CHAPTER IV

WASTE TREATMENT FOR ENVIRONMENTAL PROTECTION

4.1 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 saleable 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, as
direct discharge of the unwanted material into the ecosystem will bring about
detrimental effects. 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 of waste treatment plant becomes important with regards to
environmental pollution. Thus, waste treatment is important in order to contribute to
a safe environment.

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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
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:

™ Waste minimization
™ 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 Nanas,
Negeri Sembilan. In this chapter, we will deal with the wastes (liquids and gases)
generated by the ethylene production.

4.2 Regulations

Basically waste treatment plants are non-profitable. Hence, an optimum plant

is needed to apply in order to minimize the expenses occur from the waster treatment
plant. It must be effective too in order to comply with the standard sets by the
authorities. The waste must be treated according to the parameter set as in example.

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Table 4.1: Environment Quality Act 1974

Standard
Parameter
A B
o
Temperature, C 40 40
pH value 6.0-9.0 5.5-9.0
BOD at 20oC,mg/L 20 50
COD, mg/L 50 100
Suspended Solids 50 100
*Environmental Quality (Sewage and Industrial Effluents) Regulations
1978[Regulations 8(1), 8(2), 8(3)] Parameter limits of Effluents of Standard A and B

The wastewater is essentially the water supply of the community after it has
been fouled by a variety of processes. From the standpoint of sources of generation,
waste water may be defined as a combination of the liquid or water carried wasted
removed from the residences, institutions and industrial establishments, together with
groundwater, surface water and other means may be present (Vernick, 1981). If
untreated wastewater is allowed to accumulate, the decomposition of the organic
materials it contains can lead to the production of malodorous gases. In addition,
untreated wastewater usually contains numerous pathogenic microorganisms 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.
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4.2.1 Air Standards

A. 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 is 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 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 Air Quality Standards for six principal pollutants, which are called
“criteria” pollutants. They are listed in Table 4.2. 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 (µg/m3).

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4.2.2 National Ambient Air Quality Standards

Table 4.2: 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 (100µg/m3)** Primary & Secondary
OZONE (O3)
1-hour average* 0.12 ppm (235µg/m3)** Primary & Secondary
8-hour average* 0.18 ppm (157µg/m3)** Primary & Secondary
LEAD (Pb)
Quarterly average 1.5 µg/m3 Primary & Secondary
PARTICULATE < 10 MICROMETERS (PM-10)
Annual Arithmetic Mean 50 µg/m3 Primary & Secondary
24-hour average 150 µg/m3 Primary & Secondary
PARTICULATE < 2.5 MICROMETERS (PM-2.5)
Annual Arithmetic Mean 15 µg/m3 Primary & Secondary
24-hour average 65 µg/m3 Primary & Secondary
SULFUR DIOXIDE (SO2)
Annual Arithmetic Mean 0.03 ppm (80 µg/m3)** Primary
24-hour average 0.14 ppm (365 µg/m3)** Primary
3-hour average 0.50 ppm (1300 µg/m3)** Secondary
Source: Environment Quality Act 1974
* 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.
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4.3 Waste Management

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 lead 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.

Figure 4.1 Hierarchy of Waste Management

The four options of waste management above are more clearly defined as listed
below:

Table 4.3: Four Option of Waste Management

Procedures that either reduce or eliminate the generation of
Source Reduction
hazardous waste before the waste is produced
Reuse of waste stream as an ingredient in a productive
Recycling
process or recovery of a reusable
The use of physical, chemical, biological, or thermal
Treatment technologies to reduce the volume, toxicity and/or mobility of
waste.
The placement of waste into landfill or the underground
Disposal
injection of waste.

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4.4 Waste Minimization

Waste minimization 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 minimized. Waste minimization reduces waste treatment cost and
reduces raw materials costs. Table below is the significant of waste minimization
versus waste treatment.

Table 4.4: Significant of Waste Minimization versus Waste Treatment

The reduction to extent feasible, of any solid or hazardous
Waste Minimization
waste prior to any treatment, storage, or disposal
The dealing of waste by means of certain techniques to
Waste Treatment achieve reduction of volume, toxicity and/or mobility of
waste after the waste has been generated and prior to disposal.

4.4.1 Objective of Waste Minimization

The waste minimization and treatment plant also have to fulfill the following
objective below:

1. Save money by reducing waste treatment and disposal cost, raw material
purchases, and other operating costs including utility costs.
2. Meet state and national waste minimization policy goals.
3. Reduce potential environmental liabilities.
4. Protect public health and workers health.

