University of Tabriz

Faculty of Chemical and Petroleum Engineering

Department of Chemical Engineering

Proposing a dissertation research plan to receive a doctorate degree in

Chemical Engineering

Title:
Prediction of emission and exposure of Poly Aromatic Hydrocarbons in a
petroleum refinery for providing a suitable control method

Supervisor:
Dr. Leila Khazini

Researcher:
Warga Abdul Reza Kazem

July 2023

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Table of Contents Page

A) Abstract……………………………………………………………...……………………..3

b) problem Statement …………………………………………………………………………4

C) Research questions…………………………………………………………………...……11

D) Research hypotheses……………………………………………………………….….…..11

E) Literature review…………………………………………………………………..………11

F) Materials and methods ………………………………………………………………...….16

G) Expected resulted……………………………………………………………………...….17

H) Reference.............................................................................................................................18

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A) Abstract

Volatile organic compounds have various definitions and limitations provided by regional and/or
international regulations to control indoor air quality (IQA) and outdoor air pollution (OAP).
These standards aim to impose restrictive policies on specific industries to reduce their VOC
emissions, and to protect their VOC-exposed workers by effective personnel protective
equipment (PPEs). Polycyclic aromatic hydrocarbons (PAHs) are a large group of organic
compounds with two or more fused aromatic rings. PAHs have received increased attention in
recent years in air pollution studies because some of these compounds are highly carcinogenic
or mutagenic. Eight PAHs (Car-PAHs) typically considered as possible carcinogens are:
benzoanthracite, chrysene, benzo fluoranthene, benzo fluoranthene, benzo pyrene,
dibenzoanthracene, indeno (1,2,3-cd) pyrene and benzoperylene. In particular, benzo pyrene has
been identified as being highly carcinogenic. The main sources of PAHs in the aquatic
environment are due to the incomplete combustion of fossil fuels such as petroleum, diesel,
leakage of the units flanges, emissions from petrolume units (towers,furnaces,heat
exchengers,pipes,tanks ) and waste water pons emissions . Other sources include natural forces
such as forest fires, volcanic eruptions, and the diagenesis of organic materials, which can also
result in the production of PAHs. Adsorption is a recognized effective technique for removing
PAHs from produced water. Carbon materials such as biochar, activated carbon, graphene, and
carbon nanotubes are used as adsorbents. Biochar is a carbonaceous solid derived from petroleum
sludge, wastewater sludge, and agricultural waste. When adsorption is used as remediation
technology, the most important design consideration is the selection of an appropriate adsorbent,
which is largely dependent on the chemical nature of the gaseous stream. Activated carbon (AC)
is the most commonly used adsorbent for VOCs , PAHs removal. Adsorbents materials such as
biomass , activated carbons, polymers, biopolymers and molecularly imprinted polymer
materials , graphene and graphene oxide , clay and modified clay minerals , carbon nanotubes ,
silica-based materials , have been extensively studied as possible replacement to the conventional
adsorbents for wastewater remediation. The application of mussel inspired chemistry to modify
the adsorbents to improve the adsorption capacity has also been proposed . Air emissions from
light oil plant (naptha unit,LPG unit, kerosen unit, isomerisation unit ) and evaporation from
wastewater treatment plants (WWTPs) often consist of a combination of odor and volatile
organic compounds(VOCs) and it can be treated in different strategies. For wastewater from
WWTP: prediction and treating by Adsorption unit using absorbent such as activated carbon
with biochair unit is one of the major treatment processes for odor and VOCs control. some
absorbers was set up at a wastewater treatment plant in dura refinery/Baghdad .
keywords: Prediction, Emission, Exposure, VOC, refinery

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4
 B) Problem Statement
Volatile organic compounds are compounds that have a high vapour pressure and low water
solubility [1]. The US Environmental Protection Agency (EPA) has promulgated 16 un substituted
PAHs (EPA-PAH) as priority pollutants. Thus, exposure assessments of PAHs in the developing
world are important Exposure to PAHs can occur by Breathing air containing, Motor vehicle exhaust,
Cigarette smoke, Wood smoke, Fumes from asphalt roads, Consuming grilled or charred meats or
foods [2].

Environmentally VOCs has attracted increasing attention because of their important roles in the
formation of ozone and secondary organic aerosols, which can impact climate change and air quality
and are hazardous to human health and production [3].

PAHs are classified as low molecular weight (LMW) and high molecular weight (HMW)
compounds. LMW PAHs contain two or three aromatic rings, while HMW PAHs contain four or
more aromatic rings. The U.S. Environmental Protection Agency (EPA) classifies PAHs into sixteen
forms based on their hazardous nature. PAHs can also be classified as alternant and non-alternant,
where their structure is composed entirely of benzene rings with the involvement of four, five, and
six-member non-aromatic rings. The physical and chemical properties of PAHs are determined by
their conjugated π-electron structures, which depend on the number of aromatic fused rings and their
molecular weight [4]. The types of LMW and HMW PAHs, their formulas, structures, and molecular
weights [5].

