INTRODUCTION

Petroleum industry is one of the largest industries in the world and a

vital part of the world’s largest economy. Petroleum as an energy
source use is a necessary part of the modern world and will be a
primary source of energy for the next several decades. The
petrochemicals sector is a major segment of manufacturing industry as
it has several connections with other sectors of an economy. However,
potential environmental hazards associated with refineries have caused
increased concern for communities. Furthermore, the capacity of the
environment to absorb the effluents and other impacts of process
technologies is not unlimited and the environment should be
considered to be an extremely limited resource, and discharge of
chemicals into it should be subject to severe constraints.

Air pollution and air quality impacts have

been studied for many years now, and there are significant concerns
around the world to varying degrees. These air pollutants can have a
wide array of public health impacts, such as increasing the rate of
certain cardiovascular (heart) and pulmonary (lung) diseases, cancers,
and strokes. This has led to the creation of Air Quality Indices (AQI),
which are used to analyze the severity of air pollution and the level of
risk to health, arising from particulate and gaseous air pollution.
Though air quality management has been somewhat successful in
developed nations, there is further room for improvement. In the case
of developing nations, increased energy demands, industrialization and
population growth call for better air quality management.
A variety of indices have been in use in various regions around the
world. For instance, the Pollutant Standards Index (PSI) established by
the United States Environmental Protection Agency (US EPA), the
Common Air Quality Index in European countries, and the Air Quality
Health Index in Canada, to name a few . Many countries follow the AQI
established by US EPA with an assigned value of 0 to 500, and it can be
divided into the categories.

AQI Values Levels of Health Concern

0–50 Good

51–100 Moderate

101–150 Unhealthy for Sensitive Groups

151–200 Unhealthy

201–300 Very Unhealthy

301–500 Hazardous

The AQI can also signify the exposure of people to pollutants, which
although the pollutants are mainly outdoors can also affect the indoor
environment.
 Environmental Hazards of
Petroleum Refineries

Environmental hazards of petroleum refineries Refineries are generally

considered a major source of pollutants in areas where they are located
and are regulated by a number of environmental laws related to air,
land and water. Some of the regulations that affect the refining industry
include the Clean Air Act, the Clean Water Act, the Safe Drinking Water
Act, CERCLA (i.e.Comprehensive Environmental Response,
Compensation, and Liability Act), Emergency Planning and Community
Right-to-Know (EPCRA), OSHA (Occupational Safety & Health
Administration), TSCA (Toxic Substances Control Act), Oil Pollution Act
and Spill Prevention Control and Countermeasure Plans. Here is a
breakdown of the air, water, and soil hazards posed by refineries:

Air pollution hazards

Petroleum refineries are a major source of hazardous and toxic air
pollutants such as BTEX compounds (benzene, toluene, ethylbenzene,
and xylene). They are also a major source of criteria air pollutants:
particulate matter (PM), nitrogen oxides (NOx), carbon monoxide (CO),
hydrogen sulfide (H2S), and sulfur dioxide (SO2). Refineries also release
less toxic hydrocarbons such as natural gas (methane) and other light
volatile fuels and oils.

Some of the chemicals released are known or suspected cancer-causing

agents, responsible for developmental and reproductive problems.
They may also aggravate certain respiratory conditions such as
childhood asthma. Along with the possible health effects from exposure
to these chemicals, these chemicals may cause worry and fear among
residents of surrounding communities. Air emissions can come from a
number of sources within a petroleum refinery including: equipment
leaks (from valves or other devices); high-temperature combustion
processes in the actual burning of fuels for electricity generation; the
heating of steam and process fluids; and the transfer of products.

Many thousands of pounds of these pollutants are typically emitted

into the environment over the course of a year through normal
emissions, fugitive releases, accidental releases, or plant upsets. The
combination of volatile hydrocarbons and oxides of nitrogen also
contribute to ozone formation, one of the most important air pollution
problems in the United States.

Water pollution hazards

 Refineries are also potential major contributors to ground water and
surface water contamination. Some refineries use deep-injection wells
to dispose of wastewater generated inside the plants, and some of
these wastes end up in aquifers and groundwater. These wastes are
then regulated under the Safe Drinking Water Act (SDWA). Wastewater
in refineries may be highly contaminated given the number of sources it
can come into contact with during the refinery process (such as
equipment leaks and spills and the desalting of crude oil).