The summary of waste minimization and pollution prevention is presented in

Figure 4.2.
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Waste Minimization Techniques

Recycling
Source Reduction (Onsite and Offsite)

Product Changes Source Use and Reuse Reclamation

• Product substitution Control
• Return to original • Processed for
• Product conservation
process resource
• Change in product
• Raw material recovery
composition
substitution for • Processed as a
another processes byproduct

Input Material Technology Changes Good Operating

Changes • Process changes Practice
• Material purification • Equipment, piping or • Procedural measure
• Material substitution layout changes.
• Additional automation

Figure 4.2 Waste Minimization Techniques (Besselievre, 1976)

4.4.2 Waste Sources and Effect to Human and Environment

The waste from the plant contains various types of chemical compounds.
This chemical compounds must be ensured to comply with the Malaysia
Environment Quality Act 1974 before discharged to the environment. 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 product or not. Secondly, we have to consider from the safety reason, whether
it is dangerous to the environment or not.

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Specifically there only one stream that contain waste material in this process
that contains gaseous waste. A major chemical manufacturer required a pollution
control system with minimal operational cost to destroy the Hazardous Air Pollutants
by-product. A key issue was system reliability; plant operates 24 hours a day and
only shut down once per year for plant wide preventive maintenance.

In the formaldehyde production process, methanol reacts with air in the

presence of catalyst to produce formaldehyde. Some ancillary compounds are
generated in the oxidation process due to catalyst inefficiencies. The emissions by-
products that require control are carbon monoxide, methanol and unscrubbed
formaldehyde. Both formaldehyde and methanol are classified as Hazardous Air
Pollutants (HAPs) and require stringent emission reduction.

4.4.3 Risks of Exposure

On industrial level, exposure principally occurs in the form of skin contact and
dust or vapor inhalation. Excessive skin contact is easy to avoid, and the risk of
exposure to harmful concentrations of vapor or dust is rather small in practice.
Involuntary exposure to formaldehyde concentrations above 2 ppm (professional
exposure limit in Great-Britian) is improbable because of the low detection threshold
(odor and irritating effect). At 2 ppm, humans do not show any toxic effects.
Chronic exposure of humans to formaldehyde concentrations that cause nasal cancer
with rats (above 10 ppm) is unconceivable.

4.4.4 Exposure Limits

The following table lists the various exposure limits and compliance
requirements for airborne of formaldehyde.
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Table 4.5: Exposure Limits and Compliance Requirements of Formaldehyde

Formaldehyde Type of Limit Exposure Time Compliance
Level (Air) Duration Requirements
≥ 0.1 ppm Exposure Any period of Specific
Threshold time information/training about
formaldehyde
≥ 0.5 ppm “Action” limit 8-hour time- Above plus: medical
(AL) weighted surveillance; periodic
average exposure monitoring.
≥ 0.75 ppm Permissible 8-hour time- Above plus: establish and
Exposure Limit weighted post regulated areas;
(PEL) average respiratory protection;
establish engineering and
work practice controls to
lower exposures below
PEL, as feasible.
≥ 2 ppm Short-term 15-minute time- As above or PEL
Exposure Limit weighted
(STEL) average

4.5 Regulation Regarding Formaldehyde

9 Under the authority of the Federal Hazardous Substances Act, the Consumer
Product Safety Commission requires warning labels on household products
containing 1% or more of formaldehyde. It has also banned the use of urea-
formaldehyde foam insulation in residences and schools.
9 The Occupational Safety and Health Administration (OSHA) issues
permissible exposure limits for formaldehyde and regulates formaldehyde
under the Hazard Communication Standard and as a chemical hazard in
laboratories.
9 EPA regulates formaldehyde under the Clean Air Act; Clean Water Act;
Comprehensive Environmental Response, Compensation, and Liability Act

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(Superfund); Food, Drug, and Cosmetic Act; Resource Conservation and

Recovery Act; Superfund Amendments and Reauthorization Act; and Toxic
Substances Control Act.
9 EPA has designated formaldehyde as a hazardous air pollutant, water
pollutant, waste constituent, and inert ingredient of pesticide products.
9 Under Section 313 of the Emergency Planning and Community Right to
Know Act of 1986, releases of more than one pound of formaldehyde into the
air, water, and land must be reported annually and entered into the Toxic
Release Inventory (TRI).
9 Under Section 302 of the Emergency Planning and Community Right-to-
Know Act of 1986, formaldehyde is listed as an Extremely Hazardous
substance and has a threshold planning quantity of 500 pounds.
9 Facilities having a threshold quantity of 15000 pounds of formaldehyde are
subject to the Risk Management Program Rule (RMP), Section 112r of the
Clean Air Act. The RMP toxic endpoint for formaldehyde is 0.012 mg/L -
basis ERPG-2.
9 OSHA lists formaldehyde as a highly hazardous chemical under the Process
Safety Management Standard at a threshold quantity of 1000 pounds.

4.6 Formaldehyde Air Pollution Problem

A major chemical manufacturer required a pollution control system with

minimal operational cost to destroy the hazardous air pollutant (HAP) by-products of
a formaldehyde production process. A key issue was system reliability; the plant
operates 24 hours a day and only shuts down once per year for plant-wide preventive
maintenance.

