TRENDS IN TREATMENT OF GASEOUS EMISSIONS

LATEST TRENDS IN TREATMENT AND MITIGATION OF

GASEOUS EMISSIONS IN REFINERIES
T. Chris McDonald, Jacobs Engineering Group Inc.; Victor Kwentua, Jacobs
Engineering Group Inc and Paula McDonald, Jacobs Engineering Group Inc.
Abstract. Typical refinery gaseous emission source types and the latest worldwide trends in
treatment and mitigation of emissions from these sources will be discussed. These sources will
include fluid catalytic cracking units, process vents, combustion sources, gasoline loading racks,
storage tanks, wastewater treatment systems and equipment leaks. Modern technologies and
practices used to achieve various degrees of emission reduction will also be discussed.
Emissions of criteria pollutants, including volatile organic compounds (with hazardous air
pollutants as a subset), sulfur oxides, hydrogen sulfide, nitrogen oxides, carbon monoxide, and
particulate matter will be discussed for each source type to establish a basis for evaluating control
practices and trends.
Site-specific requirements including regulations permit conditions and other socio-economic
factors that typically drive a specific level of control will be discussed.
In conclusion, the worldwide trend towards further reduction of refinery gaseous emissions,
available control options, and the impact of site-specific requirements on the selection of an
emission control technology will be summarized.
level of control, the treatment and mitigation
methods are presented as increasing degrees of
control.
Site-specific requirements that typically
drive action and that are the reasons for the
greening trends are discussed.

INTRODUCTION
The greening of the petroleum
refining industry is a trend that is impacting
and will continue to impact petroleum refining
operations all over the world. Other industries
face their own environmental challenges, and
some generate more waste materials. But none,
according to recent research conducted by
Pollution Engineering magazine and Cahners
Business Information, spends more to control
its emissions and discharges than the
petroleum refining industry: a projected $8.6
billion in 2000 alone. [1]
A summary of typical (1) refinery
emission sources along with associated
pollutants and a discussion of modern
technologies and practices used to achieve
various degrees of emission reduction are
provided to establish a basis for evaluating
control practices and trends. Since there are
many different factors that can drive a specific

1.

EMISSION SOURCES AND

ASSOCIATED POLLUTANTS

A summary of the type of pollutants

typically associated with a refinery is provided
in Table 1. Table 2 provides a list of typical
refinery emission sources, along with
associated pollutants. The intent of such a
listing is not to encompass all refinery
emission sources, but to adequately represent
the most significant emission sources and
sources most typically targeted for emission
reductions.

5. Table 1 - Typical Refinery Pollutants

Volatile Organic Compounds (VOCs)
Hazardous Air Pollutants (HAPs)*
Sulfur Oxides and Hydrogen Sulfide (SOx and H2S)
Nitrogen Oxides (NOx)
Carbon Monoxide (CO)
Particulate Matter (PM/PM10/P.M 2.5 )
* Subset of VOCs (e.g., benzene, toluene, ethyl benzene, xylenes, hexane)
Table 1 Typical Refinery Pollutants

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TRENDS IN TREATMENT OF GASEOUS EMISSIONS

1.1.1. Table 2 -Typical Refinery Emission Sources and

Associated Pollutants
Associated Pollutants
PM
CO NO
1.1 Emission Source Type
SOx H2S
x

VOC

HAPS
*

Fluid Catalytic Cracking Units

X
X
X
X
X
X
Process Vents
X
X
X
Combustion Devices (Process
X
X
X
X
X
X
Heaters and Boilers)
Gasoline Loading
X
X
Storage Tanks
X
X
Waste Water Treatment Systems
X
X
X
Equipment Leaks (valves, pump
X
X
and compressor seals, safety
valves, sampling systems, openended lines and connectors)
* HAPs (e.g., benzene, toluene, ethyl benzene, xylenes, hexane) are subsets of VOC
Table 2 Typical Refinery Emission Sources and Associated Pollutants
1.2

refineries that control the releases due to a

large associated increase of SOx emissions.

