CHAPTER IV

WASTE TREATMENT AND WASTE MINIMIZATION

4.1 Introduction

Waste is general problem in a chemical plant and is global problem in

developing country. Normally, a plant takes the raw materials to produce, through
stages of processing steps, one or more products for sales with purpose to generate
income. It is seldom possible to convert 100% of the raw material into saleable
products, so there is almost always some waste or residual. It is follows the second
thermodynamics laws, which state that, more entropy are, generate when the work is
increase.

Environmental considerations are usually left to a late stage in the design.

However, early decisions often can lead to difficult environmental problems, which
later require complex solutions. Again, it is better to consider effluent problems as
the design to environment. This pollution can be in gas, liquid or solid.

The effects of pollution can be direct or indirect. The USEPA (United States
Environmental Protection Agency), (Occupational Safety and Health Act, 1994,
Government Printer, February 1994), has defined hazardous waste as waste or
combination of wastes that pose a substantial, present or potential hazards to human
or other living organisms because;
i. Such waste are non degradable or persistent in nature
ii. They can be biologically magnified
iii. They can be lethal, or
iv. They may be otherwise cause or tend to cause detrimental effects.

The problem with relying on end pipe treatment is that once waste has been
created, it cannot be destroyed. The waste can be concentrated or diluted, its physical
or chemical form can be changed, but it cannot be destroyed. Thus the problem with
end of pipe effluent treatment systems is that they do not so much solve the problem
as move it from one place to another.
Methodology
This chapter will be evaluated by following the list below:
 Define waste sources
 Find information on Air Quality Standard
 Waste Sources Description
 Select treatment method
 Treatment Plant Design

4.2 Air and Water Quality Standards

Most of the countries have set their own air quality standard that must be
followed. In air quality terminology, standards are air quality set for compliance and
enforceable by law. Guidelines are targets to be aimed without being legally binding.
The Malaysian air quality guidelines, is a guidelines in which pollutants should be
kept at certain concentration which has been set by the Department Of Environment.
Stack Gas Emission Standard from Environment Quality (Clean Air) regulation,
1978 can be used as reference.

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4.2.1 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.

 A primary standard to protect public health. The clean Air Act mandated
primary standards be based entirely on health-related information, without
considering the cost of attaining the standard.
 A second standard 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 Air Quality Standards for six principal pollutants, which are called
“criteria” pollutants. They are listed below. Units of measure for the standards are
parts per million (ppm) by volume, milligrams per cubic meter of air (mg/m3) and
micrograms per cubic meter of air at 25oC (g/m3).

4.2.1.1 National Ambient Air Quality Standards

Table 4.1 : National Ambient Air Quality Standard

POLLUTANT STANDARD VALUE STANDARD TYPE
CARBON MONOXIDE (CO)
8-hour average 9 ppm (10mg/m3)** Primary
1-hour average 35 ppm (40mg/m3)** Primary
NITROGEN DIOXIDE (NO2)
Annual Arithmetic Mean 0.053 ppm (100g/m3)** Primary & Secondary
OZONE (O3)
1-hour average* 0.12 ppm (235g/m3)** Primary & Secondary
8-hour average* 0.18 ppm (157g/m3)** Primary & Secondary

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LEAD (Pb)
Quarterly average 1.5 g/m3 Primary & Secondary
PARTICULATE < 10 MICROMETERS (PM-10)
Annual Arithmetic Mean 50 g/m3 Primary & Secondary
24-hour average 150 g/m3 Primary & Secondary
PARTICULATE < 2.5 MICROMETERS (PM-2.5)
Annual Arithmetic Mean 15 g/m3 Primary & Secondary
24-hour average 65 g/m3 Primary & Secondary
SULFUR DIOXIDE (SO2)
Annual Arithmetic Mean 0.03 ppm (80 g/m3)** Primary
24-hour average 0.14 ppm (365 g/m3)** Primary
3-hour average 0.50 ppm (1300 g/m3)** Secondary

* The ozone 1-hour standard applies only to areas that were designated non-
attainment when the 8-hour standard was adopted in July 1997. This provision allows
a smooth, legal and practical transition to the 8-hour standard.
** Parenthetical value is an approximately equivalent concentration.

4.2.2 Water Quality

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
behavior of water is revealed. The trend is toward production of 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. Below is the optimum and maximum
value of water characteristics for industrial uses.

