ExxonMobil Proprietary

AIR POLLUTION CONTROL Section Page

XVIII-A2 1 of 42
CONTROL OF HYDROCARBONS, VOC
DESIGN PRACTICES AND AIR TOXICS EMISSIONS December, 2001

Changes shown by ➧

CONTENTS
Section Page

SCOPE ............................................................................................................................................................4

REFERENCES.................................................................................................................................................4

DEFINITIONS ..................................................................................................................................................6

BACKGROUND...............................................................................................................................................7

CONTROLLING FUGITIVE EMISSIONS ........................................................................................................9

INSPECTION AND MAINTENANCE PROGRAMS .................................................................................9
Procedures .........................................................................................................................................10
Monitoring Instruments .......................................................................................................................11
Data Handling.....................................................................................................................................11
VALVES ................................................................................................................................................12
PUMPS..................................................................................................................................................14
COMPRESSORS ..................................................................................................................................14
CONNECTORS / FLANGES .................................................................................................................14
PRESSURE RELIEF VALVES ..............................................................................................................15
SAMPLING CONNECTIONS.................................................................................................................15
OPEN-ENDED LINES AND VALVES....................................................................................................15
PRODUCT ACCUMULATOR VESSELS...............................................................................................15
AGITATORS..........................................................................................................................................16
CLOSED VENT SYSTEMS AND CONTROL DEVICES .......................................................................16

CONTROLLING TANK EMISSIONS .............................................................................................................16

SOURCES OF VAPOR EMISSIONS ....................................................................................................16
SELECTING APPROPRIATE CONTROLS ...........................................................................................17
Selection of Tank Roof Type ..............................................................................................................17
Floating Roof Seal Selection ..............................................................................................................18
Primary Seals .....................................................................................................................................18
Secondary Seals ................................................................................................................................18
Controlling Emissions from Roof Fittings ............................................................................................19

CONTROLLING LOADING EMISSIONS ......................................................................................................21

MARINE LOADING ...............................................................................................................................22
TRUCK LOADING .................................................................................................................................22
RAIL CAR LOADING.............................................................................................................................22
CONTROL SELECTION........................................................................................................................22
VAPOR RECOVERY.............................................................................................................................23
Vapor Balancing .................................................................................................................................23
Carbon Bed Adsorption ......................................................................................................................23
Lean Oil Absorption ............................................................................................................................24
Refrigeration (Condensation)..............................................................................................................24

ExxonMobil Research and Engineering Company – Fairfax, VA

ExxonMobil Proprietary
Section Page AIR POLLUTION CONTROL
XVIII-A2 2 of 42
CONTROL OF HYDROCARBONS, VOC
December, 2001 AND AIR TOXICS EMISSIONS DESIGN PRACTICES

CONTENTS (Cont)
Section Page
VAPOR DESTRUCTION.......................................................................................................................25
Flares .................................................................................................................................................25
Thermal Oxidizers ..............................................................................................................................25
Catalytic Oxidizers..............................................................................................................................26
Biofilters .............................................................................................................................................27

CONTROLLING WASTEWATER TREATING AIR EMISSIONS ..................................................................28

EMISSION SOURCES ..........................................................................................................................29
Drains.................................................................................................................................................29
Manholes............................................................................................................................................30
Junction Boxes ...................................................................................................................................30
Lift Stations ........................................................................................................................................30
Trenches ............................................................................................................................................30
Sumps ................................................................................................................................................31
Weirs ..................................................................................................................................................31
Oil / Water Separators........................................................................................................................31
Equalization Basins ............................................................................................................................31
Clarifier...............................................................................................................................................32
Biological Treatment / Aeration Basin ................................................................................................32
Treatment Tanks ................................................................................................................................32
Surface Impoundments ......................................................................................................................32
Air Emissions from Sludges or Waste Solids .....................................................................................32
EMISSION CONTROL TECHNIQUES..................................................................................................32
Stripping and Other Techniques to Reduce Concentrations ..............................................................33
Air Stripping........................................................................................................................................34
Biological Treatment...........................................................................................................................34
Other Technologies ............................................................................................................................35
Collection and Treatment System Controls ........................................................................................35
Fixed and Floating Roofs ...................................................................................................................35
Floating Membranes...........................................................................................................................36
Add-On Controls.................................................................................................................................36

MISCELLANEOUS SOURCES .....................................................................................................................36

VACUUM SYSTEMS.............................................................................................................................36
TURNAROUNDS ..................................................................................................................................37
COOLING TOWERS.............................................................................................................................37

RESPONDING TO ODOR COMPLAINTS ....................................................................................................37

ODOR: PERCEPTION, EFFECT, AND CHARACTERIZATION ..........................................................37
STEPS FOR ADDRESSING ODOR PROBLEMS.................................................................................39

ExxonMobil Research and Engineering Company – Fairfax, VA

 ExxonMobil Proprietary
AIR POLLUTION CONTROL Section Page
XVIII-A2 3 of 42
CONTROL OF HYDROCARBONS, VOC
DESIGN PRACTICES AND AIR TOXICS EMISSIONS December, 2001

CONTENTS (Cont)
Section Page

TABLES
Table 1 Major Sources Of Vocs Released To The Air From Process Plants ................................7
Table 2 Controls For Hydrocarbon And Air Toxics Emissions ......................................................8
Table 3 Control Effectiveness Of Inspection And Maintenance (I&M) Programs
(From EPA-625/R-93-005 & EPA-625/6-91-014)...........................................................10
Table 4 Data Collection Suggestions For I&M Programs............................................................12
Table 5 Comparison Of Emission Control Efficiencies For Different Tank Control Options ........19
Table 6 External Floating Roof Tank Seal System Control Efficiencies......................................20
Table 7 Controls For External Floating Roof Tank Deck Fittings ................................................20
Table 8 Internal Floating Roof Tank Seal System Control Efficiencies .......................................21
Table 9 Controls For Internal Floating Roof Tank Deck Fittings .................................................21
Table 10 Comparison Of Vapor Control Options ..........................................................................27
Table 11 Advantages And Disadvantages Of Vapor Control Options...........................................28
Table 12 Steps For Addressing Odor Problems ...........................................................................41

Revision Memo
12/01 1. Editorial revisions.
2. References updated.
3. Revised tank emission reduction tables based on new emission estimating procedures.
4. Fugitive section revised pump guidance and pressure relief valves guidance.
5. Tanks section new guidance on slotted guidepoles.

ExxonMobil Research and Engineering Company – Fairfax, VA

ExxonMobil Proprietary
Section Page AIR POLLUTION CONTROL
XVIII-A2 4 of 42
CONTROL OF HYDROCARBONS, VOC
December, 2001 AND AIR TOXICS EMISSIONS DESIGN PRACTICES

SCOPE
This section of Design Practices discusses the selection of equipment and procedures for controlling air emissions of
hydrocarbons, air toxics and other materials from fugitive sources, atmospheric storage tanks, wastewater collection and
treating systems, and loading operations. It also includes guidance on how to respond to odor complaints.
Detailed design procedures and specifications are, in general, not contained in this DP section. For each of the technology
areas described, the reader is referred to the appropriate DP and GP sections where the additional information is provided.
The reader should also consult with a technology specialist for help in the selection and design of specific control equipment.

REFERENCES
DESIGN PRACTICES
DP II Design Temperature, Design Pressure and Flange Rating
DP X-G Pumps, Shaft Sealing
DP XI Compressors
DP XV-C Safety in Plant Design-Pressure Relief Devices
DP XV-J Safety in Plant Design-Docks, Loading Racks and LPG Storage Facilities
DP XVIII-B Industrial Hygiene
DP XIX-A1 API Separators
DP XIX-A2 Flotation Units
DP XXII Atmospheric Storage
DP XXIII Basic Loading Systems

GLOBAL PRACTICES
GP 3-2-1 Industrial Sewer Systems
GP 3-2-4 Pressure Relief Systems
GP 3-2-7 Manual Sampling Systems
GP 3-6-4 Vents, Drains, Flushing and Cleaning Connections
GP 3-12-1 Valve Selection Criteria
GP 3-12-8 Block Valve Packing Systems
GP 3-15-1 Pressure Relief Valves
GP 3-16-1 Flanges, Gaskets, Bolting and Fittings
GP 9-4-1 Atmospheric Storage Tanks
GP 9-7-1 Accessories for Atmospheric Storage Tanks
GP 9-7-3 Vents for Atmospheric Storage Tanks
GP 9-7-4 Internal Floating Covers for Atmospheric Storage Tanks
GP 10 Pumps, Compressors
GP 15-9-1 Control Valves
GP 15-8-1 Process Stream Analyzers

COMPANY MANUALS, APPLICATION GUIDES AND REPORTS

TMEE-23 EMRE Manual Pump Sealing Technology Manual
TMEE-46 EMRE Manual Emissions Estimating Guide
TMEE-61 EMRE Manual Leak Detection and Repair (LDAR) Manual
EE.72E.94 ER&E Report Odor Control
EE.58E.94 ER&E Report Valve Packing Fire Tests Reinforce Recommendation Not to Use All-Braided Packings

ExxonMobil Research and Engineering Company – Fairfax, VA

 ExxonMobil Proprietary
AIR POLLUTION CONTROL Section Page
XVIII-A2 5 of 42
CONTROL OF HYDROCARBONS, VOC
DESIGN PRACTICES AND AIR TOXICS EMISSIONS December, 2001

REFERENCES (Cont)
EE.19E.94 ER&E Report Biofilters for Air Pollution Control
EE.84E.93 ER&E Report New Low Emission Control Valve Packings Successfully Demonstrated in Plant Performance
Tests
EE.35E.93 ER&E Report Selection Guide for Storage Tank Emission Controls
EE.34E.93 ER&E Report Low Emission Block Valve Packing Guidelines Updated
EE.15E.93 ER&E Report Improved Valve Stem Packing Design Criteria and Materials Selection for Block Valves
EE.101E.92 ER&E Report Plant Performance Evaluation of Traditional Versus New Low Emission Control Valve Packings
EE.38E.92 ER&E Report Testing Low Emission Valve Packings - Results of PERF Project 90-05
EE.32E.92 ER&E Report Five Ring Graphite Packing Systems Effective in Reducing Emissions from Rising Stem Block
Valves
EE.19E.92 ER&E Report Identification and Abatement of Machinery Fugitive Emissions
EEOP ExxonMobil Chemical Company Environmental Engineering & Operating Practices

AMERICAN PETROLEUM INSTITUTE PUBLICATIONS

Manual of Petroleum Measurement Standards, Chapter 19 - Evaporative Loss Measurement.
API 342 Fugitive Emissions from Equipment Leaks I: Monitoring Manual, May 1998.
API 343 Fugitive Emissions from Equipment Leaks II: Calculation Procedures for Petroleum Industry Facilities, May
1998.

CONCAWE REPORTS
85/54 Hydrocarbon Emissions from Gasoline Storage and Distribution Systems
87/52 Cost Effectiveness of Hydrocarbon Emission Controls in Refineries from Crude Oil Receipt to Product
Dispatch
90/52 VOC Emissions from Gasoline Distribution and Service Station in Western Europe Control Technology and
Cost Effectiveness
92/52 VOC Emissions from the Loading of Gasoline into Ships and Barges in EC-12: Control Technology and
Cost Effectiveness

SOCIETY OF TRIBOLOGISTS AND LUBRICATION ENGINEERS PUBLICATIONS

SP-30 Guidelines for Meeting Emission Regulations for Rotating Machinery with Mechanical Seals
SP-32 Guidelines for Meeting Emission regulations for Compressors with Advanced Sealing Systems
SP-33 Guidelines for Controlling Fugitive Emissions with Valve Stem Sealing Systems

UNITED STATES ENVIRONMENTAL PROTECTION AGENCY DOCUMENTS

AP-42 Compilation of Air Pollutant Emission Factors, Fifth Edition, 1995
EPA-454/R-93-032 National Air Pollutant Emission Trends, 1900 - 1992
EPA-625/6-91-014 Control Techniques for Hazardous Air Pollutants
EPA-453/R-95-017 Protocol for Equipment Leak Emission Estimates
EPA-625/R-93-005 Control Techniques for Fugitive Emissions from Chemical Process Facilities
EPA-453/D-93-056 Control of Volatile Organic Compound Emissions from Industrial Wastewater
EPA-453/D-93-057 Control of Volatile Organic Compound Emissions from Volatile Organic Liquid Storage in Floating
and Fixed Roof Tanks
EPA-600/R-92-047 Reference Guide to Odor Thresholds for Hazardous Air Pollutants Listed in the Clean Air Act
Amendments of 1990

ExxonMobil Research and Engineering Company – Fairfax, VA

ExxonMobil Proprietary
Section Page AIR POLLUTION CONTROL
XVIII-A2 6 of 42
CONTROL OF HYDROCARBONS, VOC
December, 2001 AND AIR TOXICS EMISSIONS DESIGN PRACTICES

REFERENCES (Cont)

OTHER LITERATURE
Godish, T., Air Quality, Lewis Publishers, 1991.
Buonicore, A. J., and Davis, W. T., Air Pollution Engineering Manual, Eds., Van Nostrand Reinhold, 1992.
Rethinking the Ozone Problem in Urban and Regional Air Pollution, National Research Council, National Academy Press,
1991.
Lipfert, F. W., Air Pollution and Community Health, Van Nostrand Reinhold, 1994.
Patrick, D. R., Toxic Air Pollution Handbook, Ed., Van Nostrand Reinhold, 1994.
Dravnieks, A., Odor Perception and Odorous Air Pollution, Tappi, Vol. 55, No. 5, 737, May 1972.
Martin, A. M., Nolen, S. L., Gess, P. S. and Baesen, T. A., Control Odors from CPI Facilities, Chemical Eng. Prog., Vol. 88, No.
12, 53, December 1992.
Mukhopadhyay, N. and Moretti, E. C., Current and Potential Future Industrial Practices for Reducing and Controlling Volatile
Organic Compounds, AIChE, 1993.
Turk, A. and Hyman, A. M., Odor Measurement and Control, Patty's Ind. Hyg. Toxicol. (3rd Rev. Ed.) Ed: Clayton, G. D. and
Florence, E., Vol. 1, 665 - 707, 1978.
Odor Thresholds for Chemicals with Established Occupational Health Standards, American Industrial Hygiene Association,
1989.
Toxic Air Emissions from Wastewater Treatment Facilities, Water Environment Federation and American Society of Civil
Engineers, 1995.
Odor Control in Wastewater Treatment Plants, Water Environment Federation and American Society of Civil Engineers, 1995.
Thibodeaux, L. J., Environmental Chemodynamics, 2nd Edition, McGraw-HiII, 1995.

DEFINITIONS
Air Pollutant - Any substance in ambient air which is present above its normally occurring standard concentration. This
pollutant may or may not be harmful and can include naturally occurring substances such as volcanic dust. Air Pollutants
generally include the emissions from industrial and agricultural activities; from transportation sources such as cars, buses,
trains and ships; and also from the treatment of human and animal wastes. Almost any human or animal activity, or any natural
occurrence, can generate an air pollutant. Many regulatory agencies have developed lists of specific air pollutants which they
have the authority to control.
Air Toxic - A pollutant that has the potential to cause adverse effects in the general population or the environment above a
specified concentration.
Ambient Air Quality - A measure of the relative concentration of species in air compared to a concentration limit which may
have an adverse effect on humans, animals, vegetation, materials, structures, visibility, or the quality of life. Many regulatory
agencies have developed concentration limits for specific air pollutants. These limits are often different for indoor and outdoor
air as well as for worker and community exposure. There may also be more than one limit based on the adverse effect being
considered.
Anthropogenic Emissions - These are emissions from “man-made" sources or activities. They include industry,
manufacturing, transportation, agriculture, waste treatment, households, and all other sources which are not naturally occurring.
Ozone (Tropospheric or Ground Level) - A compound, O3, that is a principal component of smog and that can be formed in
the atmosphere from the reaction of volatile organic compounds and nitrogen oxides in the presence of sunlight.
Primary Air Pollutant - An air pollutant that is in the same chemical form as when it was released, although the concentration
of the pollutant may be changed.
Secondary Air Pollutant - An air pollutant that is present in a form other than as originally released. Secondary Air Pollutants
are formed in the atmosphere by the reaction of one or more Primary Air Pollutants.
Smog - A complex mixture of substances that form in the atmosphere as a result of chemical reactions involving volatile
hydrocarbons, nitrogen oxides and sunlight. Ozone is a predominant species in smog.
Volatile Organic Compound (VOC) - Compounds containing carbon that react with nitrogen oxides in the presence of sunlight
to form ozone.

ExxonMobil Research and Engineering Company – Fairfax, VA

 ExxonMobil Proprietary
AIR POLLUTION CONTROL Section Page
XVIII-A2 7 of 42
CONTROL OF HYDROCARBONS, VOC
DESIGN PRACTICES AND AIR TOXICS EMISSIONS December, 2001

BACKGROUND
Since refineries and chemical plants handle large quantities of volatile organic compounds (VOCs), some emissions of these
compounds occur during normal operations. The largest source of VOCs is typically fugitive emissions (e.g., valves, flanges /
connectors, pumps, compressors and other “piping" components). VOC emissions also come from storage tanks, loading
operations, and wastewater treating. Table 1 shows the major sources of VOC emissions to the air from process plants. The
relative percents vary depending on the specific processes employed and the type of emissions controls installed. In almost all
cases, fugitive emissions are the largest source of VOCs and air toxics. In those locations with large uncontrolled marine, rail,
or truck loading facilities, loading emissions may also be high. In locations that have implemented a fugitives control program,
and have large but uncontrolled loading emissions, the contribution from loading may exceed that from fugitives. Air emissions
from tanks and wastewater treating are usually smaller than those from fugitives and loading.
TABLE 1
MAJOR SOURCES OF VOCS RELEASED TO THE AIR FROM PROCESS PLANTS

SOURCE TYPICAL PERCENTAGES*

Fugitive Equipment Leaks 40 - 60
Loading 20 - 30
Wastewater Treating 5 - 15
Storage Tanks 5 - 15
Process Vents 5 - 15

* Actual values vary based on plant configuration and existing controls.

Emissions of VOCs often must be controlled due to regulations which limit the emissions based on their potential to react with
nitrogen oxides to form ozone and also since some VOCs are considered toxic. Additional background on the contributions of
VOC to ground level ozone is contained in the 1991 National Research Council report. Air toxics issues are reviewed in the
1994 text by Lipfert. Some VOCs also have the potential to cause annoying odors in the communities surrounding process
plants.
The most applicable and economic control system will depend on the specific emission source, the level of controls already in
place, and the target emission level. Controls range from increased monitoring and maintenance frequency for valve leaks, to
replacing rim seals on floating roof tanks, to installing a complete vapor control system at a loading facility. The costs can vary
widely. Table 2 lists options for controlling emissions of hydrocarbons and air toxics. These are discussed in more detail in the
remainder of this DP section.
Health effects from exposure to air pollutants above certain concentrations include irritation of the eyes, nose, and throat, and
respiratory and cardiovascular distress. Different effects may result from either short or long term exposures. The effects of
exposure to air pollutants is discussed in Section XVIII-B1. More detailed information may be obtained from your local
industrial hygienist or from ExxonMobil Biomedical Sciences, Clinton, N.J.
Regulations to control air pollution may require the application of specific control equipment or practices, place limitations on
the emission rates of specific chemicals, or require the assessment of risk. It is important to determine which specific
regulations may apply in each situation before selecting any air pollution controls. Contact the plant environmental coordinator
for the most recent applicable regulations.
When equipment or practices are specified, it is often possible to substitute alternatives which result in an equivalent effect on
the quality of the ambient air. In most cases, these alternatives include the choice of equipment on a specific emissions source
or a nearby source of the same pollutant. More recently, emissions trading between different companies and even different
pollutants has been utilized. Check with the local regulatory agency to determine if these alternatives are an option.
The following subsections provide details on control equipment and procedures for the sources listed in Table 1. Care should
be taken in applying these approaches that all the requirements of the appropriate GPs and DPs are considered. Check the
reference list for GPs and DPs related to this DP section. In addition, a technical specialist in each area should be consulted
for help in selecting and designing specific control equipment.