Fluid Catalytic Cracking Units

(2)

Fluid Catalytic Cracking Units

(FCCU) are a major source of PM, NOx, SOx
and CO emissions. As such, FCCUs are a
primary target for emission reduction
programs and regulations. The current trend
suggests that these units will be further
regulated and will be a focal point for
enforcement actions in the future.
1.3

1.4

Combustion Sources

(4)

Combustion sources typical of

refinery operations include process heaters,
boilers, engines and thermal destruction
control devices such as flares and thermal
oxidizers. These sources result in emissions of
NOx, SOx, CO, PM and VOCs. The quantity
of emissions is highly dependent on the type of
fuel and the nature of the contaminants in the
material to be burned. For example, natural gas
and desulfurized refinery fuel gas are clean
fuels relative to coal, fuel oils or refinery fuel
gas, which have not been desulfurized.
Removing sulfur from fuel sources reduces
NOx, PM, CO and VOC emissions in addition
to the obvious SOx emission reductions.
Therefore, a clean fuel strategy can be an
important strategy for refinery emission
reductions. This desulfurized fuel fact is also
the driver for the trend towards gasoline sulfur
removal.
The majority of emissions from
combustion sources in refineries come from
process heaters and utility boilers with high
firing rates. The primary pollutant of concern
with respect to emission control trends for
these types of sources is generally NOx.

Process Vents

Process venting can be a primary

source of VOC, HAPs, and H2 S emissions in
refineries. (3) Refinery process vents include
those from reactors, absorbers, distillation
towers, condensers, and vacuum hotwells.
Historically, the no condensable portion of the
vapours has been or in some cases still is
vented to the atmosphere. Some of these
emission points contain significant levels of
H2S as well as VOCs since they are not
typically desulfurized prior to venting.
Another trend with respect to process
venting that should be factored into emission
reduction planning is the control of start-up,
shutdown and malfunction emissions. This is
an area that continues to get more and more
attention, especially for refineries that do not
have refinery-wide flare systems and/or have
what is viewed as an excessive amount of
start-up, shutdown or malfunction release
events. Problems with acid gas (H2S) removal
equipment are of particular concern even with

1.5

(5) Gasoline Loading Racks

Refinery product loading and

unloading operations result in emissions of
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TRENDS IN TREATMENT OF GASEOUS EMISSIONS

allow gravity flow. VOC and HAP emissions

result from these vents as fluid is drained to
the sewer.
Emission rates decrease through the
collection and treatment train equipment as
more and more free phase oil is removed.
Therefore, emission reduction priorities
typically correspond accordingly.
Sour water streams containing high
levels of H2S are typically segregated from the
refinery wastewater treatment system and
routed to a sour water stripper.

VOCs and HAPs. Since gasoline is a highvapour pressure material with a high
concentration of HAPs, gasoline-loading
operations are typically primary targets for
emission control.
1.6

Storage Tanks

(6)

Storage tanks in refineries are

significant sources of VOC and HAP
emissions. Storage tanks that vent to the
atmosphere have air and organic vapour inside
the tank. As the temperature rises and falls, the
tank breathes. The vapour pressure and
storage temperature of the stored fluid
therefore directly relates to the amount of
material that results in emissions. Typically,
control requirements for these sources become
more stringent as fluid vapour pressure and
storage temperature increase.
1.7

1.8

Equipment Leaks

(8)

Equipment leaks or fugitive

emissions result in emissions of VOCs and
HAPs. Fugitive emissions of VOCs from a
single piping component are small. However,
there are such a large number of components
in a typical refinery that fugitive emissions in
total are significant. In many refineries that
have controlled other sources, fugitive
emissions are actually the largest source of
VOC and HAP emissions. Equipment types
that typically are targets for emission control
in this category include valves, pump and
compressor seals, safety valves, sampling
systems, open ended lines and connectors or
flanges.