Table 4.2 : Optimum and maximum characteristics of water for industrial uses
CHARACTERISTICS VALUE

Bacteria-per ml
Coliform (opt) 1.0
Coliform (max) 10

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 Organic-ppm
BOD (opt) 5
BOD (opt) 10
DO (opt) 3.0
DO (opt) 1.0
Oil (opt) 5
Oil (opt) 10

Reaction
pH (opt) 4.0-10.0
pH (critical) 4.0-10.0

Physical-ppm
Susp. Solids (opt) 50
Susp. Solids (max) 150
Float Solids (opt) None
Float Solids (max) Slight

Chemicals-ppm
Total Solids (opt) 1000
Total Solids (max) 1500
Na ratio (%) (opt) 90
Na ratio (%) (max) 90
Hardness (opt) 100
Hardness (max) 500
Temperature – oF Obnoxious

4.3 Government Specifications

Environmental Quality Act, 1979

Environmental Quality (Sewage and Industrial Effluents) Regulation, 1979.

Regulation 8(1), 8(2), 8(3)

Table 4.3 : Government Standards

STANDARDS
PARAMETER
A B
o
Temperature, C 40 40

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PH Value 6.0-9.0 5.5-9.0
BOD5 at 20oC, mg/L 20 50
COD, mg/L 50 100
Suspended solids 50 100

4.4 Type of Pollutants

Natural or air is considered to be approximately 20.9% oxygen, 78%

nitrogen, 0.9% argon and the reminder is carbon dioxide, hydrogen and other trace
elements. Two basic types of pollutant can contaminate this air:

4.4.1 Gaseous Pollutants

Any gaseous material found in the atmosphere in concentration higher than

those normally found in air a gaseous pollutant; whether it is dangerous or not really
depends upon the concentration. These gaseous pollutants are generally various types
of hydrocarbon materials, carbon monoxide, the oxide of sulfur, the oxides of
nitrogen, chlorine, others halogens and compounds of these halogens, ozone and
photochemical oxidants. The photochemical oxidant is not really an industrial
pollutant because it is not manufactured within the industrial complex.

4.4.2 Particulate Pollutants

Particulate are, of course, solid or liquid particles, which because of their size
and specific gravity become airborne either in a gas stream or are blown by the wind.
Particulate could be inert materials, such as finally divided soil or crushed stone; they
could be chemically reactive materials, such as calcium carbide or cement dust or
lime: or they might be hazardous or toxic materials, such as powdered lead, zinc or
asbestos. The effect of these materials on health and plant equipment (in terms of
erosion or corrosion). Particulate are not always solid particles; they may be fine
liquid mists or aerosols.

83
 Therefore standards for gaseous pollutant levels are based on 24 hour
exposure periods with a maximum concentration during that period. For example, the
long term primary ambient air quality standards for sulfur oxide are 80 g/m3, which
is 0.03 ppm. This is an annual arithmetic mean. The sort term primary ambient air
quality standard for sulfur oxide in a maximum 24 hour period is a concentration of
365 g/m3, which is 0.14 ppm; this is not to be exceeded more than once per year.

The typical annual, average particulate level in nonurban areas ranges from
10-60 g/m3 . Particulate, just gaseous pollutants, have an effect on human health,
but in the case of the particulate, the size rather than the quantity of the particles is
the governing factor. This is because filtration mechanisms of the respiratory tract
remove particles above 5-10  in diameter and of course, there is a wide difference in
the toxicity of various particulate. Air quality standards vary depending upon the area
but are in the same general range of 50-75 g/m3. (Handbook of industrial waste
disposal by Richard A. Conway and Richard D. Ross 1980, pg.484-488).
4.5 Ammonia Activated Sludge System

Ammonia that generated is alkaline and reacts corrosively with all body
tissues. For a 25% solution of ammonia in water, the aqueous ammonia is a colorless
liquid with pungent odor. It forms strong base, which corrodes aluminum and zinc.
The over exposure to this liquid in closed area may extremely destructive to tissues
of the mucous membranes and upper respiratory tract (if inhaled). Symptoms may
include burning sensation, coughing, wheezing, shortness of breath, and so on.

For this plant, we have chosen the activated sludge treatment system. There is
a constraint for activated sludge system, i.e. the contents of the active component (for
chemical plant, usually organic in nature) in the liquid cannot exceed a certain value.
It is because in activated sludge, microorganisms (bacteria and protozoa) are used to
biodegrade the organic components in wastewater. High concentration of waste in
the effluent destroys the proper biological functions/operations of those
microorganisms, killing them eventually. Therefore, laboratory examination of the
effluent is needed to determine the content and concentration of the effluent to be
treated.