ExxonMobil Research and Engineering Company – Fairfax, VA

ExxonMobil Proprietary
Section Page AIR POLLUTION CONTROL
XVIII-A2 8 of 42
CONTROL OF HYDROCARBONS, VOC
December, 2001 AND AIR TOXICS EMISSIONS DESIGN PRACTICES

BACKGROUND (Cont)
TABLE 2
CONTROLS FOR HYDROCARBON AND AIR TOXICS EMISSIONS
FUGITIVE EMISSIONS
Initiate a leak detection and repair program.
Install new packing sets in block and control valves.
Upgrade pump and compressor seals.
Consider “on-line" valve repair for large leakers.
Route pressure relief valves to flare system or install rupture disks upstream.
Use of leakless technology such as bellows valves and canned pumps.
TANK EMISSIONS
Fixed Roof Tanks
– Install vapor balance system.
– Install vapor recovery / destruction.
– Install internal floating roof.
External Floating Roof Tanks
– Check condition of existing seals.
– Replace vapor-mounted primary with liquid-mounted primary seal.
– Control losses from roof fittings.
– Install sleeve on slotted giodepole.
– Install secondary rim seal.
– Convert tank to internal floating roof design.
– Install vapor recovery / destruction after conversion to internal floating roof design.
Internal Floating Roof
– Check condition of existing seals.
– Replace vapor-mounted primary seal with liquid-mounted seal.
– Control losses from roof fittings.
– Install secondary rim seal.
– Install vapor recovery / destruction.
WASTEWATER TREATING EMISSIONS
Decrease wastewater volume and organic concentrations by improved housekeeping and source reduction.
Optimize stripper operation.
Install sewer system emission suppression (e.g., P-traps on drains).
Reduce air / water contact area (covering, nitrogen blanketing, etc.).
Replace API separator with covered corrugated plate separator.
Replace DAF with covered IAF.
LOADING EMISSIONS
Use “submerged" loading in place of “splash" loading.
Use vapor balancing during loading.
Install vapor recovery / destruction system.
VENTS
Route to flare.
Install vapor recovery / destruction system.

ExxonMobil Research and Engineering Company – Fairfax, VA

 ExxonMobil Proprietary
AIR POLLUTION CONTROL Section Page
XVIII-A2 9 of 42
CONTROL OF HYDROCARBONS, VOC
DESIGN PRACTICES AND AIR TOXICS EMISSIONS December, 2001

CONTROLLING FUGITIVE EMISSIONS

Fugitive emissions, also known as “equipment leaks", are emissions from valves, connectors / flanges, pump and compressor
seals, pressure relief valves, and other “piping components" located throughout any process plant. Although these emissions
are sometimes visually detected, they are most often located with sensitive gas detection instruments placed adjacent to the
leak point. When environmental engineers refer to levels of fugitive emissions, they typically use parts-per-million (ppm) values
measured with these instruments.
Although fugitive emissions from a single piping component are in most cases extremely small, there are such a very large
number of components throughout a process plant that fugitive emissions are usually the largest source of hydrocarbons and
air toxics. Approximately half of the total fugitive emissions are from valves. The next largest contributors to fugitive emissions
are generally connectors and flanges. As locations continue to reduce valve and pump emissions through monitoring and
better equipment, connectors and flanges may become a much larger percentage of the total fugitive emissions.
Fugitive emissions can be controlled in several ways. In order of increasing cost these are: monitoring and maintenance; use
of lower leak equipment; collecting emissions; and use of “leakless" technology. The choice will depend on the current and
anticipated need for emissions control; equipment configuration; and the current plant performance.
Control techniques for fugitive emissions can be work practice and/or equipment related. The most cost effective control
measure to reduce fugitive emissions is to initiate an inspection and maintenance (I&M) program (also known as Leak
Detection and Repair - LDAR or monitoring and maintenance - M&M). For those locations without any current controls,
instituting an annual I&M program may, in some cases, reduce losses an amount exceeding the cost of the program. Actual
emission reductions depend on the current condition of the components, with reductions of at least 50 to 75 percent being
typically achieved compared to average factor emission estimates. These programs can be optimized by more frequent
inspection of those components found to be leaking more frequently.
An I&M program consists of using a sensitive gas detection instrument and sampling each piping component individually to
determine the concentration of hydrocarbon adjacent to a potential leak point (e.g., the packing gland on valves or the seal on
pumps). If the instrument detects hydrocarbon above a predetermined “leak" level, the equipment is repaired. The definition of
“leak" level depends on local regulations, although 10,000 ppm is a generally accepted leak level. In some US locations, new
regulations set the “leak" definition as low as 100 ppm for valves and connectors / flanges and 500 ppm for pumps and
compressors. Two European Plastics Plants have used trained dogs as a pre-screening technique to reduce the number of
components that need to be monitored using instruments.
Initial repairs for valves include tightening the packing gland to further compress the packing and seal the leak path (The
packing gland should not be so over tightened that it prevents movement of the valve stem). If this is not successful then, when
the valve is next out of service, the packing may need to be replaced with a new improved “low emission" packing design. In
cases where the valve stem is corroded or there are other mechanical problems, the valve may need to be replaced during the
next turnaround. Pump emissions may be reduced by using a multiseal design with a fluid barrier or essentially eliminated by
the use of “canned" or magnetic drive designs. Additional equipment controls include rupture discs and soft seats for pressure
relief valves, plugs, caps, and blinds for open ended lines and closed loop sampling systems.

INSPECTION AND MAINTENANCE PROGRAMS

The emissions reduction potential for an I&M program depends on several factors including the frequency of monitoring, the
leak definition level, and the current performance. Programs that have higher monitoring frequencies and lower leak definitions
will generally result in a greater reduction of fugitive emissions. The following subsection provides guidance in establishing an
I&M program. For additional details see the Leak Detection and Repair Manual, TMEE-061.
Although fugitive emissions for plants with an I&M program have been found to be at least 50 to 75% lower than emissions
estimated using “average" factors, the actual reductions attributable to the I&M program are smaller. This is due to the
application of newer technologies and practices as compared to when the original data that was used to develop the average
emission factors were collected in the late 1970s. Table 3 provides estimates of the range of I&M program control
effectiveness (i.e., the reduction that can be achieved when implementing a program where none previously existed) based on
studies in both refineries and chemical plants.

ExxonMobil Research and Engineering Company – Fairfax, VA

ExxonMobil Proprietary
Section Page AIR POLLUTION CONTROL
XVIII-A2 10 of 42
CONTROL OF HYDROCARBONS, VOC
December, 2001 AND AIR TOXICS EMISSIONS DESIGN PRACTICES

CONTROLLING FUGITIVE EMISSIONS (Cont)

TABLE 3
CONTROL EFFECTIVENESS OF INSPECTION AND MAINTENANCE (I&M)
PROGRAMS (FROM EPA-625/R-93-005 & EPA-625/6-91-014)

PERCENT EMISSIONS REDUCTION

COMPONENTS ANNUAL QUARTERLY MONTHLY
MONITORING MONITORING MONITORING

Valves - Gas 24 59 - 64 70 - 73

Valves - Light Liquid NA 44 - 63 59 - 73

Pumps - Light Liquid NA 33 - 71 61 - 83

Pressure Relief Valves NA 44 53

Compressors NA 33 NA

NA: Not available

Procedures
The purpose of a monitoring program may be to reduce emissions, collect data, or both. In locations without reporting
requirements, it is to identify leaking components and conduct repairs so that emissions are reduced. The first step in starting a
program is to determine which components will be included. Initially some programs may only include valves and pumps, or
just valves in light liquid service. Components in heavy liquid services and connectors and flanges are usually not monitored.
Components may be identified based on a piping and instrumentation flow diagrams and unit inspections. Process streams
should be followed in a logical order to identify all potential fugitive leak sources which may be included in the monitoring
program. Tags or other markings on the components to be monitored greatly facilitate the effort if there is a need to collect and
report the monitoring data on an individual component basis.
One method of monitoring is described in US EPA Method 21 and associated manuals (see EPA-453/R-95-017 and the API
Monitoring Manual, Publication 342). Using this method, monitoring readings for non-moving components (e.g., valves,
flanges, connectors) are obtained by placing the instrument probe at the surface of the leak interface where leakage could
occur and within 1 cm of the leak interface for moving components (e.g., pumps, compressors). The probe must be
perpendicular, not tangential, to the leak interface. The probe should be moved along the entire leak interface to find the
maximum reading.
Fouling of the probe with grease, dust, or liquids should be avoided. A short piece of flexible plastic tubing can be used as a
probe tip extender and snipped off as the tip is fouled. The probe may also be packed with untreated fiberglass to act as a
particulate filter, but the instrument should then be calibrated with the “filter" in place.
For valves, the most common leak source is at the seal between the valve stem and the housing. To screen this source, the
operator should place the probe where the stem exits the packing gland, and move it around the stem circumference. The
screening value is the maximum recorded instrument reading. The probe should also be placed at the packing gland take-up
flange seat, and moved along the periphery. Valve housings of multipart assemblies (bonnet flanges) should also be screened
at the surface of all points where leaks could occur.
For flanges, the probe should be placed at the outer edge of the flange-gasket interface, and moved along the circumference of
the flange. Bolts should also be checked. For screwed fittings, the threaded connector interface should also be monitored
along its entire interface.
Pumps and compressors are monitored with a circumferential traverse at the outer surface of the pump or compressor shaft
and seal interface where the shaft exits the housing. If the source is a rotating shaft, the probe inlet is positioned within 1 cm of
the shaft seal interface. If the housing configuration prevents a complete traverse of the shaft periphery, all accessible portions
should be sampled, as well as all other joints on the pump or compressor housing where leakage could occur.
The configuration of most pressure relief devices prevents monitoring at the sealing seat. Because of their design and function,
pressure relief devices should not be monitored during likely upset conditions or at other times when they are likely to activate.
Instrument readings are taken with the probe tip placed at approximately the center of the exhaust area. The plant safety
engineer should be involved in establishing proper procedures for monitoring fugitive emissions from pressure relief devices.

ExxonMobil Research and Engineering Company – Fairfax, VA

 ExxonMobil Proprietary
AIR POLLUTION CONTROL Section Page
XVIII-A2 11 of 42
CONTROL OF HYDROCARBONS, VOC
DESIGN PRACTICES AND AIR TOXICS EMISSIONS December, 2001

CONTROLLING FUGITIVE EMISSIONS (Cont)

Monitoring Instruments
There are many different types of analyzers which can be used to measure fugitive emissions leaks. These analyzers operate
on a variety of principles, but the three most common types are flame or photo ionization, infrared absorption, and combustion.
The choice of device should be based on the types of compounds to be measured, convenience, and any local regulatory
requirements. A list of some of the available instruments consistent with using EPA Method 21 is contained in TMEE-061.
Ionization detectors are the most popular fugitive emission detector type. They operate by ionizing the gas sample and then
measuring the charge (number of ions) produced. Flame ionization and photo ionization are the two methods of ionization
currently used. Photo ionization detectors use ultraviolet light (instead of a flame) to ionize the organic vapors. Certain organic
compounds containing nitrogen or oxygen are difficult to measure with a flame ionization device and an alternate method must
be used. For example, since flame ionization detectors are not sensitive to formaldehyde, photo ionization detectors may be
used for this application.
Nondispersive infrared instruments measure light absorption characteristics of gases. These instruments, however, are subject
to interference from other gases such as water vapor and CO2 which may absorb light at the same wavelength as the
compound of interest. These detectors are generally used for streams of specific components at high concentration. The
wavelength at which a certain compound absorbs infrared radiation is predetermined and the device is preset for that specific
wavelength using optical filters.
Combustion analyzers are designed to measure either the thermal conductivity of a gas or the heat produced by combusting
the gas. A limitation is that combustion analyzers exhibit reduced response to gases that are not combusted readily.
In the US, fugitive emission monitoring instruments need to meet the requirements of EPA Reference Method 21 (see
Appendix 1 of TMEE-061). Most manufacturers sell devices which are designed to meet this requirement, and it is advisable
that only instruments that meet Method 21 be purchased so that emissions estimates can be properly interpreted. EPA
Reference Method 21 requires that the analyzer meet the following specifications:
• The VOC detector shall respond to those organic compounds being processed.
• The analyzer shall be capable of measuring at the “leak" definition.
• The scale of the analyzer shall be readable to +/- 5 percent of the “leak" definition.
• The analyzer shall take a continuous sample at a flow rate between 0.5 and 3.0 liters/minute.
• The analyzer shall be intrinsically safe for operation in explosive atmospheres.
• The instrument response factor must be less than 10 unless a correction curve is used.
• The instrument response time must be less than or equal to 30 seconds.
• The calibration precision must be less than or equal to 10 percent of the calibration gas value.
When an analyzer is calibrated with a reference gas, an equivalent instrument reading will not be obtained when measuring
emissions of other gases because the analyzer responds differently to different compounds. A “response factor" is required to
provide an accurate relationship when using an analyzer calibrated for one gas to measure leaks of other compounds. For
example, if an instrument is calibrated with methane, different values will be obtained for the same concentration of any other
gases.
A response factor of 1.0 means that the instrument readout is identical to the actual concentration of the chemical in the gas
sample. A response factor greater than 1.0 results in an instrument readout that is proportionally lower than the actual
concentration. A high response factor means that the instrument does not detect a compound very well. Many manufacturers
provide response factors for their instruments when calibrated with either methane, hexane or butane.
Response factors are for pure gases at specified concentrations using a particular instrument. A listing of response factors for
several different instruments is contained in Appendix 4 of TMEE-061. Although a pseudo response factor for a mixture may
be obtained by adding the fractional contributions of the components, the behavior of response factors for mixtures is still not
well understood.

Data Handling
Fugitive emissions monitoring often results in the collection of a very large quantity of data. The quantity depends on the
number of components included in the program, the frequency of monitoring, and the type of information recorded. A basic
system usually includes data on the type, number, service and location of components, screening values, equipment and
conditions, and emissions estimates. The quantity of data collected will depend on the purpose of the monitoring program and
local regulatory requirements. The data will usually be used by the monitoring personnel as well as the maintenance and
environmental / regulatory areas. Table 4 contains a list of suggested data that should be collected and maintained.

ExxonMobil Research and Engineering Company – Fairfax, VA

ExxonMobil Proprietary
Section Page AIR POLLUTION CONTROL
XVIII-A2 12 of 42
CONTROL OF HYDROCARBONS, VOC
December, 2001 AND AIR TOXICS EMISSIONS DESIGN PRACTICES

CONTROLLING FUGITIVE EMISSIONS (Cont)

Additional data on the components may be advantageous for planning further emissions reductions if warranted. These include
manufacturer, model and other specific component information that may be used to identify better performing components.

TABLE 4
DATA COLLECTION SUGGESTIONS FOR I&M PROGRAMS

MODE RECOMMENDED DATA

Monitoring Data • Monitored value
• Test date
• Instrument used
• Calibration gas used
• Instrument response factor
• When instrument calibrated
• Background reading
• Instrument maximum reading
• Date of repair, if required
• Instrument maximum reading after repair
• Date of repeat reading
Component Data • Component type
• Component unique identification number
• Monitoring frequency
• Process
• Stream
• Type of service (H2, gas, light liquid, heavy liquid)
• Location
• Accessible / Inaccessible

VALVES
Valves are used to control the flow of fluid through process piping. Most valve designs involve the lowering or rotating of a part
of the valve internals so as to block the flow of the process fluid. A valve stem connects these internal parts that are lowered or
rotated to outside the valve where they can be manually or automatically operated. The valve stem connection provides a
potential leak path for fugitive emissions of the process fluid. Valves and packing should be selected in accordance with the
requirements of GP 3-12-1 and GP 3-12-8.
The valve stem requires a seal surrounding the stem to isolate process fluid inside the valve from the atmosphere. This seal is
provided by a packing arrangement which, for rising stem gate valves, should be designed in accordance with GP 3-12-8.
The major factors affecting fugitive emissions from valves are the design and condition of the packing, and the design and
condition of the valve. Low emission block valve packings consisting of 5 rings, with the three die-formed center rings of lower
density flexible graphite and the bottom and top end rings being either graphite composite or interlaced braided graphite, are
recommended. The preferred 5-ring graphite design provides for 3 sealing rings with the two end rings preventing the extrusion
of the sealing rings. The lower density graphite sealing rings (70 lb/ft3, 1120 kg/m3) have performed better in leak testing than
have the higher density (90 lb/ft3, 1440 kg/m3) ones. End rings should have a minimum density of 100 lb/ft3 (1600 kg/m3).
Packing sets that consist of “all-braided" rings (either provided as sets or from spools) should not be used in VOC services due
to their relatively high emissions. In addition, some all-braided packing designs do not meet the requirements of the Exxon
valve packing fire safety test (see EE.58E.94). Braided design is acceptable for the top and bottom end rings, however. In
addition, asbestos type valve packings are not recommended due to the potential personnel health concerns and because they
do not control emissions as well as the newer graphite packing sets. Emission control performance of several different
packings are reviewed in EE.104E.98, EE.34E.93 and EE.38E.92. Valve packing for rising stem gate valves should be
selected in accordance with GP 3-12-8.