Wastewater Treatment Systems

(7)

Refinery wastewater treatment systems

are sources of VOC and HAP emissions and
for plants with uncontrolled sour water
strippers, significant H2 S emissions. They
typically consist of numerous emission
sources, including flashing losses from sewer
hubs and losses from catch basins, manholes,
sumps, lift stations, storm water and process
water surge tanks and surface impoundments,
wastewater
strippers,
oil/water/solids
separation devices (including primary and
secondary), equalization tanks, pH control
systems, biological treatment systems,
clarification equipment, and breathing losses
from recovered oil tanks. Generally,
wastewater treatment systems handle mixtures
of hydrocarbons and water that are highly
variable in composition and flow.
Sewer manholes connect networks of
sewer hubs throughout a typical refinery sewer
system. Conventional gravity-flow sewer
systems typically have water seals to prevent
the propagation of fire and explosion from one
area of a facility to another. Due to the
presence of these seals, vents are required to

2. TREATMENT AND MITIGATION

Various types of emission treatment
and mitigation methods for the source types
described previously are evaluated in this
section. Table 3 provides a summary of the
types of emission controls available for each
source type. Note that the emission controls
presented are grouped in three separate
categories, Levels 1 through 3, only for ease in
discussing different degrees of control. In
reality, there are many combinations of control
techniques that may be used for each source
type. These "level" categories should serve as
guidelines in evaluating a desired specific
degree of control.

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TRENDS IN TREATMENT OF GASEOUS EMISSIONS

2.1.1. Table 3 - Varying Levels of Emission Control

2.1 Emission
Level 1
Level 2
Level 3
Source Type
Fluid Catalytic
Cracking Units

Cyclones for PM

Process Vents

Venting
Minimization

Combustion Devices
(Process Heaters and
Boilers)

Low excess air

Low NOx
burners

Gasoline Loading

Submerged
loading
Fixed roof

Storage Tanks

Waste Water
Treatment System

Controlled
primary oil/water
separator and
controlled sour
water stripper

Equipment Leaks
(valves, pump and
compressor seals,
safety valves,
sampling systems,
open-ended lines and
connectors)

Leak detection
and repair
(LDAR)

Electrostatic
precipitators
(PM) Desox
catalyst (SOx,
NOx,)
CO catalyst
(CO)
Thermal
destruction

Ultra low NOx

burners
External flue
gas
recirculation
Vapor balancing
Fixed roof and
Internal floating
roof or external
floating roof
Sealed/controlle
d collection
systems and
controlled
dissolved gas
floatation
Leak detection
and repair
(LDAR) with
lower leak
definition

Feed desulfurization (SOx, NOx),

Gas scrubbing (PM, SOX, NOx),
Catalytic reduction (NOx, CO),
Waste heat boiler (CO)

Desulfurization and thermal

destruction
Redundant H2S removal and sulfur
recovery capacity
Selective catalytic reduction (SCR)
Non Selective Catalytic Reduction
(SNCR)

Vapor control system

Closed vent system and vapor
control

Totally sealed collection and

controlled treatment equipment
including biological treatment and
VOC strippers

Dual mechanical seals for pumps

and compressors; sealless design for
valves and pumps; rupture disk
assembly for pressure relief devices;
closed vent system for pumps,
pressure relief devices and
compressors; welded connectors;
closed-loop sampling; blinds, caps,
plugs, or second valve for openended lines; and quality
improvement for problem
equipment

Table 3 Varying Levels of Emission Control

removal of particulate matter and the use of
2.2
Fluid Catalytic Cracking Units
special catalysts to limit combustion product
formation during the catalyst regeneration
The first level of control is internal to
process. These catalysts are typically used
the FCCU regenerator. Cyclones are used to
when only a limited emission reduction is
remove particulate matter that results from the
needed or when the increased operating cost
catalyst regeneration process.
can be justified versus other control methods.
A second level of control can include
an electrostatic precipitator for additional
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TRENDS IN TREATMENT OF GASEOUS EMISSIONS