Volatile organic compounds (VOCs) can make up a major class of air

pollutants. This class includes pure hydrocarbons, but also partially oxidized
hydrocarbons (organic acids, aldehydes, ketones), as well as organics containing
chlorine, sulfur, nitrogen, or other atoms in molecule. Emissions from the
formaldehyde plant consist of gaseous of formic acid, water, nitrogen, oxygen,
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carbon monoxide and also VOCs; formaldehyde and methanol. Below is the stream
summary of the gas emissions, which is stream 20.

Table 4.6: Stream 20 components flow rate summary

Components Flow rate (kg/hr)
Methanol 0.0000
Formic Acid 0.0349
Formaldehyde 27.7638
Water 0.0024
Oxygen 1061.2230
Nitrogen 5709.0410
Carbon Monoxide 0.6822
Total 6798.7473

One method of pollution control that can be applied broadly to VOCs is

incineration. Incineration can be used for odor control, to destroy a toxic compound,
or simply to reduce quantity of photochemically reactive VOCs released to the
atmosphere.

4.7 Waste Gas Treatment

Incineration or combustion is chosen to treat the gaseous waste. It is deemed

the most appropriate disposal method for these gaseous wastes (Kroschwitz, 1985)
since the organic compounds in these streams can rapidly oxidize at high
temperature. The latter differs from the former in that is it involves recovery of
energy in the form of heat generated from the process. Decision to either operate the
unit as an incinerator or combustor weighs heavily on economic scale, with
unprofitable energy recovery not uncommon due to the high capacity and operating
costs of auxiliary equipment. Flare or incinerator, from a different point of view is
used to minimize the emission of toxic and dangerous substances as it is designed to
push the reaction as close as possible to completion, leaving a minimum of unburned

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compounds (Peavy et al, 1985). Generally, there are four basic types of gas
incineration system:

™ Direct Flame Incineration

™ Flares
™ Catalytic Incineration
™ Thermal Incineration

4.7.1 Combustion Properties

The efficiency of combustion is related to the combination of three factors,

the “three – T’s” :

™ Temperature in the furnace

™ Time residence of the combustion products at the furnace temperature
™ Turbulence within the furnace

In general a solid or liquid must be converted to gaseous phase before

burning will occur. (Examine a lit match or a burning log. The flame does not rise
directly from the solid. There is a zone immediately above the match, or log, where
the gaseous fuel phase has been generated and is mixing with combustion air prior to
burning). The three T’s are factors, which control the rapidity of conversion of solid
and liquid fuel to the gaseous phase.

For complete combustion, the oxygen must come into intimate contact with
the combustible molecule at sufficient temperature and for a sufficient length of time
for the reaction to be completed. Incomplete reactions may result in the generation
of aldehydes, organic acids, carbon and carbon monoxide.

There are few advantages and disadvantages of the combustion system. It is

summarized in the table below.
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Table 4.7: Advantages and Disadvantages of Combustion System

(Source: Perry’s Chemical Engineering Handbook, Waste Management, page 25-31)

4.7.2 Direct Flame Incineration

In direct flame incineration, waste gases are burned directly in a combustor

with or without the addition of a supplementary fuel. In some cases, heat value and
oxygen content of the waste gases are sufficient to allow them to burn on their own.
More often than not, the introduction of air or the addition of a small amount of fuel
will bring the gaseous mixture to its combustion point.

Direct flame incinerator, also refers to as fume incinerators and gas

combustors, which consists of chambers provided with supplemental fuel burners
which provide heat and retention time to destroy gaseous waste materials (Brunner,
1984). The desired combustion chamber temperature is maintained by altering the
rate of supplementary fuel entering the furnace as controlled by appropriate control
circuit. Its primary use being for odor control, toxicity elimination or visible
emissions, these incinerators are applicable for most gaseous waste.

However this treatment is not suitable for waste stream that contains high
concentration of nitrogen due to the inevitable forming of nitrogen oxides (NOx)
resulted from high temperature burning for sufficiently long period of time. Thermal

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NOx forms at temperatures well above1600K (Davis and Cornwell,1998). The

configuration of this equipment lends itself to heat recovery at which two modes are
existent. In one case, a heat exchanger utilizes the high temperatures in combust
exhaust to preheat the incoming combustion air. The second case, on the other hand,
consists of a heat exchanger heating a stream for external use, which can be gas or
water to steam.

In normal operation, incinerator is designed for complete destruction of

organic components by incineration, with particulate matter discharges almost
nonexistent. Where other components are present in the gas such as sulfur or
halogen, scrubber will usually be required.

Figure 4.3: Direct Flame Incinerator

(US EPA 670/2-73-053C, August 1973)

4.7.3 Flares

Flares can be considered a low cost means disposal of relatively large

amounts of gas containing combustible components; they are suited to processes,
which are not continuous. Continuous gas generation often lends itself towards heat
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recovery. Flares handle process upset and emergency gas releases that the base load
system is not designed to recover. Flare technique cannot be used for heat recovery.
It also can be used for controlling almost any VOCs emission stream. They can be
designed and operated to handle fluctuations in emission VOC content, inerts content
and flow rate. Flares are mostly used for the disposal of hydrocarbons.