ExxonMobil Research and Engineering Company – Fairfax, VA

 ExxonMobil Proprietary
AIR POLLUTION CONTROL Section Page
XVIII-A2 13 of 42
CONTROL OF HYDROCARBONS, VOC
DESIGN PRACTICES AND AIR TOXICS EMISSIONS December, 2001

CONTROLLING FUGITIVE EMISSIONS (Cont)

The use of more than 5 packing rings is not generally recommended under normal circumstances. Additional rings will usually
not improve sealing and may actually lead to poorer performance since gland sealing forces are not effectively transmitted
throughout the packing set when a large number of rings are utilized. In addition, the extra rings add to the packing
consolidation, potentially requiring more frequent tightening of the packing gland. Spacing rings to shorten the effective depth
of the stuffing box should be used on existing valves with large valve stuffing boxes that would normally accommodate more
rings. New valves should be specified with stuffing boxes sized to accommodate a standard 5-ring packing set. See
EE.32E.92 for additional information.
Many plants have had reservations about using the 5-ring packing sets for field replacements on existing valves due to the
perceived difficult installation or limited stocking. There are several newer types of graphite spool packings, however, that will
pass the ExxonMobil fire test and may also provide for good control of fugitive emissions. Contact EMRE's Air Quality Control
Group for the latest on recommended valve packings.
Maintaining packing gland bolt and nut tightness is a major part of reducing fugitive emissions. It should be used as a first
attempt to decrease leak rates. In addition, valve packing glands should be checked and if necessary retightened after any
shutdown or severe thermal cycling. A torque wrench should be used to tighten the gland bolts to ensure that the proper force
is placed on the packings. In most cases, the packing manufacturer will recommend the bolt torque or packing compression.
ER&E experience indicates that these recommendations do not always result in the maximum level of emissions control. The
most effective method to set packing compression is to use a monitoring instrument to detect the quantity of emissions as the
final bolt torque or packing compression is set.
Mechanical design features of the valve such as stem and stuffing box clearances and finishes may play a very important part
in controlling emissions. Stem corrosion and pitting is known to be a major cause of poor valve emission control performance
since the packing can be damaged each time the valve is cycled and the stem moves up and down. This is especially a
problem in valves that are cycled frequently. See EE.15E.93 for additional details.
Control valve designs are available that provide for high levels of emissions control. These low emission control valves are
often cost effective based on decreased maintenance alone and are recommended for all new and retrofit installations even
where there are no fugitive emission regulations. Results of emissions field testing are presented in EE.84E.93 and
EE.101E.92. When replacing the existing packing in control valves, care should be taken to determine if stem dragging
(hysteresis) will increase resulting in the need for a different actuator. An instrument specialist should be consulted when
selecting control valve types or packing. See also GP 15-9-1.
Control valve packing is sometimes designed as two sets of 4 to 5 rings each separated by a lantern ring. The lantern ring
allows monitoring of the area between the two packing sets for early signs of leakage. It may also serve as a means to collect
leakage into a vapor control system. Control valves should be selected in accordance with GP 15-9-1.
Maintenance for valves with stuffing box / packing arrangements involves periodic monitoring and retightening of the packing
gland to compensate for wear and relaxation of the packing. In many cases, the manufacturers' recommendations for packing
compression have been found to be far from the optimum. Therefore, it may sometimes be necessary to determine the correct
packing compression by leak testing at the valve stem while the gland bolts are tightened. Care should be taken so as not to
over tighten the gland bolts such that the valve becomes inoperable. When tightening of the packing gland no longer maintains
leakage at desired levels, the packing should be replaced.
Valve packing is available in many different designs and materials and almost all manufacturers now seem to advertise that
their products can meet the most stringent fugitive emissions regulations. The more expensive packings do not necessarily
provide improved emissions control performance. Testing by ER&E has indicated that some packings perform better than
others (see EE.38E.92). Contact EMRE's Air Quality Control Group when considering alternative packings for either new or
replacement installations.
A new “on-line" valve stem and flange leak repair procedure has been used successfully at some Exxon locations. Sealing is
achieved by injecting a pliable mixture of granulated graphitic material and silicone carrier through the fitting into the valve
stuffing box, or into a flange that has been mechanically enclosed. The injection fitting is permanent and multiple future
injections, if necessary, are possible. Because of the technology's relatively recent application, long term performance is not
known. Additional information on the application of “on-line" injection is available from the Environmental Engineering Group,
ExxonMobil Chemical Company, Baytown, TX.
“Live loading" is a means of applying a predetermined constant load on the packing gland to potentially reduce the frequency of
packing gland adjustment and maintain low emissions performance. The technique provides for automatic gland adjustment to
keep the packing under constant pressure, reducing the need for repeated bolt tightening. Disk or coil springs installed on the
gland stud bolts, on the gland itself, or in the stuffing box are used to maintain a continual load. The springs maintain the
predetermined load on the packing as it consolidates due to internal compression, shrinkage, wear, and thermal cycling. In
many cases, live-loading can be retrofit onto existing valves provided the bolts are of sufficient length. The benefits of live
loading have not yet been conclusively demonstrated for block valves. The technique has been incorporated, however, in
many of the new “low emission" control valve designs.

ExxonMobil Research and Engineering Company – Fairfax, VA

ExxonMobil Proprietary
Section Page AIR POLLUTION CONTROL
XVIII-A2 14 of 42
CONTROL OF HYDROCARBONS, VOC
December, 2001 AND AIR TOXICS EMISSIONS DESIGN PRACTICES

CONTROLLING FUGITIVE EMISSIONS (Cont)

The process fluid may be completely sealed from the atmosphere by the use of a “bellows" seal. This type of seal incorporates
a formed metal bellows that makes a barrier between the disc and the body bonnet joint. The bellows service life is quite
variable and the seal must be backed-up by a conventional packing. Bellows seal valves are much more expensive than
conventional designs and there is insufficient experience to determine their long term reliability for refinery or petrochemical
plant application.
An alternative method of isolating the process fluid from the atmosphere is through the use of a diaphragm which may also be
used to control the flow. In diaphragm valves, the diaphragm is pushed toward the valve bottom, throttling the flow. When the
diaphragm reaches the valve bottom, it seats firmly against the bottom, forming a leak proof seal. Fugitive emissions are
possible, should the diaphragm fail.

PUMPS
Pump emission controls should be specified in consultation with a rotating machinery specialist. Fugitive emissions from
pumps normally occur where the moving shaft penetrates the stationary casing. A sealing device is used at this point to isolate
the fluid contained in the pump interior from the atmosphere. These sealing devices are either of the packed or mechanical
design. Mechanical pump seals can be either single or dual. The mechanical seal is comprised of rotating and stationary faces
which are machined to a high degree of smoothness to maintain contact over their surface area and are held together by a
combination of pressure supplied by a spring and the pump pressure transmitted through the liquid that is being pumped. If the
seal becomes imperfect due to wear, the pumped liquid can leak between the seal faces. Descriptions and additional
information on these and other pumps seal types are contained in Section X-G, TMEE-023 and EE.19E.92. Pumps should be
selected in accordance with GP 10.
Sealless pumps include canned, magnetic drive, and diaphragm designs. Canned designs are fully enclosed units where the
process fluid is contained in the pump housing. Magnetic drive designs eliminate direct contact of the rotating motor shaft with
the process fluid by transmitting the rotation magnetically to the pump impeller which is enclosed in a sealed housing. Canned
and magnetic drive pumps should be considered for services where control levels equivalent to that of multi-seal designs are
required. Limitations on the maximum proven size and the need for clean services have so far limited sealless pump
applications. In addition, they require piping and other installation details not needed for conventionally sealed pumps.
The choice of pump design type will depend on the emission limit target and the specific gravity of the fluid. New single
mechanical seal designs can meet emission leak limits as low as 500 ppm for process fluid specific gravities above about 0.4
(STLE SP30). At lower emission levels or specific gravities, multi-seal designs are generally required. The advantage of a
single seal design, however, is the avoidance of the auxiliary equipment which must also be leak controlled. Details on seal
selection are contained in Section 1-2 of the Pump Sealing Technology Manual (TMEE-23). Section X-G , GP 10, and a
machinery specialist should be consulted for details on selecting pump seals for specific service applications.

COMPRESSORS
Compressor emission controls should be specified in consultation with a rotating equipment specialist. As with pumps, seals
are required to prevent leakage of the process fluid to the atmosphere. There are many different seal types and these are
described in DP XI and EE.19E.92. DP XI , GP-10, and an equipment specialist should be consulted for details on selecting
compressor seals for specific service applications.

CONNECTORS / FLANGES
Flanges are bolted, gasket sealed junctions used wherever pipes or other equipment such as vessels, pumps, valves, and heat
exchangers may require isolation or removal. Connectors are all other fittings that serve a similar purpose to flanges, which
also allow bends in pipes (elbows), joining two pipes (couplings), or joining three or four pipes (tees or crosses). Connectors
are typically threaded or compression fittings.
Flanges may become fugitive emissions sources when leakage occurs because of improperly chosen gaskets or poor
installation. The primary causes of flange leakage are gasket distortion or poor seating which is often caused by incorrect
installation or thermal cycling. Threaded connectors may leak if the threads become damaged or corroded or if tightened
without sufficient lubrication or torque.
Control measures include more careful make-up procedures, tightening of the flange bolts, replacing gaskets, using live-loading
to maintain torque on the bolts and seal-welding. In some cases, seal-welding has also been used as a control technique.
“On-line" repair using injection of sealant has been used at some Exxon locations and is described above under VALVE control
techniques. DP II and GP 3-16-1 should be consulted when selecting flanges or other piping system connectors.

ExxonMobil Research and Engineering Company – Fairfax, VA

 ExxonMobil Proprietary
AIR POLLUTION CONTROL Section Page
XVIII-A2 15 of 42
CONTROL OF HYDROCARBONS, VOC
DESIGN PRACTICES AND AIR TOXICS EMISSIONS December, 2001

CONTROLLING FUGITIVE EMISSIONS (Cont)

PRESSURE RELIEF VALVES

The use of pressure relief devices is required where the process pressure could exceed the maximum working pressure of the
equipment. The pressure relief valve (PRV) is the most commonly used pressure relief device. Typically, relief valves are
spring loaded and designed to open when the system pressure exceeds a pre-set value, allowing the release of vapors or
liquids until the system pressure is reduced to below the pre-set value. The valve then reseats. The seal is a disc on a seat,
and fugitive emissions are a result of leaks through this seal.
The potential causes of fugitive emissions from pressure relief valves are “simmering" (a condition that occurs when the system
pressure comes close to the set pressure of the valve), improper reseating of the valve after opening, and corrosion or
degradation of the valve seat.
Fugitive emissions from pressure relief valves can be reduced by use of improved designed seats, by the installation of rupture
discs in the inlet or discharge line, and by routing the release to a closed system. Some newer designs are available with
plastic or elastomer sealing surfaces which may partially compensate for small imperfections on the seals. These soft seats
must be compatible with all of the process fluids, however.
Rupture disks installed in series upstream or downstream of a pressure relief valve essentially eliminate emissions to the
atmosphere. When a rupture disc is installed upstream of a pressure relief valve, the overpressure first bursts the disk and
then opens the relief valve. Limitations on this arrangement include a derating of the valve capacity, the need for a non-
fragmenting type disk, and monitoring the pressure in the cavity between the disk and the relief valve to detect leaks across the
disc. A leaking disc would equalize the pressure on both sides of the disc and would prevent the disc from bursting during an
overpressurization event because rupture discs are designed to burst when applied differential pressure equal or exceeds the
stamped burst pressure. For complete control, the monitoring tell-tale leg should be routed to a vapor control device. It is very
important that the rupture disk does not interfere with the operation of the relief valve. This installations should comply with GP
3-2-4 and DP XV-C. Additional assistance with the specification of rupture disks with pressure relief valves is available from
EMRE's Safety Section.
As previously mentioned, routing the release to a control device such as a flare is another option, but it will be very site and
application specific. Vapor recovery and control options are discussed in the subsection on LOADING.

SAMPLING CONNECTIONS
Process unit operations are checked periodically by analysis of feedstocks and products. To obtain representative samples for
these analyses, sampling lines first must be purged. If the flushing liquid is not contained, it could be drained onto the ground
or into a process drain where it could evaporate or add to the waste load of the wastewater treating facility. Discharge of
organics to the sewer system should be minimized.
Closed loop sampling systems control the purged process fluid by returning it directly to the process line, collecting and
recycling the fluid, or transporting the fluid to a control device. These closed loop sampling systems typically have no
detectable emissions to the atmosphere.
Additional requirements for sampling systems are contained in GP 3-2-7. An instrumentation specialist should be consulted for
the latest techniques and equipment available.

OPEN-ENDED LINES AND VALVES

Some valves are installed in the piping system with the downstream line open to the atmosphere. These open ended lines are
used in intermittent service for purging, drainage, and sampling. Some open ended lines are needed to preserve product purity
and are installed between multi-use product lines to prevent material from collecting in tie lines due to valve seat leakage.
Fugitive emissions from open ended lines and valves are controlled by the safety requirement to equip them with caps, blind
flanges, plugs or secondary valves. The purpose of these is to provide a secondary seal except during operations requiring
use of the line. When a secondary valve is used, the valve closest to the process fluid should be closed first.

PRODUCT ACCUMULATOR VESSELS

Product accumulator vessels include overhead and bottoms receiver vessels used with fractionation columns and product
separator vessels used in series with reactor vessels to separate reaction products. Fugitive emissions from accumulator
vessels are due to venting either directly to the atmosphere or indirectly through a blowdown drum or vacuum system.
Controls for accumulator vessels include equipping them with a closed vent system capable of capturing and transporting any
leakage from the vessel to a control device. Control systems (such as vapor recovery or destruction) are described in the
section on LOADING.

ExxonMobil Research and Engineering Company – Fairfax, VA

ExxonMobil Proprietary
Section Page AIR POLLUTION CONTROL
XVIII-A2 16 of 42
CONTROL OF HYDROCARBONS, VOC
December, 2001 AND AIR TOXICS EMISSIONS DESIGN PRACTICES

CONTROLLING FUGITIVE EMISSIONS (Cont)

AGITATORS
Agitators are used to stir or blend chemicals. Like pumps and compressors, agitators may leak organic chemicals at the point
where the shaft penetrates the casing. Consequently, seals are required to minimize fugitive emissions through this path. The
four seal arrangements used with agitators are: compressed packing, mechanical seals, hydraulic seals, and lip seals. Packed
seals for agitators are very similar in design to packed seals for pumps.
Although mechanical seals are more costly than the other three types of seals, they offer a greatly reduced leakage rate to
offset their higher cost. Furthermore, the maintenance frequency of mechanical seals is one half to one fourth that of packed
seals. The mechanical seals for agitators are similar in design to the mechanical seals for pumps.
The hydraulic seal, which is the simplest agitator seal, has an annular cup attached to the process vessel that contains a liquid
that is in contact with an inverted cup attached to the rotating agitator shaft. The primary advantage of this seal is that it is a
non contact seal. Use of this seal, however, is limited to low temperatures and pressures and very small pressure fluctuations.
In addition, chemicals may contaminate the seal liquid and then be released into the atmosphere as fugitive emissions.
A lip seal can be used on a top entering agitator as a dust or vapor seal. The sealing element is a spring loaded elastomer. Lip
seals are relatively inexpensive and easy to install. Once the seal has been installed, the agitator shaft rotates in continuous
contact with the lip seal. Pressure limits of the seal are 2 to 3 psig because it operates without lubrication, and operating
temperatures are limited by the characteristics of the elastomer. Fugitive emissions can be released through this seal when the
seal wears excessively or the operating pressure surpasses the pressure limits of the seal.

CLOSED VENT SYSTEMS AND CONTROL DEVICES

A closed vent system can be used to collect gaseous emissions from seal oil degassing vents, pump and compressor seal
leakage, and relief valve leakage and discharges. The system consists of piping connectors, flame arrestors, and sometimes
flow-inducing devices. Closed vent systems are designed and operated so that all emissions are transported to a control
device without leakage to the atmosphere. Control devices for recovery or destruction of the emissions are described in the
section on LOADING.

CONTROLLING TANK EMISSIONS

The quantity of emissions from atmospheric storage tanks depends on many factors including the material stored, the types
and conditions of the tanks and their seals, the meteorological conditions and the presence of emission controls. The recent
emphasis on installing additional controls, such as secondary seals on floating roof tanks, is the result of environmental
regulations rather than material loss concerns.
The trend is for stricter regulations both in mandated equipment control measures and percent reduction requirements. In
many locations secondary seals are required on new or modified floating roof tanks. In addition, gasket and bolt roof fittings on
floating roofs may be required.
The largest source of tank emissions is generally from the floating roof types due to their large number and their use in higher
vapor pressure services. Emissions may be estimated using the techniques described in the API Publications or the Emissions
Estimating Guide, TMEE-46.

SOURCES OF VAPOR EMISSIONS

Emissions from tanks are the result of addition and removal of stock, from temperature and pressure changes, and from wind
passing over the tank. The particular emission mechanisms and their contribution to total emissions depend on the tank
construction, material stored, and local meteorology. There are three types of tank designs used for the atmospheric storage of
petroleum liquids: fixed roof; external floating roof; and internal floating roof.
Atmospheric storage tank vapor emissions are due to standing losses, which occur without tank level changes and depend on
the tank environment, and working losses, which occur during the filling and emptying of the tank and are dependent on
throughput. The majority of air emissions from a floating roof tank are standing losses while the major contributor for fixed roof
tanks are working losses.
Fixed roof tanks consist of a cylindrical shell covered with a stationary, non-moving, roof. There is a volume of gas located
above the liquid stored in a fixed roof tank. The major mechanism for emissions from a fixed roof tank is from hydrocarbon
vapors that are expelled as liquid is added. Another, although usually much smaller, emission mechanism is from changes in
the atmospheric temperature and pressure causing volume changes in the tank. During these changes, air may be drawn into
the tank, become contaminated with hydrocarbon, and then be expelled. Underground storage tanks will have working losses,
but because the ground acts as an insulator to keep the tank nearly isothermal, there are usually no breathing losses from
diurnal temperature changes.

ExxonMobil Research and Engineering Company – Fairfax, VA

 ExxonMobil Proprietary
AIR POLLUTION CONTROL Section Page
XVIII-A2 17 of 42
CONTROL OF HYDROCARBONS, VOC
DESIGN PRACTICES AND AIR TOXICS EMISSIONS December, 2001

CONTROLLING TANK EMISSIONS (Cont)

Emission controls for fixed roof tanks include vapor balancing, conversion to an internal floating roof tank, and the installation of
a vapor recovery or destruction system. Vapor balancing involves transferring the vapor that would have been expelled from
tank filling to the source of the liquid. The installation of a floating roof converts the fixed roof tank into an internal floating roof
design. Collection of the vapors for recovery or destruction is the most complete, although usually the most costly, control for
fixed roof tank designs. One low cost emission control option is to paint uninsulated tanks white. Significant emissions
reductions can be obtained, for example, if medium grey tanks are painted white. Because fixed roof tanks are usually used
only for storing low vapor pressure materials, there has been limited application of improved emission controls.
Floating roof tanks consist of a cylindrical shell with a roof that floats on top of the liquid and rises and falls as the liquid level in
the tank changes. In an internal floating roof tank, there is also a stationary roof on top of the tank. The major mechanism for
emissions from a floating roof tank is from evaporation through openings in the floating roof (roof fittings) and the spaces
between the rim seal and tank wall. Another, although usually much smaller, mechanism is from evaporation of the liquid on
wetted surfaces such as the tank walls, stilling / sampling wells and other internal support structures as the roof is lowered.
Emission control efforts for floating roof tanks are directed towards minimizing diffusion through and around the rim seals and
deck fittings of the floating roof as well as reducing material clinging to the tank wall upon product removal. The first step in
controlling emissions from floating roof tanks is to inspect the condition of the primary seal for excessive space at the tank wall.
Other emissions controls include replacing a foam filled vapor-mounted primary seal with a foam filled liquid-mounted or
mechanical shoe type primary seal, the installation of a secondary seal, and controlling the losses from roof fittings. External
floating roof tanks can be converted to internal floating roof tanks to reduce wind induced emissions. Roof fitting controls
include adding gaskets to guide pole wells, gage hatches, vacuum breakers, and access hatches as well as bolting the
hatches. If a slotted guide pole is used, a sleeve surrounding the pole in the deck area can substantially reduce tank emissions
since an “uncontrolled" slotted guide pole is a relatively large emissions source.
In addition to the above losses during operation, there may be significant losses when a tank is removed from service and
“degassed", or when the roof is landed in floating roof designs. In these cases, the vapors in the tank are emitted to the
environment. Controls would include routing the vent to a recovery or destruction device.

SELECTING APPROPRIATE CONTROLS

The following are steps for identifying the major tank emission sources and selecting the appropriate tank air emission controls:
1. Identify the emission regulations that apply to facility tankage.
2. Generate a database of existing tank services. Include stored material properties, tank characteristics, and existing control
measures.
3. Estimate current emissions from each storage tank to identify main contributors and provide a basis for potential
reductions.
4. Calculate emission reductions and cost effectiveness of potential control solutions.
5. Recalculate emissions with selected controls in place to assure compliance with identified emission regulations.
Discussion of the procedures used to evaluate alternative emission control options are discussed in EE.35E.93. Consult
Section XXII for details on design of tank control systems Selections should be in accordance with GPs 9-4-1, 9-7-1, 9-7-3
and 9-7-4.