effective in refineries than costly flue gas

treatment. However, emissions from some
combustion sources (e.g., boilers) can also be
controlled using flue gas treatment. Carbon
monoxide and hydrocarbon emissions are
typically minimized using good combustion
controls.
The majority of emissions from
combustion sources in refineries come from
process heaters and utility boilers with high
firing rates with NOx typically being the
pollutant of concern.
Numerous technologies are used to
control NOx. The first and second levels of
control for these sources are pre-combustion
techniques. These are the methods most
commonly used in refineries.
The first level of control includes low
excess air and low NOx burners. The low
excess air is the simplest method and yields a
moderate NOx reduction. Low NOx burners
reduce NOx by accomplishing the combustion
process in stages. The staging effect delivers a
desired air/fuel ratio, which in turn results in
low NOx emissions.
The second level of combustion
control includes ultra low NOx burners and
external flue gas recirculation. The ultra low
NOx burners are very similar to the low NOx
burner except for the addition of flue gas in the
internal of the burner and subsequent higher
NOx reduction. External flue gas recirculation
involves recycling flue gas back to the burner.
This reduces the oxygen concentration in the
combustion zone and also lowers the flame
temperature, which ultimately reduces NOx
formation.
The third level of control is the postcombustion technologies. Two types of postcombustion control technologies include
selective catalytic reduction (SCR) and
selective no catalytic reduction (SNCR). The
SCR technology uses ammonia injection
upstream of a catalytic reactor. The SNCR
technology involves injecting ammonia or urea
into the furnace exit region. These devices are
typically only used in refineries in extreme
cases. [2]

The catalysts are typically used to achieve

reductions in SOx, NOx and CO.
A third level of control can include
desulfurization of the FCCU feed. This
approach eliminates SOx emission concerns
and also results in a reduced level of other
combustion product pollutant emission
formation. This approach can be particularly
attractive in situations where FCCU feed
desulfurization is also part of refinery gasoline
sulfur reduction strategies. Other third level
controls can include add-on devices such as
scrubbers for PM, SOx and NOx; catalytic
reduction reactors for NOx and CO; and waste
heat boilers for CO. Note that wet scrubbers
are more common/proven in FCCU
applications than catalytic reduction reactors.
Emission reduction strategies for FCCU
operations can be complex and are highly
dependent on refinery specific requirements
and constraints.
2.3

Process Vents

The first level of control for process

vents is to minimize venting by routing vent
streams back into the process (e.g., the refinery
fuel gas system) and through work practices to
limit start-up, shutdown and malfunction
emissions. The trend is towards more
comprehensive
equipment
preventative
maintenance programs, written procedures and
training programs with an emission
minimization focus.
The second level of control involves routing
vent streams to a control device. In refineries,
thermal destruction devices are typically used.
The third level of control involves
H2S removal and use as refinery fuel gas. In
this case only excess fuel gas is then vented to
the control device. Another third level concept
for problem equipment is redundant processing
capacity. An example of this is refinery fuel
gas H2S removal systems, which are typically
amine units and sulfur recovery units. The
trend is towards multiple trains with redundant
capacity for these critical systems, which
prevents
high-level
sulfur
compound
emergency release events.
2.4

2.5

Combustion Sources

Gasoline Loading Racks

Emissions are generated as gasoline is

loaded. The emission level is highly dependent
on the loading method used.
The first level of control is submerged
loading. There are two types of submerged
loading, the submerged fill pipe method and
the bottom loading method. The submerged fill
pipe extends almost to the bottom of the cargo

One significant trend for refinery

combustion device pollution mitigation is the
use of clean fuels as described in Section
1.3. Eliminating the use of coal, fuel oils and
refinery fuel gas containing H2S in favour of
desulfurized fuel gas and/or natural gas is a
common trend used when emission reductions
are needed. This approach is typically more
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TRENDS IN TREATMENT OF GASEOUS EMISSIONS