In general, the volatility and solubility of PAHs decline, while their hydrophobicity increases with
an increase in the number of benzene-fused rings The sources of PAH pollution are categorized
mainly into two, such as anthropogenic emission sources and natural emission sources (Mojiri et al.,
2019). Natural emission sources such as volcanic eruptions, natural forest fire, and moorland fire
caused by lightning flashes are negligible or less important Anthropogenic emission sources are the
main determinants of PAH pollution, which can be divided into four types, i.e., industrial, mobile,
domestic, and agricultural emission sources. Incomplete combustion is the prime source of PAH
emissions by various industrial activities such as waste incineration, iron and steel production,
aluminum production, cement manufacturing, coal-tar pitch production, dye manufacturing, asphalt
industries, rubber tire manufacturing, fungicide and insecticide production, exhaust from refineries,
and power production.

The environmental problem usually referred to as the Global Warming (GW) is the enhancement of
greenhouse gases in the atmosphere. The greenhouse gases are water steam (H2O), carbon dioxide
(CO2), methane (CH4), ozone (O3), dinitrogen oxide (N2O) +and freons. As mentioned before the
VOC interference in the ozone balance leads to formation of CO2. This indicates that VOC have a
double effect on the global warming. But as mentioned earlier the net contribution of the ozone’s
effect on the greenhouse effect is zero. Methane (CH4) is second to CO2 the most important
greenhouse gas. It is 25 times more effective than CO2.In the case of an associated gas reserve, when
the construction of infrastructure to take it to market is unfeasible for technical or economic reasons,
there are three options: burning in flares (flaring), releasing into the atmosphere (ventilation), or
injection.In this way, the reduction of burning and venting of associated gas with oil (in the form of

5
carbon dioxide, or losses, in the form of methane) has two main goals: Prevent the associated gas
with oil from being produced and wasted, considering it is an important and non-renewable energy
resource, which should provide some benefit for society (as a petrochemical feedstock, for electricity
generation in thermoelectric plants, as automotive fuel, among others); Prevent greenhouse gases
(methane and carbon dioxide) from being released into the atmosphere, without generating the
benefits already mentioned, as well as reducing methane ventilation, given its greater negative
potential against CO2, as previously mentioned.

Besides the impact as greenhouse gases, pollutants from natural gas flaring or venting can cause
other problems to the environment and society, such as increasing soil acidity, promoting acid rain,
impacting human health (lung diseases), and decreasing plant growth and productivity[6].

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 [7].

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 [8]. VOC from oil refineries mainly consists of alkanes, alkenes and aromatic
compounds [1].

Reduction and treatment of VOCS , PAHS and organic hazardous air pollutant emissions are
generally accomplished by Condensation , Adsorption ,Absorption / Scrubbing , Thermal
incineration, Catalytic incineration , Flaring , Biological treatment ,Odor modification , Air dilution
, Membrane separation ,UV treatment , Ozone catalytic oxidation [9].

The methodology is usually chosen depending upon the temperature, composition and volumetric
flow rate of the emission stream, space constraints and allowable installation and operational costs.

VOC control methods are broadly classified into recovery methods, destruction techniques,
photocatalytic oxidation and plasma technology. Recovery procedures, such as membrane
separation, condensation, adsorption and absorption, aim to collect, store and reuse VOCs. The
adsorption method achieves high removal efficiency and automatic control for VOCs at low and
medium concentrations. However, it is not suitable for high concentrations and high-temperature
organic waste gas. Moreover, the adsorption materials need to be replaced regularly [10].

methane Global anthropogenic emissions for 2010 were estimated at 6,875 million metric tons of
CO2 equivalent (MMTCO2 E), 50 percent of these emissions come from the five sources targeted
by the Global Methane Initiative (GMI): agriculture, coal mines, landfills, oil and natural gas
systems, and wastewater [11].

Where refining process can be divided into four segments:

(1) crude separation; (2) light hydrocarbon processing; (3) middle and heavy distillate processing;
and (4) residual hydrocarbon processing.

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The various distillation and fractionation processes produce the largest volumes of ,wastewater, with
most of the water being discharged from three sources. The first source is the water drawn off from
overhead accumulators before recirculation or transfer of hydrocarbons to other fractionators, The
second wastewater source is discharge from oil sampling lines, and the third source is from oil
emulsions that form in the barometric condensers used to maintain reduced pressures in the vacuum
distillation units. Nearly all refineries include some type of onsite wastewater treatment system.
Previous work performed by the Agency indicates that these wastewater collection and treatment
systems are significant sources of VOC emissions.

To minimize the VOC emissions from storage of oil or volatile products there are many small but
effective measures to be taken. The color of the storage tank is of importance, a light storage tank
emits less than a dark one. Usage of pressure/vacuum valves to minimize breathing losses is another
way of easily minimizing emissions [12].

This is one of the most commonly used methods, especially for controlling emissions from small
sources. The adsorbed material can be either recovered or incinerated. Regeneration is usually
accomplished by heating or extraction/displacement.

In general, activated carbon and other adsorbents such as hollow aluminium spheres coated with a
catalyst can be employed in a fixed, moving or fluidized bed system .Activated carbon is a commonly
used adsorbent because of its high surface area and material hardness.