84
 Table 4.4 below shows the Ammonia waste treatment plant. In aeration tank
(atmosphere pressure) the waste will treat with combination bacteria and oxygen
entering, this combination make reaction occurs in aeration tank. The reaction occur
in this show as below :

Organic matter  H 2O  O 2 bacteria

 CH 4  CO 2  NH3  New boimass  Heat

Notes: Organic matter such as Ammonia

Table 4.4 : The Amount of Waste Generated from Ammonia Plant

COMPONENT COMPOSITION PERCENTAGE (%)
(kg-mole/hr.)
Ammonia 0.47708 0.09245
Water 515.5017 99.9075

Notes: P = 1 atm, T = 27 C
The ‘biomass’ from aeration tank will be pumped to Clarifier, settling tank to
separate the liquid and solid. In clarifier, the solid will go down to filter press and the
water will pass to final conditioning tank using pump. Filter Press pressed the solid
to separate it into solid and liquid form, whereas liquid is recycle back to aeration
tank. The solid produced is called sludge and sent to Quality Alam for disposal to
environment without dangerous. Since the components of in the effluent are all
organic, the concentration of BOD is taken as a guideline to determine whether the
treated effluent is safe enough to be discharged into the environment. (shown in
Table 4.5)

The wastewater treatment plant is a tapered aeration activated sludge

treatment facility. Take BOD5 = 1000. This value corresponds to the BOD5 of the
effluent of an Ammonia plant in United States.

Therefore, BOD5 before treatment,

BOD5i = 1000 mg/L

To comply with the Environmental Quality Act (Amendment 1979), B Standard, we

only allow 20 mg/L BOD5 in the wastewater effluent from our chemical plant.

85
After treatment,

BOD5f = 20 mg/L

Table 4.5 : Environmental Quality Act, 1979

PARAMETER UNITS STANDARD B
o
Temperature C 40
pH - 5.5 – 9.0
BOD5 at 20oC mg/L 50
COD mg/L 100

Oxygen is fed to
N2, H2 Water
the tank Qu - Qw
Pump 3 Xe, Se
Clarifier

Influent
Aeration
Qo, So, Oo Tank
Qo + Qr
H2O,NH3 X, S
Pump 1 Qu, Xw

NH3,N2,H2
Final tank
Qf, Sf
Pump 2 Filter Press, F1
Qw, Xw, Sw

Qr, Xw

Figure 4.1 : Flow sheet For Ammonia Waste Treatment

We use typical design values for tapered aeration activated sludge plants for
design. Typical design values (see page 429, Table 15.4 (Reynolds, 1996)):
Mixed liquor suspended solids, MLSS = 2000 mg/L
Mixed liquor volatile suspended solids, MLVSS = 1500 mg/L (75% of MLSS)
Sludge density index, SDI = 10000 mg/L

Table 4.6 : Properties of Influent Flow

PROPERTY UNIT VALUE 20% OF OVER
DESIGN

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 Mass Kg/hr 9287.1570 11144.5884
Volume M3/day 223.3384 268.0061

4.5.1 Material Balance Calculations for Waste Treatment Plant

From result and literature (refer to flow sheet of treatment plant),

Qo = flow rate to aeration tank = 223.3384 m3 / d
X = biomass concentration in aeration tank = 2000 mg / L
S0 = Influent BOD5 = 1000 mg / L
S = Required effluent BOD5 = 20 mg / L
Øc = Mean cell residence time = 10 days
kd = decay rate = 0.06 day-1
Ý = yield coefficient = 0.6

Volume of aeration tank,

 c Qo Y  So  S   10( 223.3384)0.6  1  0.02 

V    1  0.06(10) 
2
X  1  K d c   
= 410.3843 x 1.2 (factor)
= 492.46 m3
 495 m3

V 495m 3
   2.22days  53hours
Qo 223.3384m 3 / d

Hydraulic Retention Time,

Volume of sludge wasted daily (Qw),

VX 495( 2)
Q w  9.9   9 .9 m 3 / d
Q w X w  c X wx1010
 (410
.1250
) kg / h
24

Mass of sludge wasted daily (QwXw),

Biological Solid Balance on Clarifier,

(Qo  Qr ) X  (Qo  Q w ) X e  Qu X w  (Qo  Q w ) X e  (Qr  Q w ) X w

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 Set that Xe = 0, then,

Qo X  Q w X w ( 223.3384)( 2)  99
Qr    43.4596m 3 / d
Xw  X 10  2

Ratio for feed to recycle,

Qr 43.4596
  0.19  19%
Qo 223.3384

Water discharge out from Clarifier,

Qo - Qw = 213.4384 m3/d
Balance around Clarifier,
QU Xw = ( Qo + Qr ) X
Qu ( 10 ) = ( 223.3384 + 43.4596 )( 2 )
Qu = 53.3596 m3 / d
F Qo S o
  0.23mg / mg.day
M VX