device). Care in the design with respect to

explosive mixtures should be taken any time
refinery wastewater systems are covered.
Vapours stripped from sour water are routed to
sulfur recovery.
A second and greater level of control
includes sealed and/or controlled collection
systems, and a controlled dissolved gas
floatation unit. Emissions from manholes and
sewer system vents can be controlled using
granulated
activated
carbon
canisters.
However, numerous carbon canisters result in
significant capital cost, they require routine
monitoring and tend to be high-maintenance
items. In addition, carbon canisters are not
practical for systems with high surges, which
can rapidly exhaust the capacity of the carbon.
[4] Dissolved gas floatation units are typically
controlled using a thermal destruction device.
A third level of control consists of a
totally sealed (usually hard piped) collection
system and controlled treatment equipment
including biological systems and in some cases
VOC strippers. These hard piped collection
systems cost more but have the added benefits
of storm water segregation and the reduction in
the potential for site soil and groundwater
contamination.

tank. In the bottom loading method, a

permanent fill pipe is attached to the cargo
tank bottom. The pipe in both of these loading
systems significantly helps to control liquid
turbulence, resulting in lower vapour
generation.
A second level of control is vapour
balancing. This method involves routing
vapours generated back to another vessel or
storage. Vapour balancing is usually not
practiced with marine vessels due to routing
distances.
A third level of control includes a
vapour control system, which in a refinery is
typically a vapour collection system and a
thermal destruction device.
2.6

Storage Tanks

The first level of control is a fixed

roof. Fixed roof tanks consist of cylindrical
shells with permanently affixed roofs. These
tanks are typically used for lower storage
temperature vapour pressure fluids (5 to 20
kPa depending on tank size).
A second level of control is a fixed roof with
an internal floating roof (IFR) or an externalfloating roof (EFR). The floating roofs are
equipped with floating decks designed to float
in contact with the stored liquid and primary
and secondary seals that close the space
between the floating roofs and the tank shells.
This minimizes the free liquid surface, which
in turn minimizes emissions and under surface
corrosion. The type of seal used also affects
the degree of emission control. Typically, the
second level of control is used on larger tanks
(greater than 75 m3) with liquid storage
temperature vapour pressures below 76 kPa.
A third level of control includes closed
vent systems and add-on control equipment
(vapour recovery or thermal destruction
depending on site specifics). Typically, the
third level of control is used on larger tanks
(greater than 75 m3) with liquid storage
temperature vapour pressures above 76 kPa.
[3]
2.7

2.8

Equipment Leaks

The first level of emission control for

equipment leaks, or fugitive emissions, is
through implementation of a leak detection and
repair (LDAR) program, which utilizes
periodic monitoring to locate leaking
components, followed by prompt repair of the
leaking equipment. A first level program
would typically use a higher leak definition
and would not include monitoring of
connectors. A second level program includes a
lower leak definition and monitoring of
connectors.
A third level of controlling fugitive
emissions
includes,
in
addition
to
implementation of an LDAR program, various
equipment improvements. Dual mechanical
seals for pumps and compressors, or sealless
designs of valves and pumps are examples.
Rupture disks installed upstream of safety
relief devices are used in some cases where
monitoring is not feasible. Other control
methods include closed vent systems for
pumps,
pressure
relief
devices
and
compressors; welded connectors; closed-loop
sampling; blinds, caps, plugs, or second valves
for open-ended lines; and quality improvement
programs for problem equipment.

Wastewater Treatment Systems

The first level of emission control for

wastewater treatment systems includes a
controlled primary oil/water/solids separator
and a controlled sour water stripper, usually
the largest individual emission sources of a
typical refinery wastewater treatment system.
Emissions from the primary oil/water/solids
separation system are typically controlled
using a floating roof or a fixed roof with a
control device (usually a thermal destruction
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TRENDS IN TREATMENT OF GASEOUS EMISSIONS

3.

As shown in Colombia, China, and the

Philippines, plants will choose greater
pollution control when faced with high
payments for emissions. Pollution charges also
generate public revenue, which then support
local efforts for further pollution control.