Flares use open flames for disposing of waste gases during normal operation
and emergencies. They are typically applied when the heating value of the waste
gases cannot be recovered economically because of the intermittent or uncertain
flow, or when process upsets occur. In some cases, flares are operated in conjunction
with base load gas recovery systems. Flares handle process upset and emergency gas
releases that the base load system is not designed to recover. In most flares,
combustion occurs by means of a diffusion flame. A diffusion flame is one in which
air diffuses across the boundary of the fuel combustion product stream toward the
center of the fuel flow, forming the envelope of a combustible gas mixture around a
core of fuel gas. This mixture, on ignition, establishes a stable flame zone around the
gas core above the burner tip. This inner gas core is heated by diffusion of hot
combustion products from the flame zone.

There are several types of flares, the most common of which are steam-
assisted and pressure head flares. Steam-assisted flares are very common and
typically employed in cases where large volumes of waste gases are released. Air-
assisted flares are generally used for moderate relief gas flows. Pressure head flares
are small; they are used in arrays of up to 100 individual flares. Normally, only a
few of the flares operate. The number of flares operating is increased as the gas flow
increases.

Typically flare operations can be classified as ‘smokeless’, ‘non -smokeless ‘,

‘fired’ or ‘endothermic’. For smokeless operation, flares use outside momentum
sources (usually steam or air) to provide efficient gas/air mixing and turbulence for
complete combustion. Smokeless flaring required for destruction of organics heavier
than methane. Non-smokeless operation is used for organic or other vapor streams,
which burn readily and do not produce smoke. Fired or endothermic flaring required

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additional energy in order to ensure complete oxidation of the waste stream such as
for sulfur tail gas and ammonia waste streams.

There are two types of flares are currently in use, namely the ground level
and elevated or tower flares. Ground flares can be used where there is sufficient
space around the flare to provide for safety of personnel and equipment. The tower
flare is more preferred choice where space is limited as it keeps the flame above the
level of surrounding equipment and personnel, as well as to promote the dilution of
its products of combustion into the air. Temperature developed in flare system
normally ranges from 1100-1370°C (Brunner,1984). Figure 4.4 below shows the
typical Steam-Assisted Flare System.

Figure 4.4 Typical Steam-Assisted Flare System (US EPA Handbook, Sept. 1986)

A typical stream-assisted flare system off-gases enter the flare through the
collection header. When water or organic droplets are present, it may be necessary
to pass the off-gases through a knock-out drum, since these droplets can create
problems. Water droplets can extinguish the flame and organic droplets can result in
burning particles. Once the off-gas enter the flare stack, flame flashback can occur if
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the emission stream flow rate is too low. Flashback may be prevented, however,
by passing the gas through a gas barrier, a water seal, or a stack seal. Purge gas is
another option.

At the flare tip, the emission stream is ignited by pilot burners. If conditions
in the flame zone are optimum (oxygen availability, adequate residence time, etc.),
the VOCs in the emission stream may be completed burned (~100% efficiency). In
some cases, it may be necessary to add supplementary fuel (natural gas) to the
emission stream in order to achieve destruction efficiencies of 98% and greater if the
net heating value of the emission stream is less than 300 Btu/scf.

I. Steam-Assisted Flare

Steam-assisted flare is a single burner tip, elevated above ground level for
safety reasons the burn the vented gas in essentially a diffusion flame. They
reportedly account for the majority of the flares installed and are the predominant
flare type found in refineries and chemically plants (Guide for Pressure-relieving and
Depressurizing Systems, 1982). To ensure an adequate air supply and good mixing,
this type of flare system injects steam into the combustion zone to promote
turbulence for mixing and to induce air into the flame. Steam is provided for a
number of reasons, as follows (Brunner):

™ To generate turbulence and momentum, promoting good mixing with the

surrounding air.
™ As a source of heat to help in cracking complex molecules within the gas
stream,
™ As a reactant in the combustion process to help oxidize carbon to a gases
state, simplified as:
ƒ C + H2O (steam) CO + H2

The CO and H2 produced will readily combust burning clean in the presence
of air.

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II. Air-Assisted Flares

Some flares use forced air to provide the combustion air and the mixing
required for smokeless operation. These flares are built with a spider-shaped burner
(with many small gas orifices) located inside but near the top of a steel cylinder two
feet or more in diameter. Combustion air is provided by a fan in the bottom of the
cylinder. Varying the fan speed can vary the amount of combustion air. The
principal advantage of the air-assisted flares is that they can be used where steam is
not available. Although air assist is not usually used on large flares (because it is
generally not economical when the gas volume is large) the number of large air-
assisted flares being built is increasing.

