A second standard is to protect public welfare. Public welfare includes soils,
water, crops, vegetation, buildings, property, animals, wildlife, weather
visibility, transportation and other economic values as well as personal
being.
The Clean Air Act, which was last amended in 1990, requires EPA to set
National Ambient Air Quality Standards for pollutants considered harmful to public
health and the environment. The EPA Office of Air Quality Planning and Standards
(OAQPS) has set National Ambient. (Appendix 7F: National Ambient Air Quality
Standard). Units of measure for the standards are parts per million (ppm) by volume,
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384
7.3.2 Water Quality Standards
Water quality criteria based on present –

–day standards and guides are presented to
assist in the establishment of water system performance goals for any plant. Quality
criteria are expected to change as new information on the nature and behaviour of
water is
is revealed.
revealed. The trend is toward production of water
water of higher quality. The
quality of raw-water sources is not expected to improve substantially and indeed
may worsen in many places as greater use is made of streams for waste disposal.
The water treatment plant, therefore, will have an increasingly important role of
production of water of high quality. (Appendix 7H: Optimum and Maximum
Characteristics of Water for Industrial.).
7.4 WASTE MANAGEMENT HIERARCHY
The best waste management is illustrated by the waste management hierarchy.

Pollution prevention or source reduction is always the top priority option in waste
management decisions. The waste management is begin by source reduction and
followed by recycling. Source reduction means the reduction of waste at the spot
and this is most preferable because in recycling the generation still occurs. If these
two preferred options are not possible then waste treatment should be considered
before the final preferable option disposal is considered.
Source
Reduction
Recycling
Treatment
Disposal
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385
The four options of waste management above are more clearly defined as
listed below:
Source reduction
- Procedures that either reduce or eliminate the generation of hazardous
waste before the waste is produced.
Recycling
- Reuse of waste stream as an ingredient
ingredient in a productive process or recovery
recovery
of a reusable.
Treatment
- The use of physical, chemical, biological, or thermal technologies to
to reduce
the volume, toxicity and/or mobility of waste.
Disposal
- The placement
placement of
of waste into landfill or the underground injection
injection of
of waste.
7.5 WASTE MINIMIZATION AND POLLUTION PREVENTION

PREVENTION
Waste minimisation is at our top priority option in effluent solution. The best solution
to effluent problem is not to produce the waste in the first place or the waste
production is minimised. Waste minimisation reduces waste treatment cost and
reduces raw materials costs. Waste minimization and waste treatment can be
defined as below:
Waste Minimization
Minimization
- The reduction to extent
extent feasible,
feasible, of any solid or hazardous waste prior to any
treatment, storage, or disposal.
Waste Treatment
- The dealing of waste by means of certain techniques to achieve reduction of
of
volume, toxicity and mobility of waste after the waste has been generated
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386
7.6 OBJECTIVES OF MINIMIZATION AND TREATMENT
The waste minimization and treatment plant also have to fulfil the following objective
below:
1. To reduce potential environment liabilities.

2. To protect public and workers health from any harmless regarding the
pollution.
3. To meet and complies with the waste minimization
minimization standard set up by
Department of Environment (DOE).
4. To minimize the cost of plant by reducing waste treatment and disposal cost,
raw material purchases and other operating costs including utility costs.
7.7 METHODOLOGY
This chapter deals with the methodology of the evaluation work of waste
minimization in Butyl Acetate plant. It consists of:
1) Waste Sources Definition

2) Waste Sources Description
3) Selection of Waste Management Methods
4) Waste Treatment Process
Process Flow Diagram and Description
5) Calculation: Mass Balance
6) Wastewater Equipment Sizing
7) Wastewater Equipment Costing
8) Plant layout for the Waste Treatment System
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387
7.7.1 Waste Sources Definition
In the production of Butyl Acetate, there are two types of waste generate in Butyl
Acetate plant:
1. Liquid waste (Figure 10.2: Source of Liquid Waste from Butyl Acetate Plant )
2. Gaseous waste (Figure 10.3: Source of Gaseous Waste from Butyl Acetate
Plant )
Figure 10.2: Source of liquid waste