This contaminated water may be process wastewaters from desalting,

water from cooling towers, stormwater, distillation, or cracking. It may
contain oil residuals and many other hazardous wastes. This water is
recycled through many stages during the refining process and goes
through several treatment processes, including a wastewater treatment
plant, before being released into surface waters.

The wastes discharged into surface waters are subject to state

discharge regulations and are regulated under the Clean Water Act
(CWA). These discharge guidelines limit the amounts of sulfides,
ammonia, suspended solids and other compounds that may be present
in the wastewater. Although these guidelines are in place, sometimes
significant contamination from past discharges may remain in surface
water bodies.

Soil pollution hazards

Contamination of soils from the refining processes is generally a less
significant problem when compared to contamination of air and water.
Past production practices may have led to spills on the refinery
property that now need to be cleaned up. Natural bacteria that may
use the petroleum products as food are often effective at cleaning up
petroleum spills and leaks compared to many other pollutants.

Many residuals are produced during the refining processes, and some
of them are recycled through other stages in the process. Other
residuals are collected and disposed of in landfills, or they may be
recovered by other facilities. Soil contamination including some
hazardous wastes, spent catalysts or coke dust, tank bottoms, and
sludges from the treatment processes can occur from leaks as well as
accidents or spills on or off site during the transport process.

Air Pollution from Petroleum and

Oil refineries
Refineries and petrochemical industries are one of the contributing
sources to the degradation of air quality, by releasing various pollutants
like Volatile Organic Compounds (VOCs) into the surrounding
environment.

Oil refineries convert crude oil into a vast array of products, requiring a
range of operations that emit a variety of pollutants, both through
normal operations and in accidents.

Six major pollutants produced directly or indirectly by burning fossil

fuels (in addition to other human activities) are required by law to be
regulated by the EPA under the Clean Air Act: Carbon monoxide (CO),
Nitrogen oxides (NOx ), Sulfur oxides (SOx ) Ozone (O3 ), Particulate
Matter (PM), and Lead (Pb). To be specific:

1.Nitrogen dioxide

2. Sulfur dioxide

3. Particulate matter (PM10, PM2.5)

4. Volatile organic compounds

5. BTX compounds.

6. Moderate percentage of carbon monoxide

The EPA and states also set standards for 187 other “air toxics” with
serious known or suspected health effects. These include some oil and
gas components, such as benzene, which is found in gasoline. Oil and
gas-related air toxics may be emitted during petroleum exploration,
production, refining and processing, and combustion.
Among the pollutants released by these sites, the main ones are
Volatile Organic Compounds (VOCs), particulate matter and greenhouse
gases. VOCs found in the ambient air near petrochemical sites are both
of aromatic and aliphatic types. Pollutants are released in various areas
and sources in the petroleum refining and petrochemical industries,
starting from process emissions to storage and handling emissions. It
arises from the production process, pipelines, flanges, valves, storage
tanks, and waste zones. Pollutants are released even during non-
routine operations like maintenance and shutdown, and the release of
pollutants can vary seasonally.

Sources of Air Pollution from the

Petroleum Industry
There are various sources of emissions in the petroleum refining and
petrochemical industries, and the following are the major categories of
emission sources.
 Process Emissions
In petroleum refining and petrochemical industries, the typical
processes that take place include separations, conversions, and treating
processes like cracking, reforming, isomerization , to name a few. The
emissions arising from these processes are termed as process
emissions, and are typically released from process vents, sampling
points, safety valve releases, and similar items.

Combustion Emissions
Combustion emissions are generated from the burning of fuels, which is
done for production and transportation purposes. The nature and
quantity of emissions depends upon the kind of fuel being used.
Generally, combustion emissions are released from stationary fuel
combustion sources like furnaces, heaters and steam boilers, but they
can also be released from flares, which are used intermittently for
controlled release of hazardous materials during process upsets.

Fugitive Emissions
Fugitive emissions include sudden leaks of vapors from equipment or
pipelines, as well as continuous small leaks from seals on equipment.
These emissions are not released from vents and flares, but may occur
at any location within a facility. Sources of fugitive emissions are mostly
valves, pump and compressor, and piping flanges. Fugitive emissions
are a source of growing concern, as their effective control requires
good process safety mechanisms for mitigation, as well as ongoing lead
detection and repair (LDAR) programs. They can be minimized by
proper design, and procedure alterations

Storage and Handling Emissions

These emissions are released from the storing and handling natural gas,
oil, and its derivatives. This is a potential problem in every petroleum
refining and petrochemical industry, including any product distribution
sites. Handling mainly includes loading and unloading operations for
shipping products to customers. Though transport of many refinery
products is through pipelines, some other means like marine vessels
and trucks also exist. In these cases, there might be emissions during
material transfer to these vehicles.