(9) EMISSION CONTROL DRIVING

FACTORS

The overall worldwide trend is

towards greater emission reduction. It is a
simple fact of business that most refineries will
use the minimum acceptable control level in
order to minimize costs. Increased emission
reductions result only when driving factors
force increased pollution control. What are the
driving factors behind this trend? Driving
factors include regulation; regional pollution
problems that result in more stringent permit
conditions and enforcement, and socioeconomic conditions such as economic
incentives and community awareness. [5]

3.3 Community Awareness

Regulators in some countries are
pressuring plants towards greater control
through community awareness. Simple rating
systems are used to publicly identify plants
that meet and those that do not meet local and
national pollution standards. Other systems
rank plants based on total annual emissions
and publish the information. These public
disclosure programs can be successful even in
countries where there is little or no formal
regulation, and have proven successful in
countries such as Indonesia and the
Philippines.
Public disclosure programs can result
in indirect economic incentives for emission
reductions such as credit refusals from bankers
worried about liability, reduced sales to
consumers who care about the environment,
and social exclusion by communities outraged
by pollution.
An example of the effect of
community awareness on pollution control was
obvious in Indonesia. In the 1980's, the
country's national pollution control agency,
BAPEDAL, was charged with enforcing
standards on industrial plant discharges. Due
to a lack of funds and court corruption, the
agency created a program called PROPER Program for Pollution Control, Evaluation, and
Rating. This program rated plants based on
five performance levels, and the country's Vice
President congratulated the best performers in
a public ceremony. As a result of this program,
50 percent of the plants in the lowest
performance level made improvements to
move from that group within six months. Other
countries, including Mexico, Colombia,
Venezuela, India, Bangladesh, Thailand,
China, Philippines, and Papua New Guinea are
developing or have implemented similar
programs as a result of its success.
Community awareness also plays an
important role in industrialized countries,
where public information is readily available
and the regulation/permitting process requires
public notice and allows comments. This
offers a mechanism for community
participation. Another recent trend to be aware
of is the increase in civil law suits. In many

3.1 Regulations, Permit Conditions and

Enforcement
Some developing countries have just
begun to regulate pollution, while more
developed countries are further reducing
pollution through more stringent regulations,
permit conditions and enforcement programs.
In highly industrialized countries such as the
United States, Japan, France, and Germany
with regional pollution problems this trend is
apparent. There is strong evidence that
economic development correlates with
increased regulation, more stringent permit
conditions and enforcement. It can be
predicted that this trend will continue as
developing countries become more highly
industrialized.
3.2 Economic Incentives
In industrialized countries, capital
markets have been shown to be a factor in
pollution control. Investors may presume that a
high level of pollution relates to an inefficient
production process, and may also weigh
potential financial losses from regulatory
penalties and liability settlements. Therefore,
the environmental performance of a company
can have direct bearing on its stock value.
Studies of the markets of United States,
Canada, Argentina, Chile, Mexico, and
Philippines have proven this to be true. The
resulting trend is towards increased regulatory
compliance, which results in greater pollution
control.
Environmental
regulators
in
developing countries are discovering that it is
difficult to reduce pollution through traditional
regulation and enforcement practices and are
trying other approaches. Regulators in some
countries are turning to financial incentives by
charging polluters for every unit of emissions.
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TRENDS IN TREATMENT OF GASEOUS EMISSIONS

country. Trends towards higher levels of

control are driven by social factors while
operating
company
economics
drives
resistance. These conflicting forces along with
a highly variable playing field explain why
site-specific conditions and requirements play
such a major role in ultimately driving a
specific level of control.
In conclusion, the worldwide trend
towards further reduction of refinery gaseous
emissions is a trend that can be expected to
continue as each refinery with time is impacted
by greening driving factors.

cases, this type of community action has

resulted in increased pollution controls.
4. CONCLUSIONS
Refinery emission treatment and
mitigation techniques for the most part are
well established and readily available
throughout the world. But the simple facts are
that pollution control costs money and
operating companies are forced to balance the
minimization of costs with an acceptable level
of performance to remain competitive. An
acceptable level of performance is a highly
variable concept from country to country and
even from location to location with in the same

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