Water comes in direct contact with organic compounds through many different chemical processing
steps, resulting in wastewater streams that must be discharged for treatment or disposal. Direct
contact wastewater includes: Water used to wash impurities from organic compound products or
reactants; Water used to cool or quench organic compound vapor streams ; Condensed steam from
jet eductor systems pulling vacuum on vessels containing organic compounds; Water from raw
material.and product storage tanks; Water used as a carrier for catalysts and neutralizing agents (e.g.,
caustic solutions); and Water formed as a byproduct during reaction steps. Two additional types of
direct contact wastewater are landfill leachate and water used in equipment washes and spill
cleanups. This wastewater is normally more variable in flow rate and concentration than the streams
previously discussed, and it may be collected for treatment differently from the wastewater streams
discharged from process equipment such as scrubbers, decanters, evaporators, distillation columns,
reactors, and mixing vessels [13].

The problem of atmosphere pollution from wastewater treatment plants caused by odor and VOCs
has gained much attention for years. At WWTPs, an appreciable amount of odor and VOCs can be
emitted during the wastewater collection and sludge handling processes. And many countries have
already made the related laws and regulations to control the emission of odors strictly. The biological
method has attained more and more attention in the research and practical application, for its
characteristics of high efficiency, low treatment cost, convenience to operate and maintain and
without secondary pollutants . Biofilter, biotrickling filter and bioscrubbling are three types of
biological treatment technologies. Biofilters have been successfully applied to the removal of
different odor and VOCs at WWTPs widely, because of its ability to treat low concentration
compound.

7
Aromatic hydrocarbons are compounds that consist of aromatic rings. Some of these are of high
toxicity to humans. Poly Aromatic Compounds (PAH) can be urgently toxic, geneotoxic,
carcinogenic or a combination of the above. The PAH are actually not carcinogenic in their original
form but when transformed in the metabolic process they become toxic. During the metabolic
process the PAH can be transformed to free reactive radicals like epoxides that cause cancer.
Benzene is one of the more hazardous PAH causing leukemia and other types of cancer. Toluene can
cause damages for example on inner organs, the central nerve system, or fetus damages. Toluene can
also contribute to the formation of photochemical smog that is very dangerous to water living
organisms. Both Benzene and Toluene are included in the VOC group .

Typical refinery wastewater treatment system Tanks or treatment units upstream of any benzene
removal or destruction systems at most petroleum refineries are regulated under BWON (Benzene
Waste Operations NESHAP) and thus should be covered and vented to appropriate control devices.
Equalization tanks, oil/water separators, and flotation units typically fall into this category.

Biological treatment units are typically the first uncovered process in the wastewater treatment.
There are three primary estimation methods: (1) direct measurement, (2) predictive modeling, and
(3) engineering estimates. Direct measurements can only be taken from process units that are covered
and vented to a control device. Predictive modeling can be accomplished using analytical [13, 14].

Three mechanisms affect the removal of organic compounds in aeration basins. These mechanisms
are biodegradation, adsorption onto the sludge, and air emissions. Because these three mechanisms
compete against each other, factors affecting biodegradation and adsorption mechanisms will have
an effect on air emissions, 20 The greater the biomass concentration in the basin, the greater the
removal of organic compounds will be by both biodegradation and adsorption mechanisms [15].

Reduction technology of VOC :

-Internal solutions: internal solutions that affect the VOC emissions is that an isomerization step was
added in 1991 where carbon chains with six carbons or less are isomerized to increase the octane
number. This results in less benzene being produced in the process [16].

- External solutions Carbon filters There are plans to install carbon filters on the heavy oil tanks to
eliminate the smell of oil. Initially one tank will be equipped with a filter and if it proves to be
effective two more tanks will receive carbon filters. This is mainly an odor control action but will
capture VOC [17].

Leaks throughout the plant are the greatest problem for VOC control. Leak searching then becomes
important to identifying sources of emission. This can be done by TCT measuring or utilizing a
GasFindIR camera or other portable leak searching instruments [10].

A variety of methods exist to remove volatile organic compound:

(VOC) air pollutants from contaminated gas streams known as vapor recovery units , The use of
these methods depends on the precise nature of the VOCs, the concentration levels, and the
conditions (temperature, pressure, flow rate) [18].

8
 These have been described in a general manner in a number of articles and books. They are briefly
described below and will be covered in more detail in subsequent chapters with particular emphasis
on their applications to VOCs.

1- Adsorption: This is one of the most commonly used methods, especially for controlling emissions
from small sources [17].

2- The adsorbed material can be either recovered or incinerated. Regeneration is usually

accomplished by heating or extraction/displacement [19].

In general, activated carbon and other adsorbents such as hollow aluminium spheres coated with a
catalyst can be employed in a fixed, moving or fluidized bed system .Activated carbon is a commonly
used adsorbent because of its high surface area and material hardness.

The main types of adsorption processes are fixed-bed adsorption, rotary wheel adsorption and
fluidized bed adsorption.

- The fixed-bed is the most common adsorption process in gas treatment. The gas flow is often
conditioned by cooling upstream, partial condensation and heating to reduce the relative humidity.
This is done to minimize co-adsorption of water.

- A fluidized-bed process uses adsorbent beads that, by utilizing the velocity of the gas, are in a
fluidized state throughout the tank. This technique is not very common due to the high energy
consumption it requires.

-A continuous moving-bed process is much like the fluidized bed, except for the adsorbent not
floating on the gas but continuously being fed on top of the tank. The most common adsorbents types
are: Granular Activated carbon (GAC), Combustible Silica gel, Zeolites and polymers adsorbent [4,
20].