Selection of Tank Roof Type

The type of tank roof that is selected is a major factor in establishing the potential quantity of vapor emissions from the tank.
Fixed roof tanks should only be used to store low vapor pressure stocks and generally do not present an attractive opportunity
for reducing vapor emissions. For storage of higher vapor pressure stock, such as mogas, a floating roof design should be
used. Where odor is a problem with low vapor pressure material, options include disposal to a flare, an incinerator, or vapor
recovery unit.
If additional controls are required on an external floating roof tank, upgrading the primary seal, then installation of a secondary
seal, then controls on roof fittings, and finally an aluminum geodesic dome should be considered. The geodesic dome may in
some cases be added with the tank in service. A dome roof eliminates the wind effects on the primary seal. However, it is very
expensive and upgrading the primary rim seals and adding secondary seals achieve similar air emission reductions at a fraction
of the cost. A significant advantage for the domes, however, is that they can prevent rainwater infiltration into the tank. Dome
roofs have been justified based on benzene-contaminated water source reduction. In addition, dome roofs are increasingly
used to preserve product quality in marketing terminals and eliminate snow / freezing water problems in very cold climates. In
new tank construction, a geodesic dome / internal floater combination can be cost competitive with an external floating roof
design in some situations.

ExxonMobil Research and Engineering Company – Fairfax, VA

ExxonMobil Proprietary
Section Page AIR POLLUTION CONTROL
XVIII-A2 18 of 42
CONTROL OF HYDROCARBONS, VOC
December, 2001 AND AIR TOXICS EMISSIONS DESIGN PRACTICES

CONTROLLING TANK EMISSIONS (Cont)

Floating Roof Seal Selection

Controlling rim losses in floating roof tanks is most cost effectively handled by proper seal selection. Different types of seals
are available and vendors offer a wide selection of proprietary designs. Almost all designs fall into three major categories of
primary seals: vapor-mounted, liquid-mounted, and mechanical shoe; and two categories of secondary or auxiliary seals: rim-
mounted, and shoe-mounted.
Factors to consider in upgrading seals include oil losses, maintenance, expected life and mechanical condition of tank shell (out
of roundness), environmental requirements, tank availability, possible loss of tank capacity, and possible change in future tank
service in addition to the material and installation costs. If a new or replacement seal can be installed without the need to clean
and gas-free the tank, it would offer a significant advantage over one that would require taking the tank out of service.

Primary Seals
The function of the primary seal is to separate the stored liquid from the atmosphere by sealing the gap between the floating
roof and the tank shell. Vapor-mounted seals are characterized by a flexible fabric covered sealing “log" which can be foam or
gas filled. The seal is mounted above the liquid level leaving a vapor space between the bottom of the seal and the liquid. This
vapor space becomes saturated with material stored in the tank and is a major source of emissions. Liquid-mounted seals are
similar to the vapor-mounted seal except that the bottom of the seal is in contact with the product essentially eliminating the
saturated vapor space. The liquid-mounted seal is, thus, more effective in minimizing emissions than is the vapor-mounted
seal.
Vapor-mounted seals have been preferred over liquid-mounted seals in the past because of longer service life, ease of
installation, and lower installed cost. However, improvements in fabric life have increased the life of liquid-mounted seals.
Foam-filled liquid-mounted seals have been susceptible to contamination by hydrocarbons due to leaks in the protective fabric.
This presents a waste disposal problem when seals are replaced and can make gas freeing the tank difficult.
Mechanical shoe seals are a third type of primary seal commonly used in petroleum service. This type of seal is characterized
by a movable metal plate which is pressed against the tank wall and supports a sealing fabric between the shoe and the
floating roof. Its effectiveness in minimizing emissions lies between the vapor-mounted and liquid-mounted seal effectiveness.
Because of its large contact area, the mechanical shoe seal is more tolerant of sizable gaps than are the other types.
Mechanical shoe seals, while the most expensive of the three primary seal types, may be selected for any of the following
reasons:
• When combined with a secondary seal, the combination provides emissions control comparable to a liquid-mounted seal.
• They offer a longer service life which may justify the additional expense.
• They are not damaged by tank shell burrs, weld splatter, or non-flush welds as resilient seals are. Therefore, they are
usable with less attention to surface condition.
• No waste disposal problem results from seal replacement.
• Riveted tanks damage resilient seals making mechanical shoes the only viable choice for non-welded tank service.
In recent years, a modern seal design has been developed which consists of a combined primary and secondary seal. These
designs employ two compression plates for both primary and secondary seals. The constant pressure exeted by the double
compression plates helps to keep the roof centered. Both the primary and secondary seal maintain contact with the tank shell.
The installation of the seal can be carried out while the tank is in service. The emissions control is considered to be equivalent
to a vapor mounted resilient seal with a secondary seal.

Secondary Seals
Secondary seals are continuous flexible rubber or metal seals which span the gap between the tank wall and the floating roof
above the primary seal. They are usually of the “wiper" type being relatively thin compared to their width and are held against
the tank wall by the force of their flexing. Most secondary seals are mounted on the rim of the floating roof and are called rim
seals. Another type is mounted on the top edge of a mechanical shoe primary seal extending to the tank wall; this is called a
shoe-mounted seal. Rim seals are much more effective than shoe mounted seals in controlling emissions. Overlapping leaf
type weather shields have been used but are not as effective at reducing emissions as continuous secondary seals.
The main function of the secondary seal is to keep the wind away from the primary seal. The secondary seal also has the
benefit of keeping sunlight and some of the rain away from the primary seal. This reduces degradation of the primary seal
fabrics and the amount of water entering the tank.

ExxonMobil Research and Engineering Company – Fairfax, VA

 ExxonMobil Proprietary
AIR POLLUTION CONTROL Section Page
XVIII-A2 19 of 42
CONTROL OF HYDROCARBONS, VOC
DESIGN PRACTICES AND AIR TOXICS EMISSIONS December, 2001

CONTROLLING TANK EMISSIONS (Cont)

Controlling Emissions from Roof Fittings

For typical floating roof tanks, over half the air emissions are through the deck fittings because perimeter seal losses are well
controlled. The largest contributors are the guidepole / sample wells, roof legs, ladder well, sample pipe, and internal column
wells. An effective control for the roof support column fittings is a flexible fabric sleeve which attaches to the floating roof and
the top of the column providing a vapor barrier around each column. Controls available for these sources primarily involve
gasketing and seal improvement to restrict diffusion.
For external floating roof tanks, the slotted guidepole / sample well is responsible for almost all of the total air emissions due to
tank roof fittings. While using an unslotted guidepole with a gasketed cover will nearly eliminate emissions from this source, it
would also prevent the use of the guidepole for gauging and sampling. Controls for slotted guidepoles include a sleeve
surrounding the pole in the area of the deck. Use of a float provides little additional emissions control benefit. In some cases,
the cost of the sleeve will be offset by the value of the reduced hydrocarbon loss. The roof fittings other than the guidepole do
not contribute a significant amount to the emissions from external floating roof tanks.
Table 5 provides a comparison of the emission control effectiveness for the different atmospheric storage tank design types
compared to fixed roof tanks. Tables 6 through 9 list the controls available for external and internal floating roof tanks. For
primary seals, control efficiencies are compared to vapor-mounted primary seals. For deck fittings, the “uncontrolled" and
“controlled" designs are described.
TABLE 5
COMPARISON OF EMISSION CONTROL EFFICIENCIES FOR DIFFERENT TANK CONTROL OPTIONS

SEAL SYSTEM
TANK TYPE % EMISSIONS REDUCTION
PRIMARY SEAL SECONDARY SEAL
Vertical Fixed Roof N/A N/A 0% (Baseline)
EFR Vapor-mounted None 91.7
EFR Vapor-mounted Weather shield 95.4
EFR Mechanical shoe None 97.1
EFR Vapor-mounted Rim-mounted 97.4
EFR Mechanical shoe Shoe-mounted 98.4
EFR Liquid-mounted None 98.5
EFR Liquid-mounted Weather shield 98.8
EFR Mechanical shoe Rim-mounted 98.8
EFR Liquid-mounted Rim-mounted 99.0
IFR Vapor-mounted None 99.0
IFR Mechanical shoe None 99.1
IFR Vapor-mounted Rim-mounted 99.3
IFR Mechanical shoe Shoe-mounted 99.4
IFR Liquid-mounted None 99.4
IFR Mechanical shoe Rim-mounted 99.5
IFR Liquid-mounted Rim-mounted 99.5

EFR: External Floating Roof

IFR: Internal Floating Roof
Values calculated using EPA program TANKS 4.09
Contents: Mogas (RVP 10), Throughput = 171,750,150 gal/year
2
Location: Houston, TX (Wind Speed = 7.87 mph, T = 67.9°F, P = 14.7 psia, Solar Insolation Factor = 1406 Btu/ft )
Welded Tank, light rust interior, white color/shade, good tank/paint condition, 150 ft diameter, 56 ft height
Maximum liquid height = 50 ft, average height = 30 ft
Vertical Fixed Roof: - Cone, slope = 0.0625 ft/ft, tank not heated
EFR: Pontoon roof, typical deck fittings (includes unslotted guidepole w/ungasketed sliding cover)
IFR: Column supported (9 columns), welded deck, typical deck fittings

ExxonMobil Research and Engineering Company – Fairfax, VA

ExxonMobil Proprietary
Section Page AIR POLLUTION CONTROL
XVIII-A2 20 of 42
CONTROL OF HYDROCARBONS, VOC
December, 2001 AND AIR TOXICS EMISSIONS DESIGN PRACTICES

CONTROLLING TANK EMISSIONS (Cont)

TABLE 6
EXTERNAL FLOATING ROOF TANK SEAL SYSTEM CONTROL EFFICIENCIES

SEAL SYSTEM
% EMISSIONS REDUCTION
PRIMARY SEAL SECONDARY SEAL
Vapor-mounted None 0% (Baseline)
Vapor-mounted Weather shield 45%
Mechanical shoe None 65%
Vapor-mounted Rim-mounted 69%
Mechanical shoe Shoe-mounted 81%
Liquid-mounted None 82%
Liquid-mounted Weather shield 85%
Mechanical shoe Rim-mounted 86%
Liquid-mounted Rim-mounted 88%

TABLE 7
CONTROLS FOR EXTERNAL FLOATING ROOF TANK DECK FITTINGS

FITTING TYPE UNCONTROLLED CONTROLLED

Unslotted guidepole/well Ungasketed sliding cover Gasketed sliding cover with sleeve
Slotted guidepole/sample well Ungasketed (or gasketed) sliding Gasketed sliding cover with pole
cover without float sleeve and wiper
Access hatch Unbolted, ungasketed cover Bolted, gasketed cover
Gage float well Unbolted, ungasketed cover Bolted gasketed cover
Sample well Weighted mechanical actuation, Weighted mechanical actuation,
ungasketed gasketed
Vacuum breaker Weighted mechanical actuation, Weighted mechanical actuation,
ungasketed gasketed
Roof drain Open 90 % closed
Rim vent Weighted mechanical actuation, Weighted mechanical actuation,
ungasketed gasketed
Deck legs (roof legs), center or Adjustable, ungasketed, no sock Adjustable, with sock, no gasket
pontoon area

ExxonMobil Research and Engineering Company – Fairfax, VA

 ExxonMobil Proprietary
AIR POLLUTION CONTROL Section Page
XVIII-A2 21 of 42
CONTROL OF HYDROCARBONS, VOC
DESIGN PRACTICES AND AIR TOXICS EMISSIONS December, 2001

CONTROLLING TANK EMISSIONS (Cont)

TABLE 8
INTERNAL FLOATING ROOF TANK SEAL SYSTEM CONTROL EFFICIENCIES

SEAL SYSTEM
% EMISSIONS REDUCTION
PRIMARY SEAL SECONDARY SEAL
Vapor-mounted None 0% (Baseline)
Mechanical shoe None 7%
Vapor-mounted Rim-mounted 33%
Mechanical shoe Shoe-mounted 37%
Liquid-mounted None 37%
Mechanical shoe Rim-mounted 45%
Liquid-mounted Rim-mounted 47%

TABLE 9
CONTROLS FOR INTERNAL FLOATING ROOF TANK DECK FITTINGS

FITTING TYPE UNCONTROLLED CONTROLLED

Access hatch Unbolted, ungasketed cover Bolted, gasketed cover

Automatic gauge float well Unbolted, ungasketed cover Bolted, gasketed cover

Column well Built-up column-sliding cover, Pipe column-flexible fabric sleeve seal
ungasketed

Ladder well Ungasketed sliding cover Gasketed sliding cover

Vacuum breaker Weighted mechanical Weighted mechanical actuation,

actuation, ungasketed gasketed

CONTROLLING LOADING EMISSIONS

Emissions from the loading of ships, barges, rail cars, and tank trucks are caused by the displacement of a volume of vapor
due to the addition of a similar volume of liquid. In some respects it is similar to emissions from the filling of a fixed roof tank.
The quantity and composition of the vapor expelled will depend upon the previous material contained, any cleaning prior to
loading, the new material being loaded, the method of loading, and the use of any vapor collection or control devices. The
vapors displaced during loading operations consist of two components. Initially, they are predominantly due to the vapors
formed by the evaporation of the previous product (unless the holding vessel or compartment was cleaned after discharge).
Later in the loading process, the emissions are predominantly those vapors generated during loading of the new liquid.
Emissions from loading operations can be estimated using data contained in API 2514A or the Emissions Estimating Guide,
TMEE-46. A vapor growth factor of 10 % to 25 % is often used when designing vapor control systems.
Significant emissions reduction for loading operations will result from a reduction in the amount of turbulence created when the
liquid is introduced. This can be done by using bottom or submerged loading rather than splash loading. With splash loading,
liquid is introduced at the top of the container and there is significant turbulence and potential entrainment of liquid droplets in
the expelled vapor. Using bottom or submerged loading significantly reduces the turbulence, lowering the vapor generation.
Other emission controls for loading operations include vapor balancing and the installation of vapor recovery or destruction
devices. Vapor recovery technologies include balancing, condensation, absorption, and adsorption. Vapor destruction
technologies include thermal and catalytic oxidation, flares, and biofilters.
Regulations on hydrocarbon vapor emissions from loading operations are becoming common and increasingly more stringent.
Initially, these regulations applied primarily to truck loading operations. However, vapor control on marine and rail loading
operations for volatile hydrocarbons and toxic materials is now being mandated in many locations.

ExxonMobil Research and Engineering Company – Fairfax, VA

ExxonMobil Proprietary
Section Page AIR POLLUTION CONTROL
XVIII-A2 22 of 42
CONTROL OF HYDROCARBONS, VOC
December, 2001 AND AIR TOXICS EMISSIONS DESIGN PRACTICES

CONTROLLING LOADING EMISSIONS (Cont)

Safety is a prime consideration when designing a vapor control system. Facilities should be designed to minimize the risks
associated with fire, detonations, explosions, cargo tank overfilling, and cargo tank over or under pressuring. Section XV-J
discusses the safety requirements for loading facilities.

MARINE LOADING
Vapor collection manifolding is needed from each of the vessel's product compartments to deliver vapor to the onshore vapor
collection / transport system. When loading non-inerted vessels, the vapors displaced during some portion of the loading
operation may be within a flammable range. During the early phase of loading the vapors may be lean or within the flammable
range. During the latter stages of loading, the vapors will likely be rich and well above the upper flammable limit (UFL). To
minimize the potential for detonations / explosions in the shoreside vapor control system, the collected vapors are maintained
outside the flammable range throughout the loading cycle. This can be achieved by enriching with a hydrocarbon gas (typically
natural gas or mogas vapors), by inerting with nitrogen or carbon dioxide, or by diluting the stream to below the explosive
range. Diluting with air, although acceptable, is not recommended for mogas loading due to the large air rates required
resulting in higher costs. Analyzers monitor the enriched / inerted vapors and alarm and/or shutdown the vapor control system
when the hydrocarbon / oxygen concentration is outside recommended limits.
Detonation flame arrestors (i.e., devices which prevent the transmission of detonations (sonic or supersonic flame front) and
deflagrations (subsonic flame front)) are used within the shoreside system as a means of preventing the propagation of an
ignition. Detonation flame arrester should be provided at points within the vapor control system which represent potential
sources of ignition. Water seals may also be used. See Section XV-J for information on safety requirements.

TRUCK LOADING
Vapor collection facilities at truck loading racks are somewhat simpler than for marine loading. The vapor is collected from all
racks and routed to a common vapor processing system. The vapor collection systems are typically smaller than those
required for marine loading due to the lower loading rates and the shorter distances that usually exist between the loading and
vapor processing areas. The vapor is frequently displaced into the collection system by the product filling the truck without the
use of a blower. Inerting or enriching have not been provided in existing installations since the vapors from trucks are generally
well above their UFL. A detonation flame arrester is located immediately upstream of the vapor processing unit to isolate it (as
a source of ignition) from the trucks. Water seals may also be used. See Section XV-J for information on safety requirements.
The vapor collection / processing system is designed to handle a vapor rate equal to the truck volumetric loading rate. Vapor
composition is obtained from data provided by the owner or from samples. A knockout drum is frequently provided ahead of
the vapor processing unit to protect this unit from truck overfills resulting in slugs of liquid in the collection system.
For bottom loading, much of the vapor collection equipment is on the truck. This minimizes the rack collection facilities
required. The vapors are collected in a manifold on the truck and routed to a connection, which is usually located at the curb
side of the truck near the loading connections. The loading rack is provided with a hose which is attached to the truck
connector during loading. The hose may be connected to an arm or directly to a vapor return line at grade. In the latter case, a
hose lift / retraction mechanism is usually provided to store the hose off the ground when not in use.
For top loading, a more complex system is required typically consisting of a tapered conical plug assembly attached to the fill
pipe and a vapor return line which parallels the loading arm. Because of its taper, the plug fits various size truck hatches and
provides a vapor-tight fit around the hatch. The fill pipe extends down through the plug for compartment loading and the vapors
generated are forced out through a separate opening in the plug to the vapor return line. An emergency high level cutout must
be provided for overfill protection.

RAIL CAR LOADING

Where light products are loaded into railcars, vapor collection and processing may be required. The vapor collection system
must conform to the rail car configuration. The vapor collection and processing technologies and considerations described for
truck loading also apply to rail car loading. If vapor venting is permitted, an elevated vent should be provided to minimize
personnel exposure to vapors. If regulations prohibit venting, a vapor recovery or destruction system will be required.

CONTROL SELECTION
Selecting the appropriate recovery or destruction control will depend on the type of gas stream, the concentration, the required
efficiency, location, economics and other factors. Descriptions of the various control options are provided below. Table 10
provides a comparison of some of the features of the different techniques including the range of concentrations treated and the
projected control efficiency. Table 11 lists the advantages and disadvantages of each of the control technologies. More
detailed descriptions of the available technologies are provided in the remainder of this subsection. Detailed procedures for
system design are contained in Section XXIII.

ExxonMobil Research and Engineering Company – Fairfax, VA

 ExxonMobil Proprietary
AIR POLLUTION CONTROL Section Page
XVIII-A2 23 of 42
CONTROL OF HYDROCARBONS, VOC
DESIGN PRACTICES AND AIR TOXICS EMISSIONS December, 2001

CONTROLLING LOADING EMISSIONS (Cont)

Selection of a particular control technology will be mostly dependent on the regulatory requirements and capital and operating
costs. If more than one technology will meet the required control efficiency, be acceptable to the regulatory agency, and have
similar costs, other technical factors will determine the choice. These technical factors include flow rate and concentration of
the vapor, stream regularity, and the presence of inorganics, particulates and condensibles. Combinations of more than one
type of control unit is also an option.
Recent Installations for control of marine loading emissions have mostly used thermal oxidation. Controls at facilities loading
mogas onto trucks and rail cars have usually been adsorption units.