III. Non-Assisted Flares

The non-assisted flare is just a flare tip without any auxiliary provision for
enhancing the mixing of air into its flame. Its use is limited essentially to gas
streams that have low heat content and a low carbon/hydrogen ratio that burn readily
without producing smoke (USEPA, 1990). These streams require less air for
complete combustion, have lower combustion temperatures that minimize cracking
reactions, and more resistant to cracking.

IV. Pressure-Assisted Flares

Pressure-assisted flares use the vent stream pressure to promote mixing at the
burner tip. Several vendors now market proprietary, high-pressure drop burner tip
design. If sufficient vent stream pressure is available, these flares can be applied to
streams previously requiring steam or air –assist for smokeless operation. Pressure-
assisted flares generally (but nor necessarily) have the burner arrangement at ground
level, and consequently, must located in a remote area of the plant where there is
plenty of space available. They have multiple burner heads that are staged to operate
based on the quantity of gas released. The size, design, number and group
arrangement of the burner heads depend on the vent gas characteristics.
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V. Enclosed Ground Flares

An enclosed flare’s burner heads are inside a shell that is internally insulated.
This shall reduce noise, luminosity and heat radiation and also provides wind
protection. A high nozzle pressure drop is usually adequate to provide the mixing
necessary for smokeless operation and air or steam is not required. In this context,
enclosed flares can be considered a special class of pressure assisted or non-assisted
flares. The height must be adequate for creating enough draft to supply sufficient air
for smokeless combustion and for dispersion of the thermal plume. These flares are
always at ground level.

4.7.4 Catalytic Incineration

Catalytic incineration is another method available when combustible

materials in the waste gas are too low to make direct-flame incineration feasible. It
is normally used to destroy waste at low concentrations, less than 25 % of the lower
explosive limits (Brunner,1984).

Factors that affect the performance of a catalytic incinerator includes

operating temperature, space velocity, volatile organic compounds composition and
concentration, catalyst properties and finally the presence of poisons /inhibitors in
the emission stream. The important variables are the operating temperature and
space velocity (defined as the volumetric flow rate of the combined gas stream).

A catalytic incinerator generally consists of a preheating section and a

catalytic section. However, cold catalytic systems are now available that operates at
ambient temperature, eliminating the need for pre-heater. The combustion catalyst
consists of basic material, such as activated alumina, impregnated with a metallic
compound. The catalyst has the property of increasing the rate of oxidation at lower
temperatures that is the use of catalyst promotes destruction of gaseous waste at
lower temperature. Catalysts that are normally used are palladium and metal oxides.
The gas stream must be free of particulate matter to avoid the fouling of catalyst.

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Thus, pretreatment of gas in the form of cyclonic separation or electrostatic

precipitation, may be necessary upstream of the catalyst is needed.

A fan is located after burner housing to mix the gases and to distribute them
evenly over the catalyst. Supplemental fuel usage for catalyst incinerator is generally
lower than for thermal incinerators, thus reducing operating costs.

As with direct flame incineration, cost of heat exchange equipment is often

more than offset the savings in supplemental fuel consumption. Investment in larger
heat exchangers will obviously increase the rate of heat recovery. Due to its high
cost of maintenance and catalytic poisoning, this system is usually not preferred.

Figure 4.5: Schematic Diagram of Catalytic Incinerator System

(US EPA Handbook, Sept. 1986)

4.7.5 Thermal Incineration

Thermal incinerator is used when the concentration of combustible materials

is too low to make direct-flame. It is widely used as an air pollution control
technique whereby organic vapors are oxidized at high temperatures.
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The most important variables to be considered in the design of this system are
the combustion temperature and residence time since they determine the incinerator’s
destruction efficiency (DE). Thermal incinerator can achieve a wide range of
destruction efficiency, with a DE of 98 – 98+ % not uncommon (US EPPA
Handbook, September 1986).

The waste is preheated, often by the use of a heat exchanger utilizing heat
produced by the thermal incinerator itself. The preheated gas is directed into a
combustion zone equipped with a burner supplied with fuel. The temperature of
operation depends upon the nature of the pollutants in the waste gas. A thermal
incinerator requires a strict design for safe and efficient operation.

Thermal incinerator, as complex as its name sounds, requires stringently

careful design for provide safe, efficient operation. The three T’s of combustion
(time, temperature, turbulence) and oxygen level must be carefully monitored to
prevent the production of PIC (products of incomplete combustion). Ideally, the
relatively clean stream of hot air produced is used as heat source for other operations
within the industrial plant and offers the potential to be further incorporated into the
Heat Exchanger Network (HEN) for maximum recovery of heat.