 Granular Activated carbon (GAC): is the most common adsorbent in VOC reduction. It is used
for recovery of solvent vapors from gas mixes and for fractionation of hydrocarbon gases
,possible to regeneration ,Not restricted to polar, the higher the boiling point, the stronger the
attachment to the surface but it is Sensitive to humidity (65- 70 % humidity as Maximum)

 Combustible Silica gel: Silica gel is mostly used for dehydration of gases and for fractionation
of hydrocarbons. It has a polar character and adsorbs steam well,it be regenerated ,but it is Non-
combustible And with Compared to activated carbon the adsorption area is very small .

 Zeolites: Zeolites are a silicate material that has a special crystal structure gives it a large
adsorption area. Natural zeolites contain aluminium atoms, have polar character and are thus
appropriate for drying. If the aluminium atoms are removed, the material instead receives a non-
polar character. This results in the ability to tailor the adsorbent to fit the area of use [21].

 Polymer adsorbents (PA): The mechanical strength of (PA) is higher than GAC but it is much
more expensive,Large adsorption area , Regeneration is possible.

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 Incineration: Incineration or combustion is another common VOC control technology. Complete
combustion or oxidation of pure hydrocarbons produces carbon dioxide and water. Sulfur and
nitrogen compounds produce acid gases and limited air supply results in the formation of carbon
monoxide. Flares, thermal oxidizers and catalytic converters all use oxidation chemistry to treat
VOC emissions. Flares mostly treat moderate to high temperature concentrations. All of the heat
produced by the combustion process is lost when the flares are used, thermal oxidizers treat
emission streams with maximum VOC concentrations of 25% of the LEL (lower explosive limit)
and Catalyst beds used to enhance the oxidation of VOCs (usually noble metals like platinum
and palladium) must be able to withstand high temperatures and must be designed so that a
minimum pressure drop is created when the gas passes through the bed.

 Condensation: both Condensation and gas absorption are most commonly used for highly
concentrated VOC streams that are advantageous to recover and the relatively large expense is
warranted. It employs a drop in temperature and/ or increase in pressure to cause the VOCs in
the emission stream to condense. The cleaned air stream is separated from the condensate
containing target pollutants. In many cases, very large temperature drops are required to achieve
effective condensation, requiring significant energy investment to accomplish cooling.

 Flaring: is another combustion technique which involves the direct burning of an organic stream
in an open flame, it can tolerate large variations in flow rate, so is commonly employed in
transient situations such as start-up and shutdown. It is routinely used in refining as a method of
disposing of VOCs in that industry [21].

 Biological Treatment: Biological treatment consists of using microorganisms to biologically

degrade contaminants Biological purification is a relatively new technology in the field of air
pollution control although the same concept has been used for years to treat wastewater streams.
Microorganisms are grown on a substrate (biofiltration) or are suspended in a liquid scrubber
media (bio-scrubbers) is a Treatment technology for VOC emissions from oil refineries, sewage
treatment plants, it uses the ability of microorganisms to clean gas streams from VOC [22]. A
biofilter can consist of a bed of soil or compost through which the gas stream passes [23, 24].

The organic substrate provides the salts and trace elements for the bacteria whilst the VOC make
up the food. In a moist environment the organisms degrade VOC to CO2 and water while
Biodegradable compounds are removed from sewage treatment such as amines, hydrocarbons,
hydrogen sulfide, toluene, styrene and odorous contaminants. Methane is not abated due to the
long residence time this would require.

 Gas Absorption: Absorption: is a physical process consisting of the dissolution of a pollutant in

a liquid. In absorbers (or scrubbers), the vapour stream is introduced into a chamber where it is
intimately mixed with the liquid. The amount of pollutants remaining in the gas stream as it
leaves the scrubber is governed by Henry’s law, which establishes the amounts of a component
in equilibrium in the gas and water streams for dilute mixtures

 Membrane Separation: Membrane technology using the semipermeable membranes to

separate VOCs from a process stream (The permeation rate of organic compounds is about 10 to
100 times higher than that of oxygen, nitrogen, hydrogen or carbon dioxide). This technology
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 has been used in water purification. The separation is based on preferential diffusion of VOCs
across thin polymer layers wrapped around a perforated central tube. The driving force is a
pressure differential between the inner and outer portions of the tube. The method is effective for
recovering VOCs such as chlorinated hydrocarbons, chlorofluorocarbons, and hydro
fluorocarbons that have been traditionally difficult to separate because of their high volatility.
Recovery of hydrogen from refinery off gas and recovery of VOC from tank-filling are two ways
in which membrane technology can be used at refineries [25].
 UV Treatment: another emerging technology in which ultraviolet light is used to oxidize organic
compounds. The oxidation reaction is promoted by the photo catalytic effect of the UV light and
is conducted in the presence of a catalyst to activate the oxygen into highly reactive species
including ozone. After reaction, the air stream is scrubbed to perform additional oxidation, dried,
and remaining VOC compounds are adsorbed in activated carbon. The technique has been
reported to be up to 99% effective in the destruction of organic compounds [25, 26]. Problems
are activity at high flow rates and the low photo efficiencies of the catalytic process, which results
in high costs.
 Catalytic Ozone Oxidation: Ozone catalytic oxidation technology is already seeing
commercialization in a number of household applications such as the deodorization of
refrigerators and toilets and the purification of room air. A contaminated gas stream is mixed
with ozone and passed over a catalyst bed to carry out a low-temperature catalytic combustion
reaction. The process utilizes the oxidizing power of ozone together with the activity and
selectivity of oxidation catalysts to convert VOCs to CO2 and H2O. The process works at high
and low VOC concentrations, and at high flow rates. Because of the use of ozone the air stream
does not require appreciable heating. Improvements in generation equipment have decreased the
cost of the ozone substantially, and this promises to become a broadly used technology [27, 28].