w aste from Butyl Acetate plant
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388
7.7.2 Waste Sources Description
Figure 10.7.1a shows the stream waste or stream 16 which decant from the bottom
of the decanter (V-100) contains a variety of components such as butanol, acetic
acid, butyl acetate and water as a major component. The other stream discharge
from the decanter which is stream 17 will proceed to next distillation column (T-101)
for further processes. In stream 16, the waste containing mostly liquid water which is
about 98.86 mol%. The other components are butanol, acetic acid and butyl acetate.
The composition for each component can be shown by referring to (Appendix 7A:
Wastewater stream composition). In other hand, there are also a gaseous waste
produce in our plant. This waste generate from the equipment such as reboiler
especially at the distillation column. The utilities that pass through the reboiler will be
converted into gas form. Therefore, the gases that may contain a toxic acid which
must be treated first before it discharge to the environment. Figure 6.7.1b shows the
source of gases waste from reboiler in Butyl Acetate Plant).
7.7.3 Selection of Waste Management Methods
This chapter deals with the selection of waste management methods that are
considered in this Butyl Acetate plant. As mentioned above, there are two type of
waste generate in our plant which is liquid waste and gaseous waste.
Liquid waste Treatment

- The method of wastewater treatment system chosen is Conventional
Wastewater System treatment which consist of two type of treatment,
Primary Treatment (Primary settling basin) and Secondary Treatment
(Aeration Tank and Secondary Clarifier).
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389
7.7.4 Waste Treatment Process Flow Diagram

Diagram and Description
The proposed wastewater treatment which is Conventional Wastewater Treatment

System can be shown in the Figure 10.7.4b. There is one stream that produced
waste in this plant which is stream 16. This stream contains mostly liquid water
which is about 98.86 mol%. The composition of the stream 16 can be shown in (7A:
Wastewater stream composition). For the gaseous waste, the proposed treatment is
Gaseous waste treatment through direct thermal combustion. This type of treatment
can be shown in Figure 10.7.4a. For the liquid waste treatment, the biological
treatment is used because the waste that entering the treatment system contains of
organic compound. Besides that, we can also say that biological treatment is
suitable for treatment because the waste that entering the waste treatment has been
neutralized first in the neutralization tank before it undergo further treatment. In other
hand, the use of nutrients such as procaryotic sp. and eucaryotic sp. is preferable
since it ability in dealing with the highly toxic and chemical waste.
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390
P-6
11
P-8
1 2 3 5
P-5
21
E-100
V-100
MIX-100 P-22
V-101
V-102
V-100 Incinerator TITLE:

V-101 Caustic Scrubber Gaseous Waste Treatment
V-102 Neutralization Tank
MIX-100 Mixer DRAWN BY:
E-100 Heat Exchanger Mohamad Razif bin Mohamad. Rodzi
Figure 10.4: Gaseous waste treatment process flow

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391
7.7.4.1 Gaseous Waste Treatment Description
The simplify flowsheet for gas treatment process is shown in the Figure 106.7.4a.
The waste from reboiler at stream 11 and stream 21 is mixed in a mixer (MIX-100).
After that the stream mixed is heated up to 500 C in the heat exchanger (E-100)
before it been sent to incinerator (V-100) for combustion. In the incineration, waste
stream contains mixture components of butanol, acetic acid, butyl acetate and water
is mixed with fuel and combustion air.
The process begins when this mixture reacted at high temperature (650-
800 C) under control by catalyst.
catalyst. The catalyst is generally
generally platinum
platinum (noble metal)
dispersed on the surface of a catalyst support. At this stage, most of the
components are converted into NOX, CO, CO2 and H2O. Reduction of NOX in
incinerator depends on selection of catalysts. Most of the conversion is around 50 to
90 %. Treated gas temperature
temperature must
must not be below than
than 300 C in order to avoid
avoid
corrosion in the stack.
After the
t he incinerator process, the waste containing
co ntaining dry acetic acid and
an d a few
gases is passed through a caustic scrubber (V-101). The caustic solution about 73%
w/w concentrations was injected into the scrubber. The function of caustic solution is
to absorb the toxic gases so that the clean air will discharge at the top of the
scrubber. This type of clean air will be measured by comparing its concentration with
the concentration set up by the Department of Environment (DOE) or referring to (7
F: National Ambient Air Quality Standard). Besides that, the dry acetic acid that
passed through a scrubber will also be neutralized by the caustic solution so that the
products obtain from the neutralization process will not contain high percent of
water. It is easier to be sent to Kualiti Alam to be treated as a schedule waste.
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392
23
19
V-104
V-101
16 17 18
20
P-102
V-101 V-102 V-103