VAPOR RECOVERY
Vapor recovery processes control emissions while recovering the hydrocarbons for transfer, recycle, or reuse. There are four
major types of vapor recovery processes in commercial use today: vapor balancing, carbon adsorption, lean oil absorption, and
condensation (refrigeration). In addition to these, there are emerging technologies such as membrane separation. Carbon
adsorption is by far the most common; it is widely used and is well developed. In many cases, a combination adsorption /
absorption process is utilized. Lean oil absorption, has also been accepted widely. Condensation, although widely used in the
past when target recovery efficiencies were in the range of 80 to 85 percent, has been used less frequently in recent years due
to the higher recovery efficiencies required (typically 95 percent and above) and higher costs.

Vapor Balancing
In vapor balancing, vapors from the loading operation are collected and routed back to the tank from which loading is occurring.
In some cases, the vapors are temporarily stored in a holding tank called a “bladder" tank. Vapor balancing is a relatively
simple system and, depending on the vapor transport distances, is low both in investment and operating costs. It is used
mainly with fixed roof tanks and tank trucks. One major use is for LPG loading. It cannot be applied, however, to floating roof
tanks which have no vapor space.
Vapor balancing allows displaced vapors from the tank being filled to fill the vapor space in tanks or trucks that are being
emptied that would otherwise fill with air as liquid is removed. This not only reduces emissions of the vapor but also can assist
in reducing the amount of vapor present in the flammable range. One benefit of using vapor balancing is that the vapors can
be processed or recovered later at continuous, steady state conditions and a controlled rate.
In tank farm systems, vapor balancing can be accomplished by interconnecting the vapor space of tanks containing the same
or, in some cases, similar products using a piping manifold so that vapor can be exchanged for an equivalent volume of liquid
when moved between tanks. Also, the emissions from the diurnal pressure buildup from daily heating and cooling can be more
easily collected and either distributed or controlled. This could essentially eliminate the effect of small volume pressure
releases from each individual tank and allow for collective treatment of all the breathing loss vapors.

Carbon Bed Adsorption

Adsorption is the process where gas molecules contact a solid and bond by weak intermolecular forces. Hydrocarbons
penetrate the pores of the adsorbent and once inside are adsorbed exothermally. Carbon is the most commonly used
adsorbent for VOC control. Other adsorbents include silica gel, alumina, and zeolites. There are two types of adsorption
system operations based on the type of regeneration of the adsorbent: one incorporating vacuum regeneration of adsorbed
vapors and one which utilizes steam regeneration. Small and/or intermittent applications may utilize replaceable carbon
canisters when it is more economical to replace the adsorbent and dispose of the used canister rather than regenerate it.
A typical system incorporating vacuum regeneration consists of two parallel carbon beds and vacuum regeneration facilities
including a vacuum pump, an absorber, a separator, and associated valving. Hydrocarbon vapors pass through one of the two
activated carbon beds where the hydrocarbons are removed from the vapor stream by adsorption on the carbon surface.
Simultaneously the other carbon bed is vacuum or heat regenerated to desorb the recovered hydrocarbons. The desorbed
hydrocarbons are transferred via a vacuum pump to an absorber / separator where the vapors are partially condensed and
recovered. Overhead vapors from this absorber are recycled back to the carbon bed in the adsorption mode.
In the steam regeneration adsorption system, the hydrocarbon vapor stream passes through one of the two beds of activated
carbon where adsorption occurs. Concurrently, the other carbon bed is regenerated with low pressure steam which strips the
adsorbed hydrocarbons from the activated carbon in the bed. The stripped vapors are condensed and the hydrocarbon
components separated from the water in a coalescer / separator. The exit vapors from the separator are recycled to the on-
stream carbon bed operating in the adsorption mode.
Control efficiencies for adsorption depend on the gas flowrate, temperature, pressure, and humidity, and the adsorbent. In
general, adsorption capacity increases with molecular weight. Efficiency decreases with increasing temperature but increases
with increasing pressure. Streams with high humidity decrease control efficiency due to the competition of the water vapor for
the adsorptive sites.

ExxonMobil Research and Engineering Company – Fairfax, VA

ExxonMobil Proprietary
Section Page AIR POLLUTION CONTROL
XVIII-A2 24 of 42
CONTROL OF HYDROCARBONS, VOC
December, 2001 AND AIR TOXICS EMISSIONS DESIGN PRACTICES

CONTROLLING LOADING EMISSIONS (Cont)

Carbon adsorbers are not very effective for controlling highly volatile VOCs (molecular weight less than 40), which do not
adsorb well, or non-volatile compounds (molecular weight greater than 130 or high boiling point), which do not desorb well.
Carbon adsorption has demonstrated vapor recovery efficiencies of up to 99% in certain applications. In addition, this process
is commercially demonstrated, reliable, and used widely. The units are available as “packaged" systems. Disadvantages
include the inability to capture light hydrocarbons (C3 and lighter), and an inability to handle heavier hydrocarbon vapors and
those containing hydrogen sulfide (such as from crude) which will foul the activated carbon. In addition, certain compounds
(i.e., aldehydes, ketones and other reactive compounds) may result in temperature runaways or “hot spots" in the carbon beds.
This is due to the exothermic reaction on the carbon surface that causes heat to build up inside the carbon bed. Unchecked,
these “hot spots" can approach the auto ignition temperature of the hydrocarbons collected. Therefore, carbon adsorption is
used most often in relatively pure hydrocarbon product service (i.e., gasoline, benzene or other products with constant qualities
or specifications). Where vapor from multiple products (gasoline, solvents, etc.) is to be processed in a common bed, the
vendor should be consulted to avoid possible problems associated with contamination, temperature excursions, and
regeneration. In addition, testing has shown that the correct selection and initial conditioning of carbon adsorbent type can aid
in minimizing bed temperature excursions.
Capital costs for adsorbers depend on the gas rate, concentration, residence time, regeneration time, and the capacity of the
adsorbent. The key design parameters that determine the size of the adsorbent bed are the space velocity and bed depth.
The bed volume can be determined from the adsorption isotherm. There are significant operating costs due mostly to
regeneration of the adsorbent. In addition, the spent adsorbent is a solid waste and, if steam is used for regeneration, there is
VOC contaminated waste water.

Lean Oil Absorption

Absorption involves the mass transfer of VOCs from a concentrated gas stream into a liquid absorbent. The driving force is the
concentration difference between the gas and the liquid. The rate of absorption is determined by the difference between the
actual concentration and the equilibrium value. Because lean oil absorption is usually less efficient than some of the other
control techniques, it is usually used in combination with one of the other methods.
Hydrocarbon vapors enter the bottom of a counter-current absorber utilizing either a packed bed, trays, or sprays for contacting
the vapor with an absorbing liquid. Hydrocarbon is removed from the vapor based on its solubility in the absorbing liquid, which
may be simply a lean hydrocarbon stream such as mogas or a solvent which is regenerated. In the latter case, absorbent
regeneration facilities are required. These usually include absorbent heaters, vapor strippers, and either vapor condensers or
absorbers to recover the hydrocarbon vapors separated from the rich solvent. The regenerated solvent is recycled back to the
absorber.
A critical design component in selecting absorption systems is the specification of the packing material. Important factors
include the surface area, pressure drop, structural strength and weight.
The primary advantage of absorption is its ability to handle most hydrocarbon vapors. It can also accommodate variations in
vapor flow rate and hydrocarbon concentrations better than carbon adsorption systems. It is available in sizes to handle high
flow rates. The applicability of absorption is limited, however, by the availability of a suitable solvent for the VOCs being
controlled.
Recovery efficiencies range up to 95% depending on the solvent used, absorbing column size and internals, and solvent
temperature and flow. Typical efficiencies of 75 to 85% can be expected when absorbing gasoline vapors. These do not
match the higher control efficiency of carbon adsorption units.

Refrigeration (Condensation)
VOCs are removed by lowering the gas stream temperature at constant pressure or by increasing the gas stream pressure at
constant temperature. The two types of condensers are surface and direct contact. Surface condensers are shell-and-tube
heat exchangers where coolant flows inside the tubes to condense VOCs contained in the gas stream flowing on the shell side
of the exchanger. Contact condensers operate by spraying a cool liquid directly into a gas stream.
In a refrigeration system, hydrocarbon vapors enter a precooler, where most of the water vapor is removed, and then enter the
condensing column where the remaining moisture, hydrates, and heavier hydrocarbons (C4+) are condensed and separated
from the gas stream. Periodically the condensing columns must be defrosted with the circulation of deicing agents such as a
warm brine solution or methylene chloride.
Coolants used include chilled water, brine solutions, chlorofluorocarbons, liquid N2, and cryogenic solutions. Chilled water is
effective down to a temperature of about 45°F (7°C); brine to -30°F (-35°C); CFCs to -90°F (-68°C); cryogenics to -320°F
(-196°C). Note that CFCs will not likely be available due to their elimination by international agreement.

ExxonMobil Research and Engineering Company – Fairfax, VA

 ExxonMobil Proprietary
AIR POLLUTION CONTROL Section Page
XVIII-A2 25 of 42
CONTROL OF HYDROCARBONS, VOC
DESIGN PRACTICES AND AIR TOXICS EMISSIONS December, 2001

CONTROLLING LOADING EMISSIONS (Cont)

Advantages of the refrigeration process include recovery of hydrocarbons without contamination by carbon or oil absorbent.
Disadvantages include relatively low hydrocarbon removal efficiencies which are typically in the 95% range. Typical units can
cool the vapor to approximately -100°F (-70°C) at best. This will not allow collection of lighter hydrocarbons. In addition, this
process has high maintenance and operating costs.
Costs for condensation depend on the composition and concentration of the gas, the coolant used, the presence of non-
condensible gases, and stream contaminants that could foul the heat exchanger. There is also a very high operating cost
associated with the coolant system.

VAPOR DESTRUCTION
Vapor destruction processes destroy the hydrocarbons in collected vapor by either thermally oxidizing (burning) them or by
biological oxidation. Types of equipment that can accomplish this include flares, thermal oxidizers, catalytic oxidizers, and
biofilters.
While controlling hydrocarbon emissions, the thermal oxidation processes may also produce other compounds such as nitrogen
oxides (NOx), sulfur oxides (SOx), and carbon dioxide (CO2), which may also be limited by local regulations. Therefore, when
proposing a vapor destruction process, it is important to consider permitting requirements relative to all emission products.
Also, with inerted vapors, the addition of supplementary gas may be required to ensure combustibility.
In general, any process using thermal oxidation must be isolated from the vapor collection system since it represents a
continuous source of ignition. A detonation flame arrester and/or a water seal drum located upstream of the thermal oxidizer
provide the necessary protection from the flame propagating upstream into the vapor collection / transfer system.
Residence time, turbulence, temperature, and the available oxygen are the key parameters in establishing destruction
efficiency. Destruction efficiencies are generally proportional to residence time, to the second power with turbulence, and with
the fourth power of temperature. Increasing the temperature, therefore, offers the greatest potential for increased efficiency.

Flares
Flaring is a process which burns the collected vapors in an open flame. They may be either elevated and open, or ground level
and enclosed. Elevated flares have the flame located at the top of a stack and use flare tips and pilots. An elevated flare must
be located in a remote location because it is an ignition source and emits heat. Open, elevated flares are most often used for
controlling emissions from process upsets.
Flares are the least expensive vapor destruction process to construct and operate. They offer significant reduction of
hydrocarbon emissions (destruction efficiency of open flares is generally accepted as better than 98% during routine operation)
and can handle fluctuations in vapor composition and flow rate. The primary disadvantages of flares are the open flame and its
associated luminosity, possible noise and smoke, and that the emission control efficiency cannot be monitored for compliance
with regulations.
Ground level flares are enclosed and contained in an insulated shell. The shell reduces noise, luminosity, and heat radiation
and provides wind protection. Enclosed ground level flares are used for continuous flow vent streams and provide more stable
combustion conditions (temperature, residence time, mixing) than do elevated flares.
Costs for flares depend on the stack and tip diameter, the heat content of the material being destroyed, and flare height
requirements. The tip diameter is a function of the total projected flowrate, gas temperature, gas molecular weight, and tip
velocity. Flare height is selected based on safety considerations.
Destruction of VOCs using a flare results in emissions of CO2, NOx, and possibly SOx. Flares also usually require steam for
smoke suppression.

Thermal Oxidizers
Thermal oxidizers (also known as thermal incinerators) are essentially enclosed flares. They consist of a burner and pilot
assembly, a refractory lined chamber, sometimes heat recovery equipment, and a vertical stack. The chamber can be
designed either horizontally or vertically. The combustion chamber and stack are sized to completely contain the flame at
maximum firing rate. The stack reduces heat radiation, luminosity, and noise. It also provides wind protection for the burners,
and offers some residence time for more complete combustion than occurs in flares. Control efficiency depends on the
combustion temperature, residence time, and the thoroughness of feed gas mixing.
There are three different designs for thermal oxidizers based on their method of heat recovery: direct flame, recuperative, and
regenerative. Direct flame units do not recover any of the heat from the exit gases. Recuperative designs use a heat
exchanger to transfer heat from the exit gases to the feed stream. Regenerative systems transfer the heat first to a reservoir
(usually a ceramic material) for subsequent transfer to the inlet stream. The regenerative designs are generally more efficient
than the others due to the better heat transfer efficiency of the ceramic beds. Secondary heat recovery can increase thermal
efficiency to as high as 95 percent.

ExxonMobil Research and Engineering Company – Fairfax, VA

ExxonMobil Proprietary
Section Page AIR POLLUTION CONTROL
XVIII-A2 26 of 42
CONTROL OF HYDROCARBONS, VOC
December, 2001 AND AIR TOXICS EMISSIONS DESIGN PRACTICES

CONTROLLING LOADING EMISSIONS (Cont)

Certain parameters must be controlled in order to achieve high destruction efficiency. These include the supplemental air and
fuel flowrates, exit temperature, residence time, and degree of mixing. Increasing the temperature offers the greatest potential
for increased destruction efficiency since the higher the temperature, the faster the oxidation reaction proceeds. Combustion
temperature, mixing efficiency and residence time are the three most important variables affecting thermal oxidizer efficiency.
Thermal oxidizers can be specified with or without temperature control. Without temperature control, the unit relies on natural
draft through the open bottom of the stack to provide sufficient air for combustion. The resultant stack temperature will vary
with vapor throughput and composition. At low rates and/or low hydrocarbon concentration of the vapors, the exit stack
temperature can easily be down in the 300 to 500°F (149 - 260°C) range. Accordingly, any vapor not combusted right at the
burner will likely not be combusted. Therefore the mixing of the vapors with combustion air is critical to ensure good
destruction efficiency (greater than 99%). Monitoring is recommended to insure complete combustion of the VOC. In some
locations, a continuous temperature or composition monitor is a requirement.
With temperature control, the stack bottom is shrouded and the combustion air is regulated by louvers and/or forced draft
blowers. With temperature controlled units, auxiliary fuel may also be required to maintain a minimum temperature to promote
complete combustion when the vapors treated do not have sufficient hydrocarbon present. Typically, temperature controlled
units operate with a stack exit temperature in the range of 1500 to 1800°F (815 - 980°C). The stack typically provides a 0.5
second residence time. Under these conditions, destruction efficiencies of 99.9% have been demonstrated.
For low concentration VOC streams, supplemental fuel, such as natural gas, is used to maintain combustion temperature. Heat
recovery equipment may be installed to raise the temperature of the feed gas and reduce the quantity of supplemental fuel.
Thermal oxidizers represent a higher purchase cost than open flares. However, they are capable of higher vapor destruction
efficiencies and can be monitored for compliance. The primary disadvantages with thermal oxidizers are the generation of
CO2, NOx and possibly SOx and possible incomplete combustion resulting in emissions of carbon monoxide (CO) and
unburned hydrocarbons.
Costs for thermal oxidizers depend on the fuel value of the gas, the gas flowrate, the fuel used, the amount of heat recovery,
the residence time, and the presence of other contaminants. A system may include the following equipment: a combustion
chamber, heat recovery exchanger, waste heat boiler, quench / scrubber system (for halogenated streams) as well as the
ducting, fans and safety equipment to move the gas stream. Operating costs for supplemental fuel can be significant.
Destruction of VOCs using a thermal oxidizer can produce secondary emissions such as CO2, NOx, and SOx. Factors
affecting NOx formation include the amount of excess air, the peak flame temperature, the residence time, and the cooling rate.
Combustion of halogenated VOCs may result in the release of halogenated combustion products. In some locations, a
downstream caustic scrubber is required for HCI control. Temperatures above 1589°F (870°C) and residence times of one
second or more are required to ensure 98 percent destruction of halogenated VOC.

Catalytic Oxidizers
Catalytic Oxidizers (also known as catalytic incinerators) are similar to flares and thermal oxidizers except that the combustion
(oxidation) occurs at a much lower temperature due to the use of a catalyst which lowers the activation energy for combustion.
Typical catalyst materials include platinum, palladium, and some metal oxides. Catalytic oxidizers typically consist of a hot gas
heat exchanger, thermal preheat zone with a standard burner and a catalyst bed. The incoming vapor stream is heated to the
desired reaction temperature (about 600°F (315°C)) and run through the catalyst bed. The catalyst initiates and assists in the
oxidation reaction. This makes catalytic oxidizers very fuel efficient and reduces operating costs.
Catalyst materials may be designed in either a monolith or beaded configuration. Monolithic catalysts are secured to a
substrate to prevent carryover in the exhaust stream. While this configuration minimizes catalyst escape, it also reduces the
contact surface area with the feed gas. Beaded designs offer greater surface area per unit volume for oxidation, although
carryover and erosion are more of a consideration.
The catalysts are sensitive to contaminants in the vapor stream; lead, zinc, mercury and other heavy metals as well as
halogenated compounds and hydrogen sulfide. Also, heavy hydrocarbons (even in small amounts) will tend to deposit on fixed
catalyst, which causes deactivation. As the catalyst becomes less active, the efficiency of the unit cannot be restored by
increasing the combustion temperature and the catalyst must be replaced. Typical catalyst life is two to five years after which
the deactivation by inhibitors, blinding by particle entrainment, and thermal aging render the catalyst ineffective.
Control efficiency performance of catalytic oxidizers depends on the operating temperature, temperature rise across the
catalyst bed, gas flowrate, the composition and concentration of the gas, and the catalyst. The optimum temperature depends
on the gas stream characteristics and the catalyst. Catalyst activity can be reduced at higher operating temperatures.

ExxonMobil Research and Engineering Company – Fairfax, VA

 ExxonMobil Proprietary
AIR POLLUTION CONTROL Section Page
XVIII-A2 27 of 42
CONTROL OF HYDROCARBONS, VOC
DESIGN PRACTICES AND AIR TOXICS EMISSIONS December, 2001

CONTROLLING LOADING EMISSIONS (Cont)

Because they need to run at relatively low temperatures, catalytic units are most effective at treating low concentration vapor
streams. Treating higher concentration vapor streams can overheat and deactivate the catalyst. Vapor concentrations from
gasoline or similar product loading operations are usually too highly concentrated and require dilution with excessive quantities
of air and/or an inert gas prior to combustion to maintain catalyst bed temperatures within an acceptable range. Catalytic
oxidizers are, therefore, generally not suitable for most loading operations but should be considered for special applications
with a low hydrocarbon concentration (i.e., about 1 %) in the incoming vapor.
The temperature and pressure drop across the catalyst should be monitored to determine catalyst condition and performance.
A decrease in temperature rise of the gas indicates that VOC oxidation may be incomplete and the catalyst may be deactivated
or there may be some contacting problems.
Costs for catalytic oxidizers depend on the fuel value of the gas, the gas flowrate, the fuel used, the amount of heat recovery,
the residence time, and the need to remove contaminants (particulates) from the gas stream. Operating costs for supplemental
fuel can be significant.
Destruction of VOCs using a catalytic oxidizer can produce secondary emissions such as CO2, NOx, and SOx. In addition,
regeneration or replacement of the catalyst can present a secondary solid waste.