Emission Source

Dilution Air Scrubber

Combustion Air Thermal

Stack
Supplementary Incinerator
Fuel Heat
Exchanger

Figure 4.6 Schematic Diagram of A Thermal Incinerator System (US EPA

Handbook Sept 1986)

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4.8 Treatment Process selection: Steam-Assisted Flare

After taking all the considerations, our group has decided to apply steam-
assisted flare system in our gas waste treatment and control. Flaring is chosen since
the waste stream consists of hydrocarbons. Besides the quantity of waste is little, the
cost of treatment plant is cheaper and is more economic compared to treatment by
catalytic incinerator. Besides, it is safe and enough to handle the waste.
Elevating the flare can prevent potentially dangerous condition at ground
level where the open flame (i.e. an ignition source) is located near a process unit.
Further, the products of combustion can be dispersed above working areas to reduce
the effects of noise, heat, smoke and objectionable odors. As in all combustion
processes, an adequate air supply and good mixing are required to complete
combustion and minimize smoke. The various flare designs primarily in their
accomplishment of mixing.

The difference of incineration and flaring is discussed and summarized in

Table 4.8 below.

Table 4.8: Difference between Incineration and Combustion System

Incineration Flaring
High efficiency (99.95% destruction) Efficiency depends on mixing in flare tip
(Usually 98% destruction)
Smaller design Flare stacks are usually > 30 ft
Could be used to destroy toxic substances Strictly for VOCs
Expensive (usually > RM 1 million) Cheaper cost

The element of an elevated steam assisted flare generally consist of gas vent
collection piping, utilities (fuel, steam and air), piping from the base up, knock out
drum, liquid seal, flare stack, gas seal, burner tip, pilot burners, steam jets ignition
system and controls.
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4.8.1 Gas Transport Piping

Process vent stream is sent from the facility release point to the flare location
through the gas collection header. The piping generally schedule 40 carbon steel is
designed to minimize pressure drop. Ducting is not used as it more prone to air
leaks. Valving should be kept to an absolute minimum and should be ‘car sealed’
open. Pipe layout is designed to avoid any potential dead legs and liquid traps. The
piping is equipped for purging so that explosive mixtures do not occur in the flare
system either on start up or during operation. There are 3 option of seal can be
obtained in flare system which is:
™ Molecular seal
™ Liquid seal
™ Velocity seal

In some situations, a flame or detonation arrestor is preferred or necessary. If

a liquid seal cannot be used, gases are in the explosive range, and/or there are
extended pipe runs or bends in pipe, a detonation arrestor may be used.

4.8.1.1 Liquid Seal

Process vent streams are usually passed through a liquid seal before going to
the flare stack. The liquid seal can be downstream of the knock out drum or
incorporated into the same vessel. This prevents possible flame flashbacks, caused
when air is inadvertently introduced into the flare system and the flame front pulls
down into the stack. The liquid seal also serves to maintain a positive pressure on
the upstream system and acts a mechanical damper on any explosive shock wave in
the flare stack. Purge gas also helps to prevent flashback in the flare stack caused by
low vent gas flow.

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4.8.1.2 Gas Seal

Air may tend to flow back into a flare stack due to wind or the thermal
contraction of stack gases and create an explosion potential. To prevent this, a gas
seal is typically installed in the flare stack. One type of gas seal is located below the
flare tip to impede the flow air back into the flare gas network. There also ‘seals’
which act as orifices in the top of the stack to reduce the purge gas volume for a
given velocity and also interfere with the passage of air down to stack from the upper
rim. These are known by name ‘internal gas seal, fluidic seal and arrestor seal’.
These seals are usually proprietary in design and their presence reduces the operating
purge gas requirements.

Figure 4.7 Flame or Denotation Arrestor

4.8.2 Knock Out Drum

Knockout drums are provided in situations where liquid separation is likely in

the waste stream. The knockout drum will collect any liquids that are present in the
waste stream prior to entering the flare system. A knockout drum is especially
important if substantial cooling of heavy liquids is expected. If the liquid is
corrosive, non-corrosive materials of construction can be used. A level gauge and
drain connections are built into the knockout drum. The knock out or disentrainment
 4-26

drum typically either horizontal or vertical vessel located at or close to the base of
the flare, or a vertical vessel located inside the base of the flare stack.

Figure 4.8 Vertical Knock Out Drum

Liquid in the vent stream can extinguish the flame or cause irregular
combustion and smoking. In addition, flaring liquids can generated a spray of
burning chemicals that could reach ground and create a safety hazard. For flare
system designed to handle emergency process upsets this drum must be sized for
worst case condition (e.g. loss of cooling water or total unit depressurizing) and is
usually quite large. For a flare system devoted only to vent stream VOC control, the
sizing of the drum is based on vent gas flow with consideration given to liquid
entrainment.

4.8.3 Flare Stack

For safety reason a stack is used to elevate the flare. The flare must be
located so that it does not present a hazard to surrounding personnel and facilities.
Elevated flare can be self-supported (free standing), Guyed Wired stack, or
structurally supported by a Derrick.