P-101
21
22 24
MIX-100
V-101 Neutralization Tank TITLE:

V-102 Primary Settling Basin Conventional Wastewater Treatment System
V-103 Complete-Mix Reactor
V-104 Secondary Clarifier DRAWN BY:
P-101 Pump to Complete-Mix Reactor Mohamad Razif bin Mohd. Rodzi
P-102 Pump to Secondary
Secondary Clarifier
MIX-100 Mixer
Figure 10.5: Conventional wastewater treatment system using activated sludge system
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393
7.7.4.2 Liquid Wastewater Treatment Description
Like the other chemical plants, Butyl Acetate plant also produces wastewater where
in form of liquid phase. The wastes discharge from the bottom of decanter (V-100)
contains several components such as butanol, acetic acid, butyl acetate and water
which flow at the rate of 1931 kg/h. The process flow diagram of wastewater
treatment proposed is shown as in Figure 10.7.4b, we have selected Conventional
Wastewater System as our treatment of the waste since it is contain an organic
compound which can be treated through biological microorganisms. This
wastewater treatment system consists of equipment such as Neutralization Tank,
Primary Settling Basin, Complete-Mix Reactor, Secondary Clarifier and mixer.
The process begins with the incoming waste from the stream 16 is flow into a
Neutralization Tank (V-101). The function of installing this tank is to ensure that the
pH of waste is in the range required which is 5.5 – 9. The small amount of Sodium
Hydroxide (NaOH) was injected into the tank to neutralize the acidic acid. The pH
indicator must also be installed inside the tank to measure the value of pH. If the
value of pH obtain was complies with the range needed, the wastewater will then be
allowed to discharged into the Primary
Primary Settling Basin (V-102). The main objective of
this basin is to decrease the amount of BOD5 and SS by some percent and also
separate the heavy organic in form of sludge. Efficiently designed and operated
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394
The biological treatment of wastewater stream is based on the ability of a

mixed population of microorganisms to utilize organic contaminants as nutrients.
Organic constituents can be removed by aerobically converting them into carbon
dioxide and water (mineralization) or by other mean we can anaerobically
decompose them into methane and carbon dioxide; or bio transferring to less toxic
or non-toxic organic compounds. Because of aerobic process, air which contains
oxygen (O2) from atmosphere is bubbled into the tank. Besides that, the aeration
tank also equipped with the mechanical stirrer which function to saturate the
wastewater with the oxygen. Besides that, it also important for the well distribute of
the oxygen in order to ensure the biological microorganism got enough oxygen
supplied before react with the incoming influent.
Biological microorganism requires specific ratios of carbon and nutrients. The

most important nutrients are nitrogen, phosphorus, sulphur, potassium, calcium, and
magnesium. Industrial wastewater often lacks the essential macro- and
micronutrients, which must therefore be added during treatment. Commonly
biological microorganisms used in our activated sludge system are procaryotic and
eucaryotic since their ability to treat an organic toxic.
Because the bacteria deplete the substrate, flocculation takes place. The
soluble substrate becomes a solid biomass. This is the place where the mixed liquor
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395
7.7.5 Calculations
7.7.5.1 Assumptions
1. Influent and effluent biomass X concentrations are negligible compared to

biomass at other points in the system.
2. Influent food concentration So is immediately diluted to the reactor
concentrations S because of the complete mix regime.
3. All reactions occur in the reactor. Example,
Example, neither biomass production nor
food utilization occurs in the clarifier.
4. Because of assumption (3) the volume represents the volume of reactor
only.
7.7.5.2 Mass Balance
7.7.5.2.1 pH calculation
In wastewater treatment of Butyl Acetate, the pH value plays an important key to the
wastewater treatment. According to Department of Environment, the wastewater
that can be discharge to the sewage must in between pH 5.5 to 9. Thus, pH
calculation before treatment is essential to determine how much alkaline solution
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396
Table 10.1: Concentration of acetic acid