Biofilters
Biofiltration is the aerobic degradation of contaminants in an air stream using microorganisms. The major advantages of
biofilters are a low overall cost and that they result in air emissions of essentially only CO2 and water vapor. Their range of cost
effective application, however, is limited to low concentration streams (generally less than 5,000 ppm) and easily degraded
compounds. Streams which are especially applicable for control by biofiltration include gases from wastewater treating, some
process vents, and vents from strippers. They are generally not applicable for the control of emissions from large loading
operations.
Biofilters are comprised of a bed of soil, compost, engineered material, or other contact media through which the contaminated
stream is passed. A biofilm exists on the contact media and the VOCs in the gas stream are used as a “food" source by the
microorganisms. As the gas passes through the biofilter, it is absorbed onto the film where the microorganisms oxidize the
components. Biofilter designs range from a simple open soil bed to a highly engineered enclosed process type vessel with
automatic moisture control.
Biofilter installations range from completely engineered systems to a simple series of distribution pipes below the surface of a
plot of land. The more complex systems have sophisticated controls on moisture content and distribution. Some systems even
include gas pretreatment. In addition, temperature control may become an issue in some locations since biofilters tend to
perform poorly at lower temperatures. The systems work best at between about 77 to 113°F (25 and 45°C) with a lower limit of
about 50°F (10°C).
Since the biofilter is an aerobic operation, the feed stream must include sufficient oxygen for complete conversion. Although
biofilters can respond to changes in input concentration and even retain effectiveness after several weeks of non use, the
destruction efficiency is decreased as the microorganisms increase to meet the new demand.
See EE.19E.94 for additional information on the use of biofilters for controlling emissions.

TABLE 10
COMPARISON OF VAPOR CONTROL OPTIONS

SECONDARY PRETREATMENT RANGE OF CONTROL

CONTROL
IMPACTS REQUIREMENTS CONCENTRATION (PPM) EFFICIENCY %

Vapor Balance — — — —

Adsorption Solid waste, wastewater Cooling, dehumidification, 20 - 20,000 90 - 99

particulate removal

Absorption Solid waste, wastewater Particulate removal 1,000 - 20,000 50 - 95

Refrigeration Solid waste, wastewater Dehumidification 5,000 - 10,000 50 - 95

Flares CO2, SOx, NOx — — > 98

Thermal Oxidizers CO2, SOx, NOx Pre-heating 20 - 20,000 95 - 99+

Catalytic Oxidizers CO2, SOx, NOx, solid waste Pre-heating, particulate removal 50 - 10,000 90 - 98+

Biofilters CO2, solid waste Humidification 10 - 5,000 90 - 95+

ExxonMobil Research and Engineering Company – Fairfax, VA

ExxonMobil Proprietary
Section Page AIR POLLUTION CONTROL
XVIII-A2 28 of 42
CONTROL OF HYDROCARBONS, VOC
December, 2001 AND AIR TOXICS EMISSIONS DESIGN PRACTICES

CONTROLLING LOADING EMISSIONS (Cont)

TABLE 11
ADVANTAGES AND DISADVANTAGES OF VAPOR CONTROL OPTIONS

VAPOR CONTROL
OPTION ADVANTAGES DISADVANTAGES
RECOVERY
Vapor Balance Recovery of pure product; Sometimes less Can be expensive if distances are large;
expensive than other options; Can be an Eventual additional controls often required;
effective way to smooth out fluctuations in vapor Cannot be used with floating roof tanks.
that will be controlled by other means.
Absorption Less expensive; Potential to recover material in Not efficient for low concentrations or low gas
mixture; Typical process operation; Low volumes; Subject to plugging and fouling from
pressure drop; Low energy consumption. particulates in feed stream; Lower efficiencies,
Recovered product may need to be separated.
Adsorption High efficiency; Recovery of “pure" stream; Low Limited capacity for high throughput /
operating cost; No open flame; Applicable to concentration streams; Not applicable to high
very low concentration streams; Applicable to temperature or high humidity streams; Potential
batch operations. for poisoning or plugging adsorbent bed; Need to
dispose of or regenerate adsorbent bed; May
require pre-filtering of gas feed to remove
particulates. Inefficient for lighter components.
Refrigeration Recovery of pure product; No open flames; Potential high energy cost; Low to moderate
Applicable for high concentration streams. efficiency; Disposal of liquid; Less applicable to
low boiling point streams; Need steady flow and
concentration; Not applicable to low
concentration streams.
DESTRUCTION
Flares Handles wide range of concentrations and Potential generation of products of incomplete
flowrates; Low cost. combustion; Placement; NOx emissions.
Thermal Oxidation High control efficiency; Handles variable stream Supplemental fuel may be required; Potential
concentrations; Moderate operating cost; Low generation of products of incomplete
maintenance costs; Energy recovery is possible. combustion; NOx emissions, additional treatment
necessary for treated halogenated compounds;
Placement.
Catalytic Oxidation High control efficiency; Reduced fuel Catalyst poisoning; High pressure drop; High
requirements and operating costs compared to vapor concentrations cause burnout while low
thermal oxidation; Handles variable concentrations require auxiliary heating; Catalyst
concentration and flowrates; Smaller size than replacement is costly; May be incompatible with
thermal oxidation equipment. halogenated compounds.
Biofilters Potentially high efficiency; Low installation and Need to maintain stream moisture and
operating costs; CO2 and water are essentially temperature; Potentially large space required for
only emissions; Treats low concentrations. unit; Not suitable for destruction of all
compounds. Not generally applicable for
controlling emissions from large loading facilities.

CONTROLLING WASTEWATER TREATING AIR EMISSIONS

The wastewater collection and treating system includes drains, manholes, sewers, junction boxes, primary oil / water
separators, air flotation units, and biological treatment units. Emissions are caused by the evaporation from an organic
containing wastewater flowing through or being treated in this equipment. Organics enter the water either through direct or
indirect contact. Direct contact sources include processes that use water for washing (e.g., desalter), sour water stripping and
also from steam used in jet eductors to produce vacuum. Indirect sources include leaks from heat exchangers, condensers
and pumps.

ExxonMobil Research and Engineering Company – Fairfax, VA

 ExxonMobil Proprietary
AIR POLLUTION CONTROL Section Page
XVIII-A2 29 of 42
CONTROL OF HYDROCARBONS, VOC
DESIGN PRACTICES AND AIR TOXICS EMISSIONS December, 2001

CONTROLLING WASTEWATER TREATING EMISSIONS (Cont)

The most cost effective way to reduce air emissions of hydrocarbons from wastewater is to minimize the quantity of
hydrocarbon entering the system. The use of open drains and sumps as routine organic collection systems should be
minimized. Another type of pollution prevention option is to improve the performance of strippers so that the hydrocarbon
concentration of water that enters the system is lowered. During unit shut-downs, in preparation for turnarounds, liquids should
be collected to the extent practicable in order to minimize discharge into the sewer system.
Once the flow has entered the wastewater system, most emission control opportunities are focused on reducing the contact
that the water has with the ambient air. Sewer system suppression includes installing traps in drains, and covering and sealing
sewers, junction boxes, and manholes. Emissions from separators and treaters can be reduced by covering the unit, and
recovering and controlling the emissions in a safe manner.

EMISSION SOURCES
Organic compound containing wastewater streams result from the direct contact of water with organic compounds and from
contamination of non-contact wastewater through equipment leaks. Water comes in direct contact with organic compounds
through many different 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 used as a carrier for catalyst and neutralizing agents (e.g., caustic solutions), and water
formed as a by product 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 variable in flowrate and concentration, 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.
Wastewater streams that are not intended to come in contact with organic compounds in the process equipment, but become
contaminated with organic compounds through equipment leaks are defined as non-contact wastewater. Non-contact
wastewater may become contaminated as a result of leaks from heat exchangers, condensers, and pumps. These non-contact
wastewaters may be collected and treated differently from direct contact wastewaters. Pump seal water is normally collected in
area drains that tie into the process wastewater collection system. This wastewater is then combined with direct contact
wastewater and transported to the wastewater treatment plant. Wastewater contaminated from heat exchanger leaks is often
collected in different systems and may bypass some of the steps used in the treatment plant. The organic compound content in
these streams can be minimized by implementing an aggressive leak detection program.
Wastewater streams are collected and treated in a variety of ways. Generally, wastewater passes through a series of collection
and treatment units before being discharged from a facility. Many of these collection and treatment system units may be open
to the atmosphere and may allow organic compound-containing wastewaters to contact ambient air, thus creating the potential
for VOC emissions. The organic pollutants volatilize in an attempt to reach equilibrium with the vapor phase above the
wastewater. These organic compounds are emitted to the ambient air surrounding the collection and treatment units. The
magnitude of VOC emissions is dependent on the physical properties of the pollutants, the temperature of the wastewater, the
design of the individual collection and treatment units, and the ventilation rate.
Collection and treatment schemes for wastewater are facility specific. The flowrate and organic compound composition of
wastewater streams at a particular facility are functions of the processes used and influence the sizes and types of collection
and treatment units that must be employed.
Wastewater streams from various sources throughout a given process are introduced into the collection system through
process drains. Individual drains usually connect directly to the main process sewer line, but may also drain to trenches,
sumps or ditches. Some drains are dedicated to a single piece of equipment, while others, known as area drains, serve several
sources. Some of these drains may be open to the atmosphere and may not be equipped with a water seal pot or p-trap to
reduce emissions of organic compounds to the atmosphere.
There are three theoretical paths for most organic compounds that enter the wastewater stream. One is to volatilize or
evaporate, causing an emission to the air. The second is to adsorb or absorb on to solids or sludges. The third is to
biodegrade into alternative compounds. The path taken depends on the physical properties of the compound and the
operational characteristics of the wastewater collection and treatment system.

Drains
Drain emission rates are affected by a number of factors including the composition and physical properties of the organic
compounds in wastewater entering the drain and flowing through the sewer line below the drain, the temperature of the
wastewater, the design characteristics of the drain, and climatic factors. Design characteristics that affect emissions are the
diameter and length of the drain riser. Climatic factors that have an effect on emissions include ambient air temperature and
wind speed.

ExxonMobil Research and Engineering Company – Fairfax, VA

ExxonMobil Proprietary
Section Page AIR POLLUTION CONTROL
XVIII-A2 30 of 42
CONTROL OF HYDROCARBONS, VOC
December, 2001 AND AIR TOXICS EMISSIONS DESIGN PRACTICES

CONTROLLING WASTEWATER TREATING EMISSIONS (Cont)

Manholes
Manholes are service entrances into process sewer lines that permit inspection and cleaning. They are placed at periodic
lengths along the sewer line or where sewers intersect or change significantly in direction, grade, or line diameter. The lower
portion of a manhole is usually cylindrical, with a typical inside diameter of 4 ft (1.2 m) to allow adequate space for workers.
The upper portion tapers to the diameter of the opening at ground level. A typical manhole opening is about 2 ft (0.6 m) in
diameter and covered with a heavy cast-iron plate, which may contain two to four holes so that the manhole cover can be
grasped for removal.
Emission rates from manholes are affected by several factors, including the characteristics of the wastewater passing through
the sewer line below the manhole, the manhole design characteristics, and climatic factors. Wastewater characteristics
affecting emission rates include wastewater composition and temperature. Manhole design characteristics that affect emission
rates include the diameter, the distance from the cover down to the sewer line, the thickness of the cover and the number and
diameter of the vent holes in the cover. Climatic factors that affect emission rates from manholes include ambient air
temperature and wind speed.

Junction Boxes
A junction box combines multiple wastewater streams into one stream that flows downstream from the junction box. Generally,
the flowrate from the junction box is controlled by the liquid level in the junction box. Junction boxes are either square or
rectangular and are sized based on the total flowrate of the entering streams. Emissions occur when organic compounds in the
wastewater volatilize into the ambient air just above the liquid surface in an attempt to reach equilibrium between the liquid and
vapor phases. Since the organic compound vapors above the liquid are in contact with the ambient air, these organic
compound vapors can be swept into the atmosphere by wind blowing across the top of the junction box. Emission rates from
junction boxes are affected by several factors, including the characteristics of the wastewater flowing through the junction box,
the design of the junction box, and climatic factors. Junction box design characteristics that affect emissions include the fetch-
to-depth ratio, the water turbulence in the junction box and the liquid surface area. Fetch is defined as the linear distance
across the junction box in the direction of the wind flow. Depth is represented by the average liquid level in the junction box.
Water turbulence enhances liquid phase mass transfer. In completely smooth flow, pollutants slowly diffuse to the water
surface to replace the volatilizing pollutants. In turbulent flow through the junction box, the organic compounds are carried
much more rapidly to the surface by the turbulent water. Therefore, in turbulent flow more organic compounds are exposed to
the surface air and the emission rate is increased. If the sewer lines feed water to the junction box above the liquid surface, the
exposure of organic compounds to the surface air is also increased. The water spills into the junction box, causing splashing
and additional turbulence at the liquid surface which increases emissions. In addition, wind entering the sewer system through
an upstream component may exit the junction box saturated with organic compounds. These effects can be minimized by
introducing water to the junction box below the liquid surface. In open junction boxes, ambient wind speed is the predominant
climatic factor affecting air emissions.

Lift Stations
Lift stations are usually the last collection unit before the treatment system. They may accept wastewater from one or from
several sewer lines. The main function of the lift station is to collect wastewater for transport to the treatment system. A pump
provides the necessary head pressure for transport and is generally designed to turn on and off in response to preset high and
low liquid levels. Lift stations are usually rectangular in shape and greater in depth than length or width.
The factors affecting emissions from lift stations are the concentration and physical properties of the organic compounds
present in the wastewater, lift station design characteristics and climatic factors. The design characteristics that affect
emissions include the liquid surface area, the water turbulence in the lift station and the fetch-to-depth ratio. The predominant
climatic factor affecting emissions is ambient wind speed.

Trenches
Trenches are used to transport wastewater from the point of discharge from the process equipment to wastewater collection
units, such as junction boxes and lift stations. In older plants, trenches may be the primary mode of wastewater transportation
in the collection system. Trenches are often interconnected throughout the process area and handle equipment pad water
runoff, water from equipment wash downs and spill cleanups and process wastewater discharges. Trench length is determined
by the locations of the process equipment and the downstream collection systems units. Depth and width are dictated by the
rate at which wastewater is discharged from process equipment and must be sufficient to accommodate emergency
wastewater flows.
Factors that affect emissions from trenches are the concentration and physical properties of the compounds in the wastewater,
climatic factors, the depth and width of the trench and the hydraulic retention time. Wind speed is the predominant climatic
factor affecting emissions.

ExxonMobil Research and Engineering Company – Fairfax, VA

 ExxonMobil Proprietary
AIR POLLUTION CONTROL Section Page
XVIII-A2 31 of 42
CONTROL OF HYDROCARBONS, VOC
DESIGN PRACTICES AND AIR TOXICS EMISSIONS December, 2001

CONTROLLING WASTEWATER TREATING EMISSIONS (Cont)

Sumps
Sumps are used to collect and equalize wastewater flow from trenches before treatment. They are usually quiescent and open
to the atmosphere. Sumps are sized based on the total flow rate of the incoming wastewater stream. As wastewater flows
slowly through the sump, organic compounds diffuse through the water to the liquid surface. These organic compounds
volatilize into the ambient air above the liquid and can be swept into the air by wind blowing across the surface of the sump.
The factors affecting emissions from a sump include the wastewater characteristics, wind speed, sump fetch-to-depth ratio,
liquid surface area and the hydraulic retention time.

Weirs
Weirs act as dams in open channels and provide some control of the level and flowrate through the channel. The weir face is
usually aligned perpendicular to the bed and walls of the channel. Water from the channel normally overflows the weir, but may
pass through a notch, or opening, in the weir face. Weirs may also be used for wastewater flowrate measurement.
Water overflowing the weir may proceed down stair steps that serve to aerate the wastewater. This design increases diffusion
of oxygen into the water which may benefit the biodegradation process. However, this increased contact with air also
accelerates the volatilization of organic compounds contained in the wastewater.
The major factors affecting emissions from weirs include wastewater characteristics, ambient wind speed and weir design
characteristics. The concentration and physical properties of the organic compounds in the wastewater have a significant effect
on VOC emissions. The diffusivity in water of the specific organic compounds present in the wastewater may be the most
significant physical property.
Ambient wind speed has a significant effect on convective mass transfer, because as the wastewater spills over the weir and
splashes down the stair steps, increased liquid surface area is exposed. The height of the weir is the most significant design
characteristic affecting emissions.

Oil / Water Separators

Oil / water separation is often the first step in wastewater treatment. These units gravity separate and remove oils, scum and
solids from the wastewater. Most of the separation occurs as the wastewater stream passes through a quiescent zone in the
unit. Oils and scum with specific gravities less than water float to the top of the aqueous phase and heavier solids sink to the
bottom. Some of the organic compounds contained in the wastewater will partition to the oil phase and can be removed with
the skimmed oil leaving the separator.
Volatilization of organic compounds from the surface of an oil / water separator is a complex mass transfer phenomenon. The
volatilization is caused by the drive to reach equilibrium between the concentration of organic compounds in the oil layer and
the vapor phase just above this layer. Organic compounds volatilizing into the vapor phase either diffuse or are swept by wind.
Factors affecting emissions from oil / water separators include characteristics of the wastewater and oil layers, the wastewater
temperature, ambient wind speed and design characteristics of the separator. The concentration and physical properties of the
organic compounds contained in the wastewater significantly affect emissions. The thickness of the oil layer also affects
emissions since organic compounds that partition from the wastewater into the oil phase must diffuse through the oil layer to
volatilize. Ambient air speed above the oil surface affects convective mass transfer into the ambient air. Design characteristics
affecting emissions include the length and width of the oil / water separator.

Equalization Basins
Equalization basins are used to reduce fluctuations in the wastewater temperature, flowrate and organic compound
concentrations to the downstream treatment processes. Equalization of wastewater flowrate results in more uniform effluent
quality from downstream units and can benefit biological treatment performance by damping any influent concentration and
flowrate fluctuations. This damping protects biological processes from upset or failure due to shock loadings of toxic or
treatment-inhibiting compounds. Equalization basins normally use hydraulic retention time to ensure equalization of the
wastewater effluent leaving the basin. Some basins are equipped with mixers or surface aerators to enhance the equalization,
accelerate wastewater cooling or saturate the wastewater with oxygen before secondary treatment. Factors affecting
emissions from equalization basins are wastewater characteristics, wind speed, equalization basin fetch-to-depth ratio, the
liquid surface area, the hydraulic retention time and the degree of aeration.