Air Requirements,

Typical cell yield coefficient, Y = 0.6 g/g

Typical endogenous decay coefficient, from the same source is, kd = 0.06 /d
Typical mean cell residence time,  c = 10 days
Y
Observed yield, Yobs   0.375 g / g
1  k d c

Net waste activated sludge produced per day,

Px = YobsQ(So – S)  (1000 g/kg)-1
= 16.81 kg/d
Oxygen requirement,
Q( S  S o )
O2   1.42 Px  29.32kg / day
1000 g / kg

Air Requirements:

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 Compute the volume of air required, assuming that the oxygen-transfer
efficiency for the aeration equipment to be used is 8%.
i) Theoretical air requirement, assuming that air contains 23.2% O2 by weight.
ii) Density of air at 1atm, 25oC = 1.1766 g/L
Airtheoy = 107.4 m3/d
iii) Actual air requirement at 8% transfer efficiency,
Airactual = 134.26 m3/d

4.5.2 Kinetics of Bacterial Growth

Organic matter  H 2O  O 2 bacteria

 CH 4  CO 2  NH3  New boimass  Heat

dX
For first order equation,  X
dt
Where,

dX growth rate of boimass mg/L/day


dt

X = concentration of boimass mg / L
 = specific growth rate constant , d -1
Notes: requirement for microbial growth, including availability of substrate.
Limiting substrate concentration:

S 20
  m 5  1.25d 1
Ks  S 60  20

S = concentration of limiting substance = 20 mg/L

m = maximum growth rate d-1 = 5 d-1
Ks = half – saturation constant = 60 mg/L BOD5

Growth rate for bacteria,

X = X0 exp.(t)
= 10 exp. (1.25x10)
= 2683372.9 g/ L/day

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4.5.3 Nitrification-Denitrification Process in Aeration Tank

The nitrogen compounds such as ammonia can be removed from the

wastewater through the biological nitrification-denitrification process. The ammonia
is biologically converted to ammonia nitrogen by metabolic pathways. In
nitrification-denitrification, the removal of nitrogen is accomplished in two
conversion steps. In the first step, nitrification. The oxygen demand for ammonia is
reduced, by converting them to nitrate. However, the nitrogen has merely changed
forms and not been removed. In the second step, denitrification, nitrate is converted
to a gaseous product for removal.

Nitrification is an autotrophic process, where energy for bacterial growth is

derived by the oxidation of nitrogen compound, the ammonia. Nitrification of
organic and ammonium nitrogen is a two-step process involving two types of
microorganism, the Nitrosomonas and Nitrobacter. In the first step, the organic
nitrogen are converted to nitrite:
3
NH 4  O2  NO2  2 H   H 2 O
2 Nitrosomonas

In the second step, the nitrite is converted to nitrate:

1
NO2  O2  NO3
2 Nitrobacter

Denitrification is the second step in the removal of nitrogen by the

nitrification-denitrification process. The removal of nitrogen in the form of nitrate by
conversion to nitrogen gas can be accomplished biologically under anoxic (without
oxygen) conditions. Conversion of nitrate-nitrogen to a readily removable form, can
be accomplished by the bacteria, namely Achromobacter, Aerobacter, Bacillus and
others. These bacteria are heterotrophs capable of dissimilatory nitrate reduction.
The reactions for nitrate reduction are from nitrate to nitrite, nitric oxide, nitrous
oxide and finally nitrogen gas, which can be discharged to environment.

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 NO3  NO2  NO  N 2 O  N 2

Because of the high cost of external organic carbon sources, processes have been
developed in which the carbon oxidation nitrification/denitrification steps are
combined into a single process, using carbon naturally developed in the wastewater.
The advantages of this process are:
 Reduction in the volume of air needed to achieve nitrification and BOD5
removal.
 Elimination of the need for supplemental organic carbon sources (methanol)
required for denitrification.
 Elimination of intermediate clarifiers and return-sludge systems required in a
staged nitrification/denitrification system.

The process involved in wastewater treatment plant is biological treatment

with activated sludge system. Stream 16 and 19 is first brought to absorber with
pipeline and let the temperature and pressure drop to atmospheric condition which is
1 atm and 27°C. Then, the combined stream is fed to an absorber, where water is
used to absorb gas ammonia from gas nitrogen and hydrogen. Nitrogen and
hydrogen coming out from absorber is recycled to the main production system. The
water-absorbed ammonia is fed into an aeration tank, where either air from
atmosphere is bubbled into the tank or the mechanical surface aerator is used to
saturate the wastewater with oxygen. Microorganisms exist in the aeration tank to
digest the ammonia.