These facilities have tanks for storage at the production sites and
terminals for transportation, and air pollution here arises from the boil
off or evaporation losses. Breathing losses also contribute to the air
emissions, as the air within the tanks expands and contracts with daily
temperature changes. Likewise, when there is an increase in the liquid
volume in a tank, there is a corresponding decrease in the vapor phase
volume as VOC saturated air is pushed out.
 Auxiliary Emissions
Auxiliary emissions originate from units like cooling towers, boilers,
sulfur recovery units, and wastewater treatment units. Atmospheric
emissions from cooling towers mainly include gases, which are stripped
when the water phase comes into contact with air during the cooling
process. In wastewater treatment units, emissions may arise by
stripping of the VOCs from contaminated wastewater in the pond, pits,
drains or aeration basins.

In simple language we can summarise the sources of pollution due to

the following reasons:

1. The exhaust emission from engines, generators, gas compressors and

pump engine

2. Process of evaporation of crude oil vapors from oil pits during

production testing
. 3. Discharge of natural gas directly to the atmosphere during
production testing

4. Burning of oil from the effluent treatment plants

5. Burning of gas and waste water from the flare pit in the air directly
from various oil terminals

6. Oxidation of different sources of pollutants

7. Due to flaring, the temperature of the surrounding environment gets

increased 8. Discharge of associated low-pressure gas to the
atmosphere.

Major Pollutants of concern

There are lot of pollutants to be concerned about but we will discuss
some of the most harmful ones here:

Volatile Organic Compounds

Hydrocarbons, both aliphatic and aromatic, are the main VOCs (Volatile
Organic Compounds) that are generated from the petroleum industry .
Regulated emissions and leaks both contribute to the VOCs
concentration . Aromatic VOCs are mainly comprised of Benzene,
Toluene, Ethylbenzene, and Xylene (BTEX) , and benzene is of particular
concern since it is carcinogenic. VOCs are associated with a number of
potential health effects. Short term exposure to VOCs may cause
dizziness, fatigue, nausea and depression. Exposure to certain VOCs
may even result in mutations and cancers , and others may cause
damage to the central nervous system, kidneys and liver .

It is important to know the atmospheric lifetime of VOCs to gain an

understanding of the distances they might travel in air. A higher
atmospheric lifetime indicates that the VOC can travel a greater
distance in the atmosphere, possibly leading to impacts much farther
away from the emission source. VOC emission is an increasing problem,
with similar scenarios in many major regions of the world.

The methane has the longest atmospheric lifetime among the listed
VOCs and hence can travel a long distance from the source of release,
when compared to styrene, which has an atmospheric lifetime of just
4.9 h. Among the common aromatics (BTEX), benzene has the
maximum lifetime of 9.4 days, while the lifetime of m-xylene is only
11.8 h.

In urban areas close to refineries and petrochemical industries, the air

quality is lowered by the combined effect of industrial emissions and
traffic emissions. This was observed in Lithuania, which has a very large
crude oil refinery. Benzene concentrations in air in the urban region
exceeded the rural region by 0.63 ppb. Air quality at rural regions near
these industries was influenced only by the industrial emissions and
traffic emissions played a minor role. VOCs can also be aliphatic in
nature.

Greenhouse Gases
The petroleum industry consumes a significant amount of fossil fuels
for operational purposes, and this contributes to greenhouse gas
emissions. The greenhouse gases associated with the petroleum
refining and petrochemical industries are mainly methane, carbon
dioxide and nitrous oxide. In 2006, it was noted that equipment leakage
and venting of CH4 and CO2 from petroleum and natural gas industries
contributed to 317 million metric tons of CO2 equivalent (MMTCO2e).

Out of this, 261 MMTCO2e of CH4 and 28.50 MMTCO2e of CO2 were
emitted from the natural gas industry, whereas 27.74 MMTCO2e of
CH4 and 0.29 MMTCO2e of CO2 were emitted from the petroleum
industry. Many processes involved are very energy intensive, like
alkylation, isomerization and so on.