Emissions from refineries differ dependent on the activity. The tank parks and process area seem to
be the largest emitters for gasoline and diesel producing plants. From this same kind of activity
alkanes make up the largest fraction of the emission. When starting the work with VOC control the
following is recommended for all refineries.  Measuring of total plant VOC emission of Using on-
line technology as SOF o Identifying the composition of the plume through canister test etc.  Leak
searching / Maintenance [9]. Global warming the greenhouse effect is the result of the ability of
some gases in the atmosphere to absorb the long wave heat radiation form the earth. These gases are
referred to as greenhouse gases. The greenhouse effect is a natural effect and is a pre-requisite for
life on earth.

In this research the emissions of volatile organic compound from light oil units (Naphtha unit,
hydrogenation unit, isomerization unit, LPG unit) and wastewater ponds from industrials (specially
petroleum industry) is the main research topic problem, prediction, control, treating and reducing
emissions of VOCs as much as possible is the first goal, by choosing better treatment unit, and
environmentally scope is the second goal.

C) Research hypotheses

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  Adsorption is a recognized effective technique for removing PAHs from produced water.
Carbon materials such as biochar, activated carbon, graphene, and carbon nanotubes are used
as adsorbents.
 Biochar is a carbonaceous solid derived from petroleum sludge, wastewater sludge, and
agricultural waste.
 Control about VOCs (PAHs) evaporating or emissions from light oil units (naphtha,
kerosene, hydrogenation), and waste water treatment pons (physical treatment basin,
mechanical basin, biological treatment basin, API basin).

D) Literature review
This study was carried out with the aim of increasing and determining the activated zeolites’
adsorption capacity by testing their efficiency on petroleum hydrocarbons. Natural zeolite samples
were sequentially studied after thermal and chemical activations. The results indicated that after the
activations, the zeolite samples gained an increasing adsorption capacity of petroleum hydrocarbons.
Furthermore, the zeolites with small particulate sizes .Zeolites are crystalline aluminosilicates
composed of three-dimensional structures of AlO4 and SiO4 tetrahedra bound together by oxygen
ions .In the present study, the determination of the adsorption capacity of a natural zeolite
(clinoptilolite) was studied by using two activation methods: (i) thermal activation, and (ii) chemical
activation, in order to increase the petroleum hydrocarbons adsorption capacity. The activated zeolite
samples chemically activated with surfactant (methyl dodecylbenzene sulfonate) solutions were
tested to study the petroleum hydrocarbon adsorption capacity. The highest petroleum hydrocarbon
adsorption capacity is observed at samples activated with the most concentrated surfactant solution
(2.0 mmol/L). Results vary between 101-253 mg/g adsorbed hydrocarbons by zeolites [29].

The objective of this work was to obtain low-cost adsorbent materials in order to remove VOC
pollutants. Toluene was chosen as a model of volatile organic compounds for this study. Microporous
activated carbons were obtained from vegetable-tanned leather wastes (shavings, trimmings and
buffing dust) by means of chemical activation with alkaline agents (KOH, NaOH and K2CO3). A
specific BET surface area, total pore volume (VTOT) and total micropore volume (Vtot) of 2719 m2
g-1 , 1.184 cm3 g-1 and 0.829 cm3 g-1 , respectively, were obtained by KOH-activation, whereas
K2CO3-activation yielded values of 1645 m2 g- 1 , 0.712 cm3 g-1 and 0.536 cm3 g -1 , respectively.
Low-cost activated carbons with textural properties, chemical functional groups and a capacity for
toluene adsorption comparable to that of activated carbons obtained with KOH or NaOH were
produced from these wastes by means of K2CO3 chemical activation. Toluene adsorption values at
concentrations on the odour threshold-5 ppm (27 mg VOC/g), TLV-TWA-50 ppm (288 mg VOC/g)
or TLC-C-100 ppm (700 mg VOC/g) higher than commercial activated carbons such as NORIT
RB3, WV-A1100 or Centaur HSV were obtained. There is no direct relationship between the textural
characteristics, chemical functional groups and toluene adsorption capacity and a balance between
all of these features needs to be taken into account to explain the high adsorption capacities obtained
in some cases [30, 31, 32].

Adsorbents originated from biological materials play a vital role in the remediation of diverse toxic
pollutants due to their high efficacy, low cost and being environmentally friendly. The present study
focusses on the palm shell activated carbon obtained from agricultural waste precursor (palm shell)

12
with the aid of oleic acid activation along with ultrasonic assistance and its effective utilization for
acenaphthene adsorption from aqueous and real effluent [5].