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Self-supporting flares are generally used for lower flare tower heights (30ft –
100 ft) but can be designed for up to 250 ft. Guy tower are designed for over 300 ft,
while Derrick towers are designed for above 200 ft. Freestanding flares provide
ideal structural support. However, for very heights units the cost increases rapidly.
In addition, the function required and nature of the soil must be considered. Derrick
supported flares can be built as high as required since the system load is spread over
the Derrick structure. Derrick supported flares are the most expansive design for a
given flare height. The guy supported flare is the simplest of all the support
methods. However considerable amount of land is required since the Guy Wire are
widely spread apart. A rule of thumb for space required to erect a guy supported
flare is a circle on the ground with a radius to the height of the stack.

Figure 4.9 Self-Supported Flare

4.8.4 Burner Tip

The burner tip or flare tip is designed to give environmentally acceptable

combustion of the vent gas over the flare system’s capacity range. The burner tips
are normally proprietary in design. Consideration is given to flame stability, ignition
reliability and noise suppression. The maximum and minimum capacity of a flare to
burn a flare to burn a flared gas with a stable flame is a function of tip design. Flame
holder retention devices incorporated in the flare tip inner circumference can enhance
flame stability. Burner tips with modern flame holder designs can have a stable
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flame over a flare gas exit range of 1 to 600 ft/s. The actual maximum capacity of a
flare tip is usually limited by the vent stream pressure available to overcome the
system pressure drop. Elevated flares diameters are normally sized to provide
vapour velocities at maximum throughput of about 50% of the sonic velocity of the
gas subject to the constraints of CFR 60.18.

Figure 4.10 Flare Tip Detailed Design

4.8.5 Steams Jet

A diffusion flame receives its combustion oxygen by diffusion of air into the
flame from the surrounding atmosphere. The high volume of fuel flow in a flare may
require more combustion air at a faster rate than simple gas diffusion can supply.
High velocity steam injection nozzles, positioned around the outer perimeter of the
flare tip, increase gas turbulence in the flame boundary zones, drawing in more
combustion air and improving combustion efficiency. For the large flares, steam can
also inject concentrically into the flare tip. The injection of steam into a flare can
produce other results in addition to air entrainment and turbulence.
Briefly, one theory suggests that steam separates the hydrocarbon molecule,
thereby minimizing polymerization and form oxygen compounds that burn at a
reduced rate and temperature not conductive to cracking and polymerization.

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Another theory claims that water vapour reacts with the carbon particles to form CO.
CO2 and H2, thereby removing the carbon before it cools and form smoke. An
additional effect of the stream is to reduce the temperature in the core of the flame
and suppress thermal cracking. The physical limitation on the quantity of steam that
can be delivered and injected into the flare flame determines the smokeless capacity
of the flare. Smokeless capacity refers to the volume of gas that can be combusted in
a flare without smoke generation. The smokeless capacity is usually less than stable
flame capacity of the burner tip.

4.8.6 Pilot and Ignition System

Pilots and ignition systems in the market now are proven to be reliable, fast,
and easy to operate and maintain. The pilots are designed for continuous and
intermittent use in adverse weather conditions and extreme wind speeds. The pilots
also increase the reliability and performance of the flare system by providing flame
stability in any operating conditions.

Pilot and ignition designs can extremely energy efficient pilots using as
little as 50SCFH of fuel gas. The pilots also can are generally fabricated out of
309/310 stainless steel to extend the life of the pilot burner assembly. An air/fuel
gas mixer attached to pilot burner assembly allows for a combustible mixture of
pilot fuel gas at the pilot burner tip. The local control panel powers the ignition
transformers and automatically ignites/re-ignites the pilots.
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Ignition of the pilot can be done via:

™ Manual Ignition - the pilot is manually ignited via a push-button

activation.

™ Auto Ignition - a spark-igniting device and ignition transformer

ignites the flame front.

™ Auto Re-Ignition - the flare tip pilot temperature switches

automatically trigger the ignition transformers to re-ignite the flare
tip pilots upon loss of flame.

™ Remote Ignition - the flare system to be capable of automatic start

up and shutdown based on either local or remote initiation.

Ignition of the pilots is accomplished using one of three methods:

™ Flame Front Generator (FFG)

™ Self-Inspirited Flame Front Generator (SI-FFG)

™ Electric Spark Ignition (EFG)

4.8.7 Control

Flare system control can be completely automated or completely manual.

Components of a flare system, which can be controlled automatically, include the
auxiliary gas, steam injection and the ignition system. Fuel gas consumption can be
minimized by continuously measuring the vent gas flow rate and heat content and
automatically adjusting the amount of auxiliary fuel to maintain the requires
minimum of 300 Btu/scf for steam assisted flare. Controlling flow based on vent gas
flow rate can likewise minimize steam consumption. Steam flow can also be
controlled using visual smoke monitors. Automatic ignition panels sense the
presence of a flame with either visual or thermal sensors and reignite the pilots when
flameouts occur.