In recent years, increasing stringent fuel specifications pose a greater

challenge for the oil and gas industry. To meet these requirements, the
industry is using more energy in order to remove contaminants such as
sulfur. Heat and power are persistent needs with the former being
required at higher levels, often indirectly in the form of steam.
Many refineries meet their heat and electricity needs by producing it
themselves from gas, Fluid Catalytic Cracking coke and fuel oil. In this
case, the fuel requirement, and hence the greenhouse gases emissions,
are higher than they are for the refineries which procure these utilities
from elsewhere. Sometimes, though a few processes may be less
energy intensive, the volume of input material processed might be
high.

In 2013, the carbon dioxide emissions during oil production and

processing were estimated to be 130 kg CO2 per Ton of Oil Equivalent
(TOE). For each ton of hydrocarbon production, there would be release
of 1 kg of methane, and 0.4 kg of nitrogen oxides.There are some
solutions for minimizing the energy consumption in processes and
thereby the magnitude of greenhouse gases emitted. Two main
approaches are heat integration (heat management) and waste heat
recovery, where the existence of large temperature differences
between different streams provides an opportunity to recover heat and
reduce overall energy use.

Particulate Matter
Particulate matter (PM) is of increasing concern in recent years as
studies have shown links with a variety of health impacts such as
respiratory and cardiovascular morbidity, and even lung cancer.
According to the International Commission on Radiological Protection
(ICRP) Publication 30, particulate matter that is larger in size (over 10
µm) is intercepted by the nasal, tracheal mucus and is concentrated
mainly in the naso-pharyngeal region.
Particulate matter of very small diameter is considered to be the most
problematic as it penetrates deep into the lungs, thereby depositing in
the bronchioles and alveoli in the pulmonary parenchyma region.
Therefore, in many regions the focus of measurement and regulation is
on particulate matter with a size of less than 2.5 µm (PM2.5). According
to World Health Organization (WHO) guidelines, the annual arithmetic
mean concentration of PM2.5 should not exceed 10 µg/m3 , while the
24-h mean concentration of PM2.5 should be below 25 µg/m3 [41].

Based on the formation mechanism, particulate matter can be classified

into two types, namely primary and secondary particulate matter.
Primary particulate matter is directly emitted from the source to the
atmosphere, and a major source from the petroleum refining industry
is the Fluid Catalytic Cracking Unit (FCC). Secondary particulate matter
is mainly formed in the atmosphere from precursor gases like SO2, NOx
and VOCs, from photochemical reactions or liquid phase reactions in
fog droplets or clouds. SO2 and NOx are oxidized to form sulfuric acid
and nitric acid respectively, and SO2 oxidation can follow two routes

There is also the possibility of the presence of metals in the particulate

matter due to the emissions from this industry. A study on the effect of
oil refinery and vehicular emissions on airborne particulate matter in
Gela, Italy, revealed that there were many metals and metalloids in the
airborne particulate matter. When assessed further, it was found that
the presence of arsenic, molybdenum, nickel, sulfur, selenium,
vanadium and zinc, was attributed to the petrochemical industry
emissions.
Apart from these pollutants, petrochemical industries also produce
Persistent Organic Pollutants (POPs), which resist environmental
degradation by many processes

Ozone
Ozone is a secondary pollutant that is formed from the reaction
between VOCs, oxides of nitrogen, and sunlight. Hence, ozone
production depends on the amount of VOCs, NOx, and also the ratio of
VOC/NOx. The petrochemical industry can be a significant source of
hydrocarbons (VOCs) and NOx [10,18], and hence it contributes to a
favorable atmosphere for the formation of ozone. In the case of ozone
resulting from coal-fired power plant emissions (which contain NOx but
very little VOCs), hydrocarbons have to be provided from the
surrounding region, and the power plant location relative to sources of
reactive hydrocarbons is important in determining the impact on ozone
formation.

However, the petrochemical industry can release both ozone

precursors and therefore can have a more direct impact on regional
ozone formation. The effects can be worse in summer when
temperatures and ozone production rates are higher. Other factors
such as vehicular emissions also increase ozone formation by
contributing to high levels of ozone precursors. Hence the urban zones/
traffic prone regions near petrochemical sites are at high risk of ozone
formation.

Other than the concentration level of pollutants (VOCs and NOx),

another important parameter to be considered is their photochemical
reactivity, determined by the Relative Incremental Reactivity (RIR)
analysis [5]. In a study on concentration of VOCs and its impact on
ozone concentration at Wuhan, China, it was observed that ethane,
ethene and toluene were the most abundant VOC species, with
concentration levels 5.2 ± 0.2 ppbv, 3.3 ± 0.2 ppbv, and 2.0 ± 0.1 ppbv
respectively [5]. However, from the RIR analysis it was found that
ethene and toluene were the main species contributing to the
formation of ozone although ethane was present at higher
concentrations.