Polycyclic aromatic hydrocarbons (PAHs) in water are classified as organic micropollutants, which
are carcinogenic even in very low concentration (ppb). In this study the green synthesized iron oxide
nanoparticles (IONPs) were green synthesized at room temperature by using pomegranate peel
extract. The green synthesized IONPs were used for adsorbing benzo(a)pyrene and pyrene (PAHs)
from water. Factors affecting the adsorption were investigated. These factors are: nanoparticles dose,
pH, temperature, and initial concentration of PAHs. The investigation was extended using semi-pilot
plant to remove the studied PAHs from artificially contaminated water. The results showed that the
IONPs was capable to remove the pyrene and benzo (a) pyrene at the rate of 98.5 and 99%,
respectively. It also can be used as disinfectant [33].

Natural clays have received much attention as adsorbents due to their excellent physicochemical
properties (ion exchange capacities, swelling behaviour, and surface area), availability and the
absence of secondary by-products . Clays such as bentonite, sepiolite, montmorillonite (Mt) or
zeolite have been widely used to remove Phen, Pyr and benzo(a)pyrene (BaP) through the adsorption
process. Another approach is the use of clays to reduce the bioavailability of PAHs from solid
environmental samples such as in soils and sediments . PAHs are released into the atmosphere and
enter the water, soil, or sediment through wet and dry deposition processes. In this sense, a variety
of adsorbents including active carbon, zeolites, biochar, or clays have shown good effects in
laboratory experiments. Authors observed that activated carbon blended in clay showed higher
contaminant retention of PAHs and less negative effects on biota than activated carbon in its pure
form. In this study, the adsorption capacity of natural (Mt), synthetic (Na-Mica-4), and modified
(with octadecylamine and octadecyltrimethylamine (ODA-Mt, 18 ODA-Mica-4, and ODTMA-Mt
and ODTMA-Mica-4)) clays for the removal of 16 PAHs was evaluated. To the best of our
knowledge, this is the first time that the six selected clays have been examined and compared as
adsorbents of a high number of PAHs. Mt has attracted great interest because of its high cation
exchange capacity (CEC), large specific surface area, low price, easy availability, and good
biocompatibility [34].

Polycyclic aromatic hydrocarbons are increasingly widespread pollutants introduced into the
environment via oil spillage and incomplete anthropogenic combustion of fossil fuels. In this work,
the capacity of Steven site and sepiolite to adsorb phenanthrene (PHE) has been evaluated
experimentally by batch testing. Both clay minerals are distributed widely in the Madrid Basin, are
of low cost and can be applied with minimal environmental impact. In the context of few previous
studies, adsorption isotherms have been developed to understand the adsorption mechanisms and
were fitted to the Freundlich and linear models with virtually the same results. Although stevensite
showed greater adsorption capacity than sepiolite, the isotherms were constructed for equilibrium
concentrations up to 0.8–1.0 mg/L due to the low solubility of PHE in water. When compared to
other adsorbents the ability of stevensite to retain PAHs should be examined further in order to add
and complement novel functions in reactive barriers [35].

In this work, we reported highly porous and stable Fe-based MOFs, i.e., MIL-88(Fe) and NH2-MIL-
88(Fe) as adsorbents for the removal of CRY in water. CRY was chosen as model analyte because
of its adverse environmental impacts and toxicity to humans. Various factors affecting the

13
adsorption; kinetics, isotherms, and thermodynamics of the process were evaluated. Possible
reusability of the MOFs was also studied. Theoretical modeling of the interactions of the MOFs with
the CRY was conducted using molecular docking tools. Additionally, molecular docking was used
to unravel the nature of the adsorption between the MOFs and CRY. The reusability of the adsorbents
was evaluated using regeneration studies. In conclusion, these MOFs exhibit favorable
characteristics to be used for the removal of CRY from water [36].

Wastewater treatment plants (WTPs) are known as major sources of odor pollution due to their
activities and are subject to odor complaints .samples were collected in a biological wastewater
treatment plant (250,000 m3/d capacity ),and analyzed for VOC species in a GC-MS. A total of 18
samples were collected at six points within the plant: (1) coarse screens and pumping station, (2) fine
screens, (3) grit chambers, (4) sludge thickeners, (5) sludge drying, and (6) ozonationunit (wet
scrubber) because flue gas streams are collected from these five units. According to VOC
groupstreatment efficiencies by ozonation were determined as 74% for monoaromatics, 44% for
alkanes, 85% for halogenated VOCs, 100% for ketones, 100% for acetates, 88% for sulfur containing
VOCs. Contrary to these results alcohols values from ozonation unit are higher than values total
units.The system employs biological processes for carbon, nitrogen, and phosphorous removal [37,
38].

VOCs species in 7 groups were identified in this examination. It can be possible say that total ketones
and acetates were removed by rate of 100% because VOCs, including these groups were not
determined at the ozonation outlet. VOCs treatment perfomences for total halogenated compounds,
total sulfur compounds, total monoaromatics, total alkanes were calculated as a 85%, 88%, 74%,
44% respectively. However, in spite of very low total concentration of VOCs in alcohol group at the
ozonation inlet, total concentration at the ozonation outlet was determined too high (in contrary it
must be lower) to calculate performance for this group. As a special designed techniques allows
identification of one or two type of VOC species while there are generalized techniques of VOC
analyses that allow a wide matrix of VOCs (Lorngage et al., 2004). Aldehydes, amins, organic acids,
and sulfur-containing VOCs are the most commonly identified pollutants especially regarding odor
(Giungato et al., 2016; Kim et al., 2014; Agus et al., 2012; Krach et al.,2008)TS EN 13649:2003 and
ASTM D5504-98 methods and Agilent 6890N GC-MS system were used for analyses in this study
[30].