The outlet stream from aeration tank is then being pumped into a clarifier.
Here, the microorganism and suspended particles are given enough time to settle
down. The sludge will be recycled into the aeration tank. The purpose of recycling
the sludge is to maintain the concentration of microorganisms inside the aeration
tank. The effluent from clarifier will be nearly pure water and is safe to discharge
into drainage system.

4.5.4 Material Balance

91
 Here, the material balances are done according to the decomposition of
organic compounds in the aeration tank. Assumption made as the organic compound
is fully degradable by microorganism with long retention time in aeration tank. So,
the effluent from the wastewater treatment will be assume as nearly pure water and
ready to be discharge to public drain. Shown in Table 4.7 is the overall material
balance. Refer Appendix C for further calculation.

Table 4.7: Material balance of biological treatment with activated sludge system
MOLAR FLOWRATE (kmol/hr)
COMPONENT
S16 S19 S21 S22 S23 S24 S25
NH3 0.46492 0.012159 0.47708 0 0 0.47708 0
H2 25.98 0.23984 26.22 0 26.22 0 0
N2 8.5819 0.10946 8.6914 0 8.6914 0 0
Water 0 0 0 515.5017 0 515.5017 515.5017
35.027 0.36146 35.388 515.5017 34.9114 515.9788 515.9788

4.5.5 Energy Balance

Here the energy balance for the waste treatment plant is done. (The boundary
of balance consisted of the absorber, aeration tank and clarifier). The calculation
method is same with the method used in the energy balance in the ammonia
production plant.

Temperature of the plant is assumed to be room temperature, which is 27oC

since the tank is opened to air. Below shows the summary of the energy balance.
Refer Appendix C for further calculation.

Table 4.8 : Energy Balance Activated Sludge System

TOTAL
MOLAR TEMPERATURE ENTHALPY (∆H)
STREAM
FLOWRATE (˚C) (kJ/hr)
(kgmol/h)
S21 35.388 27.00 -9.0720E+04

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 S22 515.5017 27.00 -1.2472E+08
S23 34.9114 27.00 2.0322E+03
S24 515.9788 27.00 -1.2474E+08
S25 515.5017 27.00 -1.24716E+08

Table 4.9 : Heat Duty for Equipment Activated Sludge System

EQUIPMENT HEAT DUTY (kJ/hr)
Absorber 7.0888E+08
Activated sludge system 2.1864E+04

4.6 Summary for Sizing and Costing of Waste Treatment Equipment

The calculation is shown in Appendix C for details.

Table 4.10 : Equipment Sizing Summary In Wastewater Treatment Plant

EQUIPMENT VOLUME,m3 or m3 / d .m POWER , kW
Absorber
Aeration tank 495
Clarifier 48.15
Concrete Pole 2562
Pump 1 0.050
Pump 2 0.0093
Pump 3 0.0091

Table 4.11 : Equipment Costing Summary In Wastewater Treatment Plant

EQUIPMENT UNIT I UNIT PRICE TOTAL PRICE
( RM ) ( RM )
Pump 1 1 22302.60 22302.60
Pump 2 1 12489.40 12489.40
Pump 3 1 12489.40 12489.40
Clarifier 1 19719.70 19,719.70
Filter Press 1 102 600.00 102,600.00
Aeration tank + Concrete Pole 1 206910.00 206910.00
Piping - 17 400.00 17,400.00
Total Price 1137001.10

Table 4.12 : Summary Sheet Ammonia Wastewater Treatment Plant

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SUMMARY SHEET
Identification : Ammonia Wastewater Treatment Plant using activated sludge system
Function : Bio-oxidized organic waste from plant effluent

Specification Data
Design type Activated sludge system
BOD5 inlet 1000 mg/L
BOD5 outlet 20 mg/L
Volumetric flow rate of inlet feed 54.28 m3/d
Operational Parameter Data
Mean cell residence time,  c 10 days
Order of reaction First order
Mixed liquor suspended solids, MLSS 2000 mg/L
Mixed liquor volatile suspend solids, 1500 mg/L (75% of MLSS)
MLVSS 53 hr.
Residence time
Recycle ratio (Recycle stream volumetric 19%
flowrate/Influent volumetric flowrate) 2.4 m3/day
Mass of Sludge produced
Aeration Tank Data
Volume 120 m3
Mixed liquor depth at normal operating 3.0 m
condition 5.0 m
Tank width 8m
Length of tank
Clarifier to separate solid and liquid Data
Tank diameter 1.6 m
Tank width 3.4 m
Air Requirement in aeration tank Data
Volume/day 29.32 kg/day
Oxygen transfer efficiency 8%

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