Recommendations for Emissions

Reduction

Petroleum refining and petrochemical industries produce emissions at

many stages of the operations. These emissions can significantly lower
the air quality and cause short-term and long-term health impacts for
workers, and people living near the sites and in the same region. The
only way the situation can be improved is to analyze the process and
operations in detail and identify areas where control measures can be
taken to reduce these emissions.

Emissions from storage can be greatly reduced by employing measures

such as vapor recovery systems, and using double seals in storage
tanks. Leaks due to faults or seal failures in equipment are a common
maintenance problem, and periodically checking or maintaining the
equipment through a leak detection and repair program can minimize
this. Likewise, fugitive emissions can be reduced through proper design,
procedures, and good maintenance practices. In portions of the
processes using combustion, lower NOx burners are available, and SOx
emissions can be minimized by desulfurization of fuels, or by directing
the sulfur-containing fuels to units that are equipped with SOx emission
control technologies. Combustor and furnace efficiency should be
improved, as it can also reduce emissions.

There are some Best Available Techniques (BATs) for the reduction of
NOx. They include the usage of low NOx burners, gaseous fuel usage,
selective catalytic reduction, and energy integration [56]. Usage of low
NOx burners lowers the flame temperature and reduces NOx
generation. A few burners employ recirculation of flue gas in order to
reduce flame temperature. Replacing liquid fuels with almost N2 free
gaseous fuels, also tends to lower NOx. Selective catalytic reduction is
another way to achieve lower emissions, using V2O5/TiO2 catalysts
where oxides of nitrogen react to form nitrogen and water.
 Laws and regulations governing
refineries
The Atmospheric Pollution Prevention Act, No 45 of 1965, is the main
law governing air pollution. The Act is very outdated and needs to be
revised to be in line with international standards. In terms of this Act,
no one may operate a refinery without having a registration certificate
(or permit) from DEAT. The permit sets a limit to the amount of
pollution that the refinery is allowed to emit. If the refinery emits more
than the permit allows it to, then it is breaking the law and can be
punished. Presently, SA refineries do not have to actually measure their
air emissions but may simply estimate or calculate the amount they are
emitting through their stacks. These estimates do not include fugitive
emissions. Remember that very often pollution from fugitive emissions
can by higher than the emissions coming out of the stacks.

Conclusions
In common with various other industrial activities, refineries and
petrochemical industries can affect air quality. They may release
pollutants like VOCs (Volatile Organic Compounds), particulate matter,
greenhouse gases and contribute to ozone formation, mainly from
separation, conversion, treating, combustion, storage, sudden leakages
from process equipment, or even from auxiliary sources like cooling
towers, boilers, and sulfur recovery units. These emissions lower the
quality of air—quantified by Air Quality Indices and air quality
management is critical to resolve this problem and minimize the
impact.Although air quality management has been successful in many
developed nations, it has more scope for improvement. In developing
countries, factors like increased energy demands and rapid
industrialization have made it necessary to achieve better air quality
management before the condition worsens further.

Industrial areas have the highest concentration of VOCs when

compared with urban and background areas. This could be attributed to
emissions from industries and traffic emissions. In urban areas,
vehicular emission is the main source of VOCs. Rural areas have the
least amount of VOCs when compared to other industrial and urban
regions. The level of exposure to polluted air is important in
determining the potential effects on people, and as the World Health
Organization has identified polluted air as the largest single
environmental health risk, we need to ensure that air quality is well
managed and improved.

Exposure to poor air quality appears to contribute to health conditions

and deaths from COPD (Chronic Obstructive Pulmonary Disease),
respiratory infection, lung cancer, and heart damage. The direct
contribution of refining and petrochemical emissions to health effects
cannot be determined for certain, as many other factors such as
population lifestyle and habits, and other emission sources also need to
be considered before drawing any firm conclusions. This needs more
research and extensive studies before we can infer more from any
associations between specific emissions and health effects, but it is
clear that any positive impacts on air quality can be beneficial.
To maximize the benefits of new legislation and policies to improve air
quality, it is desirable to carry out policy analysis using statistical
modeling . Such statistical modeling enables the analysis of the
distributional consequence of different scenarios for emission
reduction. This could thereby make it easier to conclude whether
certain emission reduction policies could lead to minor or significant
improvements.

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