The analysis of biofiltration efficiency was performed with parallel VOC, H2S and NH3 removal
using pilot two-stage biofilters including conventional biofiltration and purification on a membrane
filter. The scope of the research was to determine the relationship between the technological
parameters of the tested device (two beds and two membranes) and gases removal efficiency.
Research was carried out in a semi-technical scale in three industrial plants: mechanical-biological
municipal waste treatment (MBT), food industry (FI) and wastewater treatment (WWTP) plants.
Experimental results indicate the efficiency removal of VOCs from 89% (WWTP) to 98% (FI), NH3
from 88% (WWTP) to 100% (MBT) and H2S from 93% (WWTP) to 100% (MBT). Biofilter with
stumpwood chips-bark-compost bed, fortified with the more porous membrane was the most
effective, allowing VOC, NH3 and H2S removal with an average efficiency of 99% for NH3 and
H2S and 97% for VOCs. The application of membrane fabrics as the second stage of purification
allows high efficiency simultaneous removal of VOCs, NH3 and H2S .For The two-stage membrane

14
biofilters used Two types of packing materials were used: a mix of stumpwood chips with a grain
diameter of 20–80 mm (50%) and pine bark (50%) – denoted as CB.

The highest content of VOCs and H2S was in process gases emitted by FI. In turn, the largest NH3
content was measured in process gases emitted by WWTP , The lowest VOC, NH3 and H2S content
was reported in the gases emitted at MBT. In all sources, inlet VOC concentrations are quite low
(not exceeding 10 ppm), which may cause a weaker effect in the first stage of purification (traditional
biofilter).

The obtained RE of VOCs from gases emitted at MBP, FI and. In turn, (Pagans et al., 2007) obtained
the following VOC removal efficiency during the research: 71%–91% in the case of biofiltration of
process gases from raw sludge composting; 0–97% in the case of traditional (conventional)
biofiltration of process gases from anaerobically digested wastewater sludge composting; 0–82% in
the case of biofiltration of process gases from animal byproduct composting; and 0–57% in the case
of biofiltration of process gases from organic waste composting [39].

Central China by collected 53 VOC samples from petrochemical, surface coating, electronic
manufacturing, and gasoline evaporation using stainless canisters to develop localized source
profiles. Concentrations of 86 VOC species, including hydrocarbons, halocarbons, and oxygenated
VOCs, were quantified by a gas chromatography–flame ionization detection/mass spectrometry
system. Alkanes were the major constituents observed in the source profile from the petrochemical
industry. Aromatics (79.5~81.4%) were the largest group in auto-painting factories, while
oxygenated VOCs (82.0%) and heavy alkanes (68.7%) were dominant in gravure printing and offset
printing factories, respectively. Acetone was the largest contributor and the most frequently
monitored species in printed circuit board (PCB) manufacturing, while VOC species emitted from
integrated chip (IC) were characterized by high contents of isopropanol (56.4–98.3%) and acetone
(30.8%). Chemical compositions from vapor of gasoline 92#, 93#, and 98# were almost identical.
Alkanes were the dominant VOC group, with i-pentane being the most abundant species (31.4–
37.7%), followed by n-butane and n-pentane. However, high loadings of heavier alkanes were
observed in the profile of diesel evaporation [40-43].

Two biofilters were operated to treat a waste gas stream intended to simulate off-gases generated
during the manufacture of reformulated paint. The model waste gas stream consisted of a five-
component solvent mixture containing acetone (450 ppmv), methyl ethyl ketone (12 ppmv), toluene
(29 ppmv), ethylbenzene (10 ppmv), and p-xylene (10 ppmv). The two biofilters, identical in
construction and packed with a polyurethane foam support medium, were inoculated with an
enrichment culture derived from compost and then subjected to different loading conditions during
the startup phase of operation. One biofilter was subjected to intermittent loading conditions with
contaminants supplied only 8 hr/day to simulate loading conditions expected at facilities where
manufacturing operations are discontinuous. The other biofilter was subjected to continuous
contaminant loading during the initial start period, and then was switched to intermittent loading
conditions. Experimental results demonstrate that both startup strategies can ultimately achieve high
contaminant removal efficiency (99%) at a target contaminant mass loading rate of 80.3 g m3 hr1
and an empty bed residence time of 59 sec. The biofilter subjected to intermittent loading conditions

15
at startup, however, took considerably longer to reach high performance. In both biofilters, ketone
components (acetone and methyl ethyl ketone) were more rapidly degraded than aromatic
hydrocarbons (toluene, ethylbenzene, and p-xylene). Scanning electron microscopy and plate count
data revealed that fungi, as well as bacteria, populated the biofilters.