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Table 14.8: Design Specification Sheet of Flare

DESIGN SPECIFICATION SHEET

Identification item: FLARE
No. required: 1
Type: Steam-Assisted Elevated Flare System
Date: 07-Feb-05 By: Noor Fazira Ab Aziz
Function: To burn gaseous waste
Material of construction: Carbon Steel
Flare tip diameter, D 4.54 in = 0.115 m
Flare height, L 30 ft = 9.144 m
Purge gas requirement, FPu 139.32 Mscf/yr
Steam requirement, S 5.25202 x 106 lb/yr = 2.38228 kg/yr
Pilot gas requirement, FPi 613 scf/yr = 17.368 m3/yr
No. of burners, N 1
Knock-out drum:
(a) Maximum design vapour velocity, U 0.7721 ft/s = 0.2353 m/s
(b) Minimum vessel cross sectional area, A 1.4338 ft2 = 0.1332 m2
(c) Minimum vessel diameter, d 22 in = 0.5588 m
(d) Vessel thickness, t 0.25 in = 0.00635 m
(e) Vessel height, h 66 in = 1.6764 m

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4.9 Equipment capital cost

To calculate the flare equipment cost, it has been divided into three section
cost calculation. This consists of flare cost, vent stream piping cost and also knock
out drum cost which lead to total cost of flare system equipment. The calculation
can be refer at the appendix and below is given the summary of the flare cost.

Table 4.9: Summary of Flare Cost

Cost Item Cost (RM)
Flare Cost, CF 76 192.128
Vent Stream Piping Cost, CP 2978.34
Knock-out Drum Cost, CK 4959.00
Flare System Equipment Total Cost, EC 84 129.47

4.10 Formic Acid Waste Storage Tank

The calculation to obtain sizing and costing of formic acid waste storage tank
is shown in D.5 Appendix IV. Below is the summary of the sizing and costing of the
storage tanks.

Table 4.10: Summary of Sizing and Costing Storage Tank

Item Value
Diameter 0.309 m
Length 1.235 m
Volume 0.0927 m3
Cost RM 33 856.30
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4.10.1 Waste Treatment For Formic Acid

From Material Safety Data Sheet (MSDS) , whatever formic acid cannot be
saved for recovery or recycling should be handled as hazardous waste and sent to a
waste management center to approved waste facility. As for this reason, the formic
acid, which has been through ion exchange process, will be collect and store in
plastic drum with bunghole before it can be treat. Toxicol Sdn Bhd Sdn Bhd is
appointed by Kualiti Alam (KA) as its sole marketing agent for the collection and
transportation of Scheduled Wastes in Malaysia and International Areas. The formic
acid waste will be collected by Toxicol Sdn Bhd at Sabah branch which is located at
Kota Kinabalu, Sabah.. They will do the proper physical and chemical treatment.

From the Table 4.10, formic acid is classified as inorganic waste to Kualiti
Alam code.

Table 4.10: Waste Classification Code (Source:www.kualitialam.com.my)

Group Waste Type

MINERAL OIL WASTE
A
Waste containing lubricating oil, hydraulic oil, oil contaminated soil etc.
ORGANIC CHEMICAL WASTE CONTAINING HALOGENS AND/OR >SULPHUR
B 1%
Freon, PVC wastes, chloroform, solvents, capacitors and transformers containing PCB etc.
WASTE SOLVENTS CONTAINING HALOGENS AND/OR SULPHUR < 1%
C Acetone, alcohol(eg.ethanol, methanol), benzene, turpentine, xylene etc. Waste should be
pumpable, containing< 50% water and 18J/kg calorific value.
ORGANIC CHEMICAL WASTE CONTAINING HALOGENS AND/OR SULPHUR <
H 1%
Glue, latex, paint, phenol, printing ink, synthetic oil, soap, epoxy etc.
WASTE CONTAINING MERCURY
K
Mercury, vapour lamps, COD-fluids, mercury batteries etc.
PESTICIDE WASTE
T
Insecticides, fungus and weed killers, rat poison etc.
INORGANIC WASTE
X Acid, alkaline, sodium hypochorite, inorganic salts, metal hydroxide sludge, chromate, and
cyanide waste etc.
MISCELLANEOUS
Z
Medicine waste, lab-packs, asbestos waste, mineral sludge, isocyanate(MDI,TDI), batteries etc.

Total amount of formic acid waste in a year:

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0.0349kg m 3 24hr 1000 L

= x x330daysx
hr 1226kg 1day 1m 3
= 225.455 L

Kualiti Alam’s charge of inorganic waste for physical/chemical treatment: (refer

Appendix IV)
RM 1620 for 200 Litre Drum

∴Thus, the charges of treatment per year:

RM 1620
= 225.455litre x
200litre
= RM 1826.19 per year

4.11 Total Cost for Waste Treatment

Table 4.11 concludes the entire total cost for treat the waste in our
Formaldehyde plant.

Table 4.11: Total Cost for Waste Treatment

Cost Item Cost (RM)
Flare system equipment 84 129.47
Formic acid waste storage tank 33 856.30
Waste treatment for formic acid 1826.19
Total cost 119 811.96