ExxonMobil Research and Engineering Company – Fairfax, VA

ExxonMobil Proprietary
Section Page AIR POLLUTION CONTROL
XVIII-A2 32 of 42
CONTROL OF HYDROCARBONS, VOC
December, 2001 AND AIR TOXICS EMISSIONS DESIGN PRACTICES

CONTROLLING WASTEWATER TREATING EMISSIONS (Cont)

Clarifier
The primary purpose of a clarifier is to separate solids from the wastewater through gravitational settling. Most clarifiers are
equipped with surface skimmers to clear the water of floating oil deposits, grease and scum. Clarifiers also have sludge raking
arms that remove the accumulation of organic solids collected at the bottom of the tank. The depth and cross-sectional area of
a clarifier are functions of the settling rate of the suspended solids and the thickening characteristics of the sludge. Clarifiers
are designed to provide sufficient retention time for the settling and thickening of these solids. The factors affecting emissions
from a clarifier include wastewater characteristics, wind speed and clarifier liquid surface area, the fetch-to-depth ratio and the
hydraulic retention time.

Biological Treatment / Aeration Basin

Biological waste treatment is normally accomplished through the use of aeration basins. Microorganisms require oxygen to
carry out the biodegradation of organic compounds, which results in energy and biomass production. The aerobic environment
in the basin is normally achieved with diffused or mechanical aeration which also serves to mix the biomass. The performance
of aeration basins is particularly affected by the mass of organic compound per unit volume of wastewater, temperature and
wind patterns, hydraulic retention time, dispersion and mixing characteristics, sunlight and the amount of essential microbial
nutrients present. Other factors affecting emissions from aeration basins include wind speed and basin design characteristics.
Emissions from aeration basins are not as sensitive to wind speed effects compared to quiescent basins. Basin design
characteristics that affect emissions include the quiescent and turbulent surface areas, the depth of the basin, the design of the
aerators and the hydraulic retention time of the basin.
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
the biodegradation and adsorption mechanism have an effect on air emissions.

Treatment Tanks
Several different types of treatment tanks may be used in wastewater treatment systems. Tanks designed for pH adjustment
typically precede the biological treatment step. In these tanks the wastewater pH is adjusted using acidic or alkaline additives,
to prevent shocking the biological system downstream. Flocculation tanks are typically used to treat wastewater after biological
treatment. Flocculating agents are added to the wastewater to promote formation or agglomeration of larger particle masses
from the fine solids formed during biological treatment. In the clarifier, which usually follows the flocculation tanks in the
system, these larger particles precipitate more readily out of the wastewater. Factors affecting emissions from a treatment tank
are the wastewater characteristics, wind speed, liquid surface area, the fetch-to-depth ratio and the hydraulic retention time.

Surface Impoundments
Surface impoundments are used for evaporation, polishing, storage before further treatment or disposal, equalization, leachate
collection and as emergency surge basins. They may be quiescent or mechanically agitated. Emission factor development for
a surface impoundment will vary depending on the impoundment's purpose and design. All characteristics of the impoundment
should be reviewed to determine what type of collection or treatment system it best resembles.

Air Emissions from Sludges or Waste Solids

Sludges and other waste solids from some units in the wastewater treating system may also be sources of air toxics and
hydrocarbons. These sludges and waste solids may contain organic compounds that may be released by air emissions. The
emissions may be by evaporation from the sludge or by generation of particulates during treatment or disposal of the sludge or
solids.
Wastewater sludges and solids treatment process have the potential for emission of organic compounds that may be present.
Mechanisms include evaporation for the volatile compounds and by dusting, erosion and materials movement for semi-volatiles
and metals that are emitted with particulates. Controls to reduce the emissions of volatile compounds include pre-treatment of
the sludge or solids (i.e., drying) and increasing the biodegradation time (e.g., sub-surface injection for landfarms). The primary
control to reduce particulate air emissions of semi-volatiles and metals is to maintain a high moisture content.

EMISSION CONTROL TECHNIQUES

As discussed above, emissions of VOCs from the collection and treatment of industrial wastewater can be significant. Three
control strategies are discussed in this subsection. The first is waste minimization through process modifications, preventive
maintenance, recycling, or segregation of waste streams. The second is to reduce the organic compound content of the
wastewater before the stream contacts ambient air. The third involves reducing the water-air interface.

ExxonMobil Research and Engineering Company – Fairfax, VA

 ExxonMobil Proprietary
AIR POLLUTION CONTROL Section Page
XVIII-A2 33 of 42
CONTROL OF HYDROCARBONS, VOC
DESIGN PRACTICES AND AIR TOXICS EMISSIONS December, 2001

CONTROLLING WASTEWATER TREATING EMISSIONS (Cont)

Waste minimization is a general term that includes both source reduction and recycling. Source reduction refers to reduction or
elimination of the generation of a specific waste at the source. This may be accomplished through process or equipment
modification, stream segregation or changes in work practices. Recycling includes recovery and/or reuse of potential waste
streams.
The first step in any waste minimization program should be to identify and characterize the individual waste streams. This
should include flowrate, composition, pH and solids content. Although some of these data might need to be gathered through a
sampling program, some of them may be available from hazardous waste manifests, release reporting calculations, permits,
monitoring reports, product and raw material specifications and other records. Using baseline data, a cost allocation system
can be developed to assess treatment and disposal costs of individual waste streams. Future treatment and disposal costs can
be considered in this evaluation, as can potential liabilities associated with the waste handling and subsequent treatment and
disposal. Once the waste streams have been ranked and prioritized, methods for controlling these streams can be considered.
As waste minimization steps are implemented, it is important that good record keeping be continued to document which steps
were effective and which ones failed. Although some wastewater streams will still be generated, an effective waste
minimization program may allow more cost-effective handling of these streams.

Stripping and Other Techniques to Reduce Concentrations

Steam stripping is proven technology that involves the fractional distillation of wastewater to remove organic compounds. The
basic operating principle of steam stripping is the direct contact of wastewater with steam. This contact provides heat for
vaporization of the more volatile organic compounds. The overhead vapor, containing water and organic compounds, is
condensed and separated (usually in a decanter) to recover the organic compounds. These recovered organics are usually
either recycled to the process or incinerated in an onsite combustion device.
Steam stripper systems may be operated in a batch or continuous mode. Batch steam strippers are generally more prevalent
when the wastewater feed is generated by batch processes, when the characteristics of the feed are highly variable, or when
small volumes of wastewater are generated. In contrast to batch steam strippers, continuous steam strippers are generally
designed to treat wastewater streams that are continuously discharged from process equipment and are relatively consistent in
composition. Batch wastewater streams can also be controlled by continuous steam strippers by incorporating a feed tank with
adequate residence time to provide a relatively consistent outlet composition.
The steam stripping system includes an enclosed wastewater collection up to a covered feed tank, the steam stripping tower
and controls on tank and condenser vents associated with the steam stripping system. The non-condensables are often vented
to the feed storage tank, which may be routed to a control device. The controlled sewer system, or hard piping from the point
of wastewater generation to the feed tank, controls emissions before steam stripping. The feed tank, which can be covered
and vented to an onsite combustion device, collects and conditions the wastewater fed to the steam stripper. The desired
retention time depends primarily on the variability in wastewater flowrate, characteristics of the inlet wastewater and the amount
of wastewater conditioning needed (i.e., separation of aqueous capacity can provide retention time for wastewater streams with
highly variable flow rates (including batch flow streams)) to maintain a relatively constant feed rate to the stripper.
After the wastewater is collected and conditioned, it is pumped throughout the feed / bottom heat exchanger and into the top of
the steam stripping column. Steam is sparged directly into the stripper at the bottom of the column and as the wastewater
flows down the column it contacts the steam countercurrently. Latent and sensible heat is transferred from the steam to the
organic compounds in the wastewater, vaporizing them into the vapor stream. These constituents flow out the top of the
column with any uncondensed stream. The wastewater effluent leaving the bottom of the steam stripper is pumped through the
feed / bottom heat exchanger to heat the feed stream and cool the bottoms before discharge.
In steam stripper systems, vent lines carry organics, water vapor and non-condensables to a control device. Vent lines may be
placed between the stripper column and primary condenser, between the primary condenser and feed tank and between the
feed tank and an existing onsite combustion device. A condenser system is used to recover the organic and water vapors in
the gaseous overhead stream from the stripping column. The condensed overhead stream is fed to an overhead receiver and
the recovered organic compounds are either pumped to storage and recycled to the process unit or combusted for their fuel
values in an incinerator, boiler or process heater. The feed tank vent line may be controlled with a combustion device or a
product recovery device.
Steam stripper VOC removal efficiencies are dependent on factors affecting the degree of contact that occurs in the steam
stripping column (column dimensions - height and diameter; contacting media- trays or packing; and operating parameters -
steam to feed ratio, temperature and wastewater pH) and wastewater characteristics such as organic compound volatility.

ExxonMobil Research and Engineering Company – Fairfax, VA

ExxonMobil Proprietary
Section Page AIR POLLUTION CONTROL
XVIII-A2 34 of 42
CONTROL OF HYDROCARBONS, VOC
December, 2001 AND AIR TOXICS EMISSIONS DESIGN PRACTICES

CONTROLLING WASTEWATER TREATING EMISSIONS (Cont)

Air Stripping
The underlying principle for air stripping is vapor-liquid equilibrium. By forcing large volumes of air through the contaminated
water the air-water interface is increased, resulting in an increase in the transfer rate of the organic compounds into the vapor
phase. The technology is applicable to compounds with a wide range of volatilities. The air used to remove the organic
compounds from the wastewater is usually vented to a control device. In many cases, this add-on control is a carbon adsorber
or a combustion device. In practice, air stripping is generally applicable only for streams containing low organic compound
concentrations.
The first component is the controlled sewer system or hard piping from the point of wastewater generation to the feed tank.
The tank collects and conditions the wastewater feed to the air stripper. The tank is usually covered and vented to a control
device. Wastewater is then pumped from the feed tank through a preheater and into the air stripper column. Wastewater is
introduced into the top of the column while air is blown from the bottom.
As the wastewater flows down through the column, it contacts the air that is flowing countercurrently up the column. With the
increased air-water interface provided by packing, the rate of transfer of organic compounds to air is increased. These
constituents flow out the top of the column with the air. The overhead stream can be vented to a boiler and used as
combustion air with supplemental heating value. The bottom stream flows to a wastewater treatment plant.

Biological Treatment
Biological waste treatment is normally accomplished through the use of aeration basins. Microorganisms require oxygen to
carry out the biodegradation of organic compounds that results in energy and biomass production. The aerobic environment in
the basin is normally achieved by the use of diffused or mechanical aeration. This aeration also serves to keep the biomass
well mixed. The goal is to maintain the biomass concentration at a level where the treatment is efficiently optimized and proper
growth kinetics are induced. The performance of aeration basins is particularly affected by the mass of organic per unit area,
temperature and wind patterns, hydraulic retention time, dispersion and mixing characteristics, sunlight, characteristics of solids
in the influent and the amount of essential microbial nutrients present. Basin efficiency, measured as the degree of stabilization
of the incoming wastewater, is dependent on both biological process kinetics and basin hydraulic characteristics.
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. The greater the biomass concentration in the
basin, the greater the removal of organic compounds will be by both biodegradation and adsorption mechanisms. The
biodegradability of a compound will also affect its removal by biodegradation. As the biodegradability of the compound
increases, so does the rate of biodegradation. Also, because the microorganisms prefer some compounds more than others,
the biodegradation process is selective and depends on the compound matrix. Octanol-water partition coefficients are often
used to indicate the affinity of a compound for the organic or aqueous phase. The relative magnitude of this coefficient
provides some indication of organic compound removal by the adsorption mechanism.
Typically, aeration basins are equipped with aerators to introduce oxygen into the wastewater. The biomass uses this oxygen
in the process of biodegrading the organic compounds. Aeration of wastewater also affects air emissions. Because of the
turbulence caused by the aerators, an increased liquid surface area is exposed to ambient air. Also, the liquid and gas phase
resistance to mass transfer are reduced and convective mass transfer in both phases is increased. This transfer mechanism
significantly increases air emissions compared to quiescent, flow-through type tanks such as clarifiers.
Factors affecting emissions from aeration basins include wind speed and basin design characteristics. Increases in wind speed
increase convective mass transfer from the wastewater in the basin and therefore, increase air emission. Emissions from
aeration basins are not as sensitive to wind speed effects as those from quiescent basins. Basin design characteristics that
affect emissions include the quiescent and turbulent surface areas, the depth of the basin, the design of the aerators, the
hydraulic retention time of the basin and the location of the feed. Sometimes air emissions can be reduced by splitting the feed
and introducing it in more than one location. As the turbulent surface area of the basin increases convective mass transfer of
the organic compounds increases. Convective mass transfer in the liquid phase increases as the basin becomes more shallow
and therefore, air emissions also tend to increase. Because the aerators generate the turbulence that increases the rate of
mass transfer in the liquid and gas phases, the design of these aerators has a significant effect on emissions. Increases in
turbulence of the wastewater tends to increase air emissions. The final design parameter affecting emissions is the volume of
the basin. As the volume increases, so does the hydraulic retention time. Increases in the basin volume provide additional
time for removal by all three mechanism: biodegradation, adsorption and air emission. Therefore, the magnitude of the
increase in air emissions due to the additional retention time depends on the relative removal rates by the other two
mechanisms.

ExxonMobil Research and Engineering Company – Fairfax, VA

 ExxonMobil Proprietary
AIR POLLUTION CONTROL Section Page
XVIII-A2 35 of 42
CONTROL OF HYDROCARBONS, VOC
DESIGN PRACTICES AND AIR TOXICS EMISSIONS December, 2001

CONTROLLING WASTEWATER TREATING EMISSIONS (Cont)

Other Technologies
Although steam stripping and air stripping are the most widely applicable technologies for VOC emission reduction from
wastewaters, there are applications where other technologies may be more appropriate. In addition to steam stripping,
technologies available for removing organic compounds from wastewater include chemical oxidation, carbon and ion exchange
adsorption, membrane separation and liquid-liquid extraction. These technologies rely on a variety of mechanisms to remove
organic compounds from wastewater.
Chemical oxidation involves a chemical reaction between the organic compounds and an oxidant such as ozone, hydrogen
peroxide, permanganate, or chlorine dioxide. The applicability of this technology depends on the reactivity of the individual
organic compounds. For example, phenols and aldehydes are more reactive than alcohols and alkyl-substituted aromatics.
Halogenated hydrocarbons and saturated aliphatic compounds are the least reactive.
Adsorption processes take advantage of compound affinities for a solid sorbent medium. Activated carbon or polymeric resins
are often used as the medium. The volatile compounds are adsorbed onto the solid sorbent medium as they are contacted by
wastewater. Non-polar compounds can be adsorbed onto the surface of activated carbon. By contrast, removal by polymeric
resins involves both adsorption and ion exchange mechanism and is therefore more effective for polar compounds. With
carbon adsorption, the capacity of the carbon to adsorbed the organic compounds at a given influent concentration varies
widely for different compounds. In addition, the ease of desorption (removal) of the organic compounds and possible
wastewater contaminants from the carbon is highly variable. It is for these reasons, the feasibility of using carbon adsorption
must be evaluated on a case-by-case basis.
Two types of membrane separation processes are ultra filtration and reverse osmosis. Ultra filtration is primarily a physical
sieving process driven by a pressure gradient across a membrane. This process separates macromolecular organic
compounds with molecular weights of greater than 2,000, depending on the membrane pore size. Reverse osmosis is the
process by which a solvent is forced across a semipermeable membrane due to an osmotic pressure gradient. Selectivity is,
therefore, based on osmotic diffusion properties of the compound and the sizes of the compound and the membrane pores.
Liquid-liquid extraction, sometimes referred to as solvent extraction, uses differences in solubility of compounds in various
solvents as a separation technique. By contacting a solution containing the desired compound with a solvent in which the
compound has a greater solubility, the compound may be removed from the solution. This technology is often used for product
and process solvent recovery for two reasons. First, the solvent can usually be regenerated and second, the compound of
interest can often be recovered by distillation

Collection and Treatment System Controls

The VOC emissions from wastewater collection and treatment systems can be controlled either by hard piping or by enclosing
the transport and handling system from the point of wastewater generation until the wastewater is treated to remove or destroy
the organic compounds. Suppression techniques can be broken down into four categories: collection system controls, roofs,
floating membranes and air supported structures. Suppression of VOC emissions keeps the organic compounds in the
wastewater until they reach the next wastewater treatment operation. Therefore, these techniques are not effective unless the
VOC emissions are suppressed until the wastewater reaches a treatment device where the organic compounds are either
removed or destroyed.
Collection systems comprise components such as drains, junction boxes, sumps, trenches and lift stations that provide contact
between wastewater and ambient air. As previously described, these collection system components provide escape routes for
organic compounds contained in wastewater. Suppression controls can be applied to most of these components to reduce the
potential of VOC emissions during wastewater collection. These controls involve the use of physical covers and water seals to
minimize the contact between ambient air and the wastewater flowing through the component.
Two commonly used methods for controlling emissions from drains are p-leg and seal pot configurations. Control of emissions
can also be achieved by hard piping any source of wastewater containing organic compounds to a control device. Other
collection system components that typically require control are junction boxes, sumps and lift stations. For these components,
a gas tight cover is typically used to control emissions.

Fixed and Floating Roofs

Storage or treatment of wastewater in fixed-roof tanks instead of open-top tanks reduces VOC emissions. By covering the
tank, the wastewater surface is sheltered from the wind which decreases the mass transfer rate of organic compounds in the
wastewater to the atmosphere. The extent to which VOC emissions are reduced depends on many factors including
wastewater composition, organic compound concentrations, wind speed and the ratio of the tank diameter to the depth of the
wastewater contained in the tank.

ExxonMobil Research and Engineering Company – Fairfax, VA

ExxonMobil Proprietary
Section Page AIR POLLUTION CONTROL
XVIII-A2 36 of 42
CONTROL OF HYDROCARBONS, VOC
December, 2001 AND AIR TOXICS EMISSIONS DESIGN PRACTICES

CONTROLLING WASTEWATER TREATING EMISSIONS (Cont)

Floating roofs are appropriate for wastewater storage tanks and certain treatment tanks where the presence of the floating
cover would not interfere with the treatment process. Treatment tanks equipped with surface mixing or aeration equipment
cannot use floating roofs. Also, because floating roofs are in direct contact with the wastewater, the materials selected to
fabricate the deck and seals must be compatible with the wastewater composition. Floating roof tanks significantly reduce, but
do not eliminate VOC emissions. Organic vapor losses called “standing losses" occur at the deck seals and fitting openings.
Additional organic vapor losses called “withdrawal losses" occur from evaporation of the liquid that wets the inside tank wall as
the roof descends during emptying operations.
The most effective option for controlling VOC emissions from oil / water separators is to install either a fixed or floating roof.
These roofs control VOC emissions by reducing the oil surface exposed to the atmosphere, reducing the effects of wind
velocity and reducing the effects of solar radiation by insulating the oil layer. Fixed roofs can be installed on most oil / water
separators. This can be done without interfering with the operation of the system by mounting on the sides of the separator or
by supporting the horizontal steel beams set into the sides of the unit. Gas-tight access doors are usually installed in the roof
for maintenance and inspection. Since the vapor space below fixed roofs may constitute an explosion or fire hazard, the vapor
space is often blanketed with nitrogen and/or purged to a recovery or destruction device. For floating roofs, the effectiveness of
their emission control is primarily dependent on the effectiveness of the seals between the roofs and walls of the separator. If
these seals are not well maintained to prevent leakage, their VOC emission control capabilities will be reduced significantly.
One final concern in evaluating emissions over oil / water separators is the handling of the recovered oils. Since the oils may
contain high concentrations of organic compounds, care must be taken to minimize VOC emissions. This can be accomplished
by handling the oils and organic compounds in closed systems equipped with emission controls.

Floating Membranes
A floating membrane cover consists of large sheets of synthetic flexible membrane material that floats on the surface of the
wastewater. Individual sheets can be seamed or welded together to form covers applicable to any size areas. Floating
membrane covers have been used successfully for many years to cover the surface of potable water impoundments or
reservoirs. In the “leak tight" application, floating membrane covers have been used to cover large anaerobic digester lagoons
to collect the methane gas for energy recovery.
The effectiveness of a floating membrane cover depends on the amount of wastewater. Using a membrane material with
adequate thickness and following good installation practices will minimize tearing or puncturing of the membrane material. The
overall cover permeability is a function of the organic composition and concentration of the wastewater managed in the surface
impoundment as well as the cover material's composition and thickness.

Add-On Controls
Add-on controls serve to reduce VOC emissions by destroying or extracting organic compounds from gas phase vent streams
before they are discharged to the atmosphere. Add-on controls are applicable to vents associated with collection and treatment
covers, such as drain covers, fixed roofs and air supported structures, and with organic compound removal devices, such as air
strippers and steam strippers. Add-on controls for VOC emissions are classified into five broad categories: adsorption,
combustion, condensation, adsorption and biofiltration. The type of add-on control best suited for a particular wastewater
emission source depends on the size of the source and the characteristics of the wastewater in the source.

MISCELLANEOUS SOURCES
There are a number of smaller miscellaneous sources of hydrocarbon emissions throughout a refinery or chemical plant. In
most cases, emissions from these sources contribute minimally to the overall plant emissions. This section describes some of
these sources and suggests control alternatives.

VACUUM SYSTEMS
Vacuum distillation columns can be a source of VOC emissions from fractionation units. Vacuum in the tower is created by
removal of non-condensable gases and process steam by the use of steam jet ejectors or mechanical vacuum pumps. The
vapors are condensed and the non-condensable VOCs are a potential emission. Steam ejectors with contact condensers also
have VOC emission from their hotwells.
VOC emissions from vacuum systems can be controlled by piping the non-condensable vapors to a control device or
compressing the vapors and routing them to the refinery fuel gas system. The hot wells associated with contact condensers
can be covered and the vapors collected for recovery or destruction. Vapor recovery and destruction control options are
discussed in the LOADING section of this DP.

ExxonMobil Research and Engineering Company – Fairfax, VA

 ExxonMobil Proprietary
AIR POLLUTION CONTROL Section Page
XVIII-A2 37 of 42
CONTROL OF HYDROCARBONS, VOC
DESIGN PRACTICES AND AIR TOXICS EMISSIONS December, 2001

MISCELLANEOUS SOURCES (Cont)

TURNAROUNDS
Most process units and storage tanks are periodically shut down and emptied for internal inspection and maintenance. In order
for personnel to enter a vessel, liquids are pumped to storage, vapors purged, and the vessel is ventilated. VOC emissions
occur when the vessels are purged. Released vapors usually are routed to a blowdown stack or flare that is remotely located
to ensure that combustible mixtures will be a safe distance from process areas.
VOC emissions from process unit turnarounds can be controlled by venting the vapors to a control device until the vessel is
near atmospheric pressure. Typically, either vapor recovery or a flare is used for control. In many cases, the vessel is next
steam flushed. Small amounts of VOCs will continue to be emitted until all VOC is completely removed from the vessel.
Continued vapor control is an option, but is expensive, if release of these very low concentration vapors to the atmosphere is
not allowed.

COOLING TOWERS
Cooling towers dissipate heat from water used to cool process equipment such as reactors, condensers, and heat exchangers.
Cooling water is circulated through process unit heat exchangers and returned to a cooling tower where the water is cooled
evaporatively by forced or induced air circulation. VOC emissions from cooling towers occur as a result of leaking heat
exchangers (where process pressure is higher than cooling water pressure) and reuse of process wastewater in the cooling
system. VOCs are released at the top of the cooling tower as water vaporizes and also from the bottom where water collects
prior to recirculation.
Cooling tower VOC emissions are best controlled by minimizing the quantity of VOCs entering the cooling water system. One
technique is to reduce or eliminate the use of contaminated process wastewater as cooling tower make-up. Another technique
is to monitor total organic carbon in the cooling water to detect early indications of equipment leaks.

RESPONDING TO ODOR COMPLAINTS

Odors are usually the subject of most complaints facilities receive from their surrounding communities. In many cases, the
public perception is that an unpleasant odor indicates the presence of harmful chemical substances. Local regulatory
authorities are more likely to be notified and requested to act on odor problems than on most other environmental issues.
Thus, facilities need to rapidly address community concerns about objectionable odors to minimize the potential impact on plant
operations and maintain good community relations.
Most studies on the effects of air pollutants are usually focused on assessing long-term symptoms such as mortality and
disease or short-term, acute toxic effects. Such studies often do not include symptoms such as annoyance, irritability,
discomfort, and general dissatisfaction. These short-term, temporary reactions to air pollution are frequently triggered by
exposure to odoriferous air streams. The magnitude of contamination in these air streams may not be sufficient to cause any
acute, chronic or permanent symptoms, but may be enough to cause considerable annoyance to the exposed population.
Compared with reaction to odorless pollution, which is indirect and is delayed to later times after health and other effects are
diagnosed, reaction to odor pollution is direct and response to odoriferous air streams is immediate. Reaction to odor is aided
considerably by the robust use of the nose, which is a most powerful sampling device. The nose perceives levels of odorants
at levels that can be detected only by the most advanced analytical instruments.

ODOR: PERCEPTION, EFFECT, AND CHARACTERIZATION

Several dimensions of human responses to the odor sensation can be characterized. These are threshold, intensity, character,
and hedonic tone. Threshold, or detectability, refers to the minimum concentration of odorant that is necessary for perception.
A threshold value is a statistical average representing the mean detection limit from a group of test subjects. Two types of
thresholds can be evaluated: detection and recognition.
The detection threshold is the lowest concentration of odorant that will elicit a sensory response in the olfactory receptors of a
specified percentage, usually 50%, of the population being tested. The detection threshold is identified as an awareness of an
odor without necessarily involving its recognition. The recognition threshold is defined as the minimum concentration
recognized as having a characteristic odor quality by a specified percentage of the population, usually 50%. It differs from the
detection threshold as it is the point at which a specific odor character description can be attributed to the sensory response
The recognition threshold is usually 2 to 10 times the detection threshold.
Olfactory sensitivity in the population follows a bell curve normal distribution ranging from hypersensitive to insensitive and, for
a few, all the way to anosmic (unable to smell). In some cases individual odor threshold scores can be distributed several
orders of magnitude around the mean value. A listing of threshold values for pure chemicals is presented in EE.72E.94. There
are two documents reporting odor thresholds for a large number of chemicals: Odor Thresholds, American Industrial Hygiene
Association (1989) and EPA-600/R-92-047.

ExxonMobil Research and Engineering Company – Fairfax, VA

ExxonMobil Proprietary
Section Page AIR POLLUTION CONTROL
XVIII-A2 38 of 42
CONTROL OF HYDROCARBONS, VOC
December, 2001 AND AIR TOXICS EMISSIONS DESIGN PRACTICES

RESPONDING TO ODOR COMPLAINTS (Cont)

Odor intensity refers to the perceived strength of the odor sensation. Intensity increases as a function of concentration. The
relationship of the perceived strength (intensity) and concentration is expressed by:
n
S = KI
where: S = Perceived intensity of the odor sensation
I = Physical intensity of stimulus (odorant concentration)
n = Constant
K = Constant
Another dimension of odor is its character, or what the odor smells like. The scale uses such descriptors as: fishy, nutty,
moldy, rancid, sewer, ammonia, etc. This dimension is useful in control programs to describe the source or process
responsible for community odors because different odor characters are associated with various processes and industries.
Hedonic tone, also referred to as “acceptability", is a category judgment of the relative pleasantness or unpleasantness of the
odor. In considering community response, the hedonic tone is very important. Perception of the odor is based on the
combination of frequency of occurrence, odor character, and odor intensity. Even pleasant odors may become objectionable if
they persist long enough or occur often.
The repeated exposure to an odor can result in either an enhanced reaction described as sensitization or a diminishing reaction
defined as tolerance. If a person becomes sensitized to an odor, the result may be an increase in complaints regarding the
odor. On the other hand, tolerance of an odor may attribute to one's unawareness of the continuous exposure to a substance.
Also, a person may be more sensitive to one odorant than to another. Such differences are often caused by repeated exposure
to a particular odor. For example, this would not be uncommon for chemists or manufacturers who have been exposed daily to
an odorant over a period of years. Fatigue may also play an important role in odor perception. Repeated exposure to an
odorant would result in a desensitization to the odorant, where an observer may no longer detect an odor although it is strongly
detectable by others.
An additional problem in odor identification is that ambient odors are generally mixtures of compounds in different concentration
levels. A comparison of the perceived intensity of two chemicals presented alone at a certain concentration and the two
chemicals in a mixture at the same concentrations most commonly shows that the perceived intensity of either chemical in the
mixture is lower than it is alone at the same concentration. This known as hypoadditivity.
Human response to odor is also based upon the community, meteorology, and topography interactions. An odor with an
acceptable hedonic tone and low intensity may generate complaints when there is a lack of familiarity with the odor character,
therefore causing concern with toxicity. Conversely, in some instances high intensities of hedonically unpleasant odors are
tolerated because they are considered socially acceptable. Even pleasant odors such as perfumes or roasting coffee are
considered objectionable if they are allowed to persist for a long period of time, or are frequently present. Demographically,
awareness of air pollution problems increases with education, income / occupational level, and age. Some of this awareness is
also based on economic factors, such as property values.
Odors may serve as warning agent of potentially dangerous materials. The warning property of odor has long been
recognized. The property of odor as a warning agent has been utilized through the addition of mercaptan to odorless natural
gas The perceived connection between odors and disease persists. With attention focused on waste and chemical spills, in
the absence of specific information to the contrary, the average person will conclude that a bad smell is likely to be unhealthy.
The relationship between odor and health effects should be clarified. Many odorants are perceptible at concentrations far
below harmful concentration levels. For example, hydrogen sulfide (H2S) has been detected at concentrations as low as 0.01
parts per billion, whereas acceptable exposure limit or the Threshold Limit Value-Time Weighted Average (TLV-TWA)
recommended by the American Conference of Governmental Industrial Hygienists (ACGIH) for this compound is 10 parts per
million, six orders of magnitude greater. Thus, detection of the “rotten egg" character of H2S is not necessarily an indicator of a
potential health effect. Similarly, the TLVs for cresol and ethyl acrylate are four orders of magnitude greater than their odor
detection threshold values.

ExxonMobil Research and Engineering Company – Fairfax, VA

 ExxonMobil Proprietary
AIR POLLUTION CONTROL Section Page
XVIII-A2 39 of 42
CONTROL OF HYDROCARBONS, VOC
DESIGN PRACTICES AND AIR TOXICS EMISSIONS December, 2001

RESPONDING TO ODOR COMPLAINTS (Cont)

STEPS FOR ADDRESSING ODOR PROBLEMS

This section provides a step-by-step approach for addressing odor problems. Table 12 contains a listing of the “Steps for
Addressing Odor Problems" and the following sections provide additional details and explanation on each of the steps
suggested. These steps include:
1. Establishing the need for further action
2. Identifying the cause
3. Quantifying the ambient concentration impact from the emission
4. Reducing or eliminating the problem.
This structured approach focuses emissions reduction and control efforts on those sources that are the more likely causes of
the odor and thereby minimizes costs to solve the problem.
Odor problems are subjective. Different people detect odors at different concentrations and may disagree on whether an odor
is pleasant or objectionable. In some cases, even a pleasant odor may produce complaints if persistent or of high intensity. If
someone in the community perceives that an odor is a nuisance, it is usually advisable to accept this, look for the cause, and
reduce the problem. Since the resolution of an odor problem is often political as well as technical, the plant public affairs
specialist should be included in technical meetings aimed at solving the odor problem. This can often improve interaction with
the surrounding community and reduce the likelihood of any additional regulatory agency actions.
Table 12 lists the “Steps for Addressing Odor Problems" and may be used as a “checklist" when complaints are received. This
step by step approach allows a systematic resolution of the odor problem. For each step, issues are listed in the form of
questions that should be considered in determining what actions may be required. Since some of the issues listed may not
apply in certain situations, every issue need not be addressed.
Each of the steps recommended requires the collection of site specific information. Close coordination among the public
affairs, environmental, operations and engineering functions is recommended in order to obtain a fully workable solution that
can be implemented at the lowest cost and that will satisfy the local community and regulatory agencies.
Step 1: Establishing the Need for Further Action
In this step, the urgency and potential resources that will be required to solve the problem are determined. Those odor
problems that are characterized by frequent complaints from a large part of the community, or where local regulations restrict
the generation of odors, will require a much more rapid and comprehensive response than will problems without these
characteristics. Also, odors that may indicate health concerns for the community or plant personnel will require a rapid
response.
The approach to solving an odor problem will depend on the source of the complaint as well as the requirements of local
regulations which govern odors or other nuisances. Most odor problems that require quick action are the result of complaints
from the surrounding community. Many plants have well established relationships with a supportive community and these may
serve as a reliable indicator of the severity of the problem. In all cases, it is important to maintain open and frequent
communication with the surrounding community as the odor problem is being resolved.
In some cases, it may be possible to eliminate the need for additional follow-up by showing that the odor is benign, that it is
unlikely to continue, or that the source is not from your facility. These possibilities will be very site and situation specific. Care
should be taken, however, not to give the appearance of minimizing the importance that the facility places on achieving a
solution to the odor problem.
The sudden presence of an odor may be an indication of an operations problem that needs attention. When odor problems are
identified by plant personnel, they can often be resolved before the surrounding community is affected and before complaints
are received. Sometimes, the presence of an odor indicates that concentration of a particular chemical is above acceptable
levels, and, therefore, it may be appropriate for the plant industrial hygienist to be consulted for all odor problems.
Specific local regulations may exist for controlling odors or eliminating nuisances. In some locations, regulations require that
any offensive conditions be eliminated. Surrounding communities may be active in pressing for more stringent regulations
should severe odor problems persist. A more recent practice is for those in the affected community to initiate legal actions to
seek “damages" for the perceived reduction in the quality of their environment. Good community relations and a rapid plant
response are the best approaches to minimize the likelihood of a more costly regulatory agency enforced response to an odor
problem.

ExxonMobil Research and Engineering Company – Fairfax, VA

ExxonMobil Proprietary
Section Page AIR POLLUTION CONTROL
XVIII-A2 40 of 42
CONTROL OF HYDROCARBONS, VOC
December, 2001 AND AIR TOXICS EMISSIONS DESIGN PRACTICES

RESPONDING TO ODOR COMPLAINTS (Cont)

Step 2: Identifying the Cause
In this step, the emission sources that are causing the odor problem are identified. Sometimes the sources of the odorous
chemicals are obvious, and sometimes they are nearly impossible to determine. The first step in locating the sources is to
make an attempt at determining the chemicals present from their characteristic smell. Many classes of chemicals provide
distinctive odors that are easily recognized. Some plant personnel have become quite adept at recognizing odors from
particular process units, and they may be a good resource in locating both the source of the emission and the chemicals
involved.
Once the type of chemicals causing the odor problem are identified, the specific sources of the emission needs to be
determined. Typical sources include the wastewater treating system (including sewers, junctions, and access holes), fugitive
equipment leaks (valves, pumps, compressors, connectors / flanges, pressure relief valves, etc.), tanks (working and storage
losses), vents, loading operations, land farms and other solid waste treatment, storage or disposal units and intermittent
operations (vessel degassing, exchanger cleaning, painting). In some cases the odor may have been caused by a small spill
that is easily located and treated. When the odor is only detected outside the facility boundary, an elevated source (e.g., stack
or vent) may be the cause, with the odorous plume reaching ground level some distance from the plant.
Emission sources outside the plant should also be considered as the potential cause of the odor problem. Sometimes the
surrounding community wrongly attributes an objectionable odor to a refinery or chemical plant just because it is a large (and
perhaps historically likely) nearby source. Small adjacent facilities may be responsible for the odor problem or may contribute
significantly to the problem. If an adjacent facility is suspected, it is usually necessary to fully quantify the emissions and
resultant ambient concentrations so that contributions to the odor problem can be attributed to the appropriate internal and
external emission sources.
In some cases, the specific source of the odorous emission cannot be clearly identified. Application of low cost emission
reduction options should be considered for the more likely sources of the odor. Tracer studies, using a non-toxic identifier
included with other releases, may help to identify source and receptor location relationships and thereby reduce the number of
potential emission sources that need to be considered for further action.
Step 3: Quantifying the Ambient Concentration
In this step, the ambient concentrations of the odor causing compounds are quantified to help in determining their contributions
to the problem and to focus odor reduction efforts. This can involve ambient air monitoring as well as emissions estimating and
dispersion modeling. In cases where the odor source is not clearly identified, some combination of both approaches may be
required to fully evaluate the situation. If working with a local regulatory agency, it is prudent to acquire their acceptance of the
chosen quantification approach before proceeding with extensive and costly monitoring or modeling efforts. The modeling
impact analysis will also allow an industrial hygienist to compare the predicted concentrations of specific chemicals to the
recommended health based standards.
Ambient air monitoring is generally more costly than emissions and dispersion modeling and has some additional limitations.
These limitations include the potential for missing the plume location, and therefore the maximum concentration, by having too
few, or too widely spaced, monitors. There may also be some compounds whose odor detection threshold concentrations are
lower than can be monitored with the available equipment. If the odorous compound is detected above threshold level
concentrations, however, monitoring provides good evidence of the problem and subsequent monitoring, after mitigation steps
are implemented, can demonstrate progress.
The modeling approach involves estimating the emissions of odorous compounds from the suspect process units and using
dispersion models to predict downwind ambient concentrations. Fugitives, tanks, loading, sewers and wastewater treating are
sources to consider if the odor problem is continuous or occurs frequently. In some cases, odor complaints can be correlated
with tank filling or other loading operations.
Transient emissions, such as from vents, safety valves, spills, and maintenance operations require either a means to measure
the released quantity or a basis to determine, through engineering analysis, how much material has been released. In these
cases, a first approach is to assume the largest quantity of material available is released, and the predicted ambient
concentration is compared to the odor threshold. If this conservative approach results in predicted ambient concentrations well
below the odor threshold, then the source is not likely to be the cause of the odor problem.
For dispersion modeling, sources must be described as either points, lines, areas, or volumes. The selection of source type
has a significant impact on the magnitude of the predicted ambient concentration. Tanks, vents, and loading emissions
sources are usually treated as point sources. Wastewater treating, land farm, and spills are area sources. Fugitive emissions
are the most difficult to describe since, although they are discrete point sources, their large number precludes modeling each
release point individually. Fugitives have been modeled as single combined near ground level point source which includes all
the fugitives for an entire unit, as an area source equivalent to the “foot-print" of the unit, and as a volume source. If modeling
is required by a regulatory agency, details of the modeling procedures should be reviewed with the local authorities before
proceeding with the analysis to assure acceptance of the results.

ExxonMobil Research and Engineering Company – Fairfax, VA

 ExxonMobil Proprietary
AIR POLLUTION CONTROL Section Page
XVIII-A2 41 of 42
CONTROL OF HYDROCARBONS, VOC
DESIGN PRACTICES AND AIR TOXICS EMISSIONS December, 2001

RESPONDING TO ODOR COMPLAINTS (Cont)

Care must be taken in interpreting the results from standard dispersion models when predicting down wind ambient
concentrations of the suspected odorous compound. Most of these models predict ambient concentrations