CH3COOH CH3COO- H+
Initial 11.9192M +xM +xM
Change -xM xM xM
Equilibrium (11.9192-x) xM xM
Concentration ≈11.9192 M
ka for acetic acid = 1.8 x 10-5
(6.1)
Where x = [H+], so
pH = - log [H+]
= - log [0.01465]
= 1.83
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397
7.7.5.2.2 Neutralization Tank

S-16a
0.9527 kg NaOH /hr
S-16
1931 kg WWT /hr
1845.8429 kg H2O /hr

1.3517 kg AA /hr Neutralization
62.5644 kg BuOH /hr Tank S-17
21.241 kg BuAc /hr 1931.9527 kg WWT /hr
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398
It can be concluded that the total flow rate of waste after neutralization process is
1931.9527 kg/hr. We can see in the process that the amount flow rate of NaOH
required to neutralize the acid until it pH in the range of 5.5 – 9 is 0.9527 kg
NaOH/hr. Besides that, we also used the pH indicator to measure the value of pH.
The pH indicator will measure the reading and will released the wastewater after the
range of pH was complies with the standard.
7.7.5.2.3 Calculation of COD and BOD in waste stream
Acetic Acid
CH3COOH + 2 O2 2 CO2 + 2H2O
From the equation;

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399
7.7.5.2.4 Primary Settling Basin
S-17 S-18
Primary Settling Basin
1931.9572 Kg/hr 772.7811 kg/hr
S-22
1158.6 kg/hr
Figure 10.7: Primary settling basin configuration
Efficiently designed and operated primary sedimentation tanks should remove from
50 to 70 percent of the suspended solids and 25 to 40 percent of the Biological
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400
7.7.5.2.5 Activated Sludge System (Complete-Mix Reactor and Secondary

Clarifier)
S-23 Xe, Se
Q3=Qo-Qw
S-18 V-104
Qo, Xo S-19 S-20

V-103
X, S Qu, Xw
Qo + Qr
S-20a
O2 Qw, Xw,
S
P-101
S-21
Q r , Xw
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401
Effluent BOD5 for substrate
for substrate concentration, S was calculated as below,
(6.5)
Assume suspended solids (SS) in effluent = 20 mg/l and VSS/SS=0.8. If degradable

fraction of volatile suspended solids (VSS) =0.7, BOD5 of VSS in effluent, Xe =
0.7(0.8x20) = 11 mg/l.
Thus, total effluent BOD5 = 13.6 + 11 = 24.6 mg/L (acceptable).
The parameter for the growth constant for the Domestic wastewater can be shown
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402
Then, the food-to-mass ratios was calculated as below,
(6.7)
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403
Return Sludge flow rate, Qr . A mass balance around the secondary clarifier can be
written as follows,
(6.10)
Rearrange the equation in term of Qr ,

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404
7.7.6 Equipment Sizing
7.7.6.1 Neutralization Tank
Wastewater neutralization plays an important part in a wastewater treatment

process. It provides the optimum environment for microorganism activity between
pH 6.5 to 7, and the right waste discharge to the public sewage as mandated by
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405
Let H = 2D, therefore,

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406
By taking a sidewall depth of 3.5 m, volume of tank is approximately,
The detention time at flow rate is

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407
Length of the reactor,

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408
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409
Where,
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410
7.7.7.1.5 Utilities
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411
7.7.7.2.2 Heat Exchanger

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Chapter 7 Wastewater Treatment

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In Malaysia, Department of Environment (DOE) is responsible to make sure

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Waste minimization is to eliminate or reduce the waste generated at the

On the other hand, end-of-pipe treatment means to transform the generated

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The selected method to treat these wastes must be suitable in order to

7.3 AIR AND WATER STANDARDS

7.3.1 Ambient Air Quality Standards

Ambient air quality standard is a national target for an acceptable concentration

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7.3.2 Water Quality Standards

Water quality criteria based on present –

7.4 WASTE MANAGEMENT HIERARCHY

The best waste management is illustrated by the waste management hierarchy.

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7.5 WASTE MINIMIZATION AND POLLUTION PREVENTION

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