VOC concentrations in gas samples collected from biofilter monitoring ports using glass gas-tight
syringes (Hamilton) were measured using a Hewlett Packard 6890 series gas chromatograph
equipped with a DB-624 Special Analysis Column (60 m , 320 m, 1.80 m, Hewlett Packard) and a
flame-ionization detector (FID) as described previously.15 Calibration was performed using certified
gas standards (BOC Gases) [44, 45].
In Sweden there are three fuel producing oil refineries. On top of that there are also oil refining
facilities for other products like bitumen and lube oil. Out of the total of five oil refineries in Sweden
four lie in the Province of Västra Götaland and out of these, three are situated in the town of Göteborg
(Gothenburg) .

Emissions of volatile organic compounds (VOC) historically were only roughly calculated either as
a figure based on throughput, or on the number of certain process-units in the plant multiplied by
certain theoretical emission data. The data used in this research consists of both comparable data for
a number of years at those sites where the highest number of measurements have been carried out,
the Preem and Scan raff refineries, as well as data showing typical changes in emission levels due to
variations in the conditions of some of the equipment at the Scan raff refinery. All presented data are
exclusive of methane, as methane has a completely different environmental impact than does the
other VOC’s – although they also within themselves show big differences in environmental impact
– as methane is more of a green house gas than anything else. A rough guess is however that methane
could add some 10-20% on top of the total emission as a rough approximation, and then of course
varying with site, equipment, service and with time. Some specific measurements have also been
carried out on the Swedish refineries to indicate typical levels of methane emissions for crude oil
tanks and the waste water treatment. Methane in these exercises have amounted to 12-33% of the
total NMVOC-emissions for the crude oil storage and being as high as 50-80% of the NMVOC-
emissions from the WWT. Measurements on the Swedish sites have been carried out with two
different systems, the Spectrasyne (former BP Research) system which can measure both in the
infrared (alkanes etc.) and the ultraviolet (aromatics) and the Shell Research system which only can
measure in the infrared (alkanes etc.) [16].

Study the performance of a trickle bed reactor for phenol degradation in refinery wastewater by
investigating the applicability of a commercial 0.5% platinum/alumina catalyst, which is used
currently for desulfurization process in the North Refinery Company-Iraq. Synthetic wastewater
experimentally was prepared to simulate the specification of samples taken from North Company
Refinery. Results showed that initial phenol concentration had adverse effect on phenol removal.
The results exhibited that the highest phenol conversion of (98.47%) was obtained over 0.5% Pt/γ-
Al2O3 at the studied conditions (i.e., operating pressure 0.8 Mpa, operating temperature 1200C,
LHSV 2.5 h-1 , and air superficial velocity 0.25 m/s), with initial phenol concentration of 200 mg/L.
The present method characterized by low residence time, the end products are environmentally
harmless no sludge production which requires further treatment. Finally, the highest phenol
conversion (98.4 %) was achieved under operating conditions (LHSV=2.5h-1 ,

16
temperature=120°C,superficial gas velocity =0.25m/s, and initial phenol concentration=200mg/l), It
was found that phenol conversion increases with increasing gas flow rate . Increasing reactor
temperature from (85) to (120)˚C enhanced phenol conversion from(74%) to (88%),and that
conversion of phenol is independent of inlet phenol concentration, When phenol concentration in
solution was decreased from 5000 ppm to 900 ppm, an increase of 98% to 98.47 was obtained for
phenol conversion. The effluent of the process was merely CO2 and slight acidic water without any
sludge which favours this process over other conventional treatments [46, 47].

E) Materials and methods

The overall objectives of wastewater treatment unit at Iraqi refineries are to: (1) equalize flow
and pollutant load by buffering flow surges in large tanks, (2) separate free and emulsified oils
and solids from the wastewater by oil/water separators and flotation unit operations (e.g.,
dissolved air flotation [DAF], induced air flotation [IAF], biological treatment basin, and sludge
treatment unit

- Taking SYSTEMATIC samples from emission gases around the light oil units ,and water
samples from wwtp
- Analysing the air emissions by dragger tubes and listing VOC types in this samples.
- Analysing the waste water samples by mass-GC or HPLC.
- Estimate the emitted sources and emissions.
- Reducing these water pollutant by using adsorption unit with adsorbent (activated carbon,
catalysts)
- suggest the unit treatment

Waste Water Treatment unit in dura-refinary

17
 F) Expected resulete

1- Estimation of PAHs emissions

VOC expected to capture by dragger tubes or zenifer device (active limits) (methane VOC to non-
methane VOCs) with different concentrations.

2- Reducing of PAHs emissions:

Control and treatment for PAHs from WWTP pons emissions By ADSORBING UNIT Using
absorber such as (activated carbon) or (catalyst). It is expected to reduce the VOC (PAHs)
concentrations.

Expected Results indicated that the adsorption of VOCs from WWTP by absorbent such as activated
carbon can mainly remove VOCs efficiently in stable operation (about 50-75 %). By cost estimation,
it was demonstrated that the activated carbon unit was an economic, environmentally requirements
and effects, energy-saving and low maintenance system to improve the quality of the atmospheric
environment of the WWTPs.

Time Table:

Duration
Row Research Steps Start Finish
(month)

1 Literature Review 1401/06 1402/06 12

2 Sampling and Analysis 1402/01 1402/12 12

3 Emission and Sources Analysis 1402/10 1403/02 4

4 Adsorption Pilot Preparation 1403/01 1403/03 2

5 Adsorption and analysis 1403/03 1403/08 5

6 Dissertation compilation 1403/08 1403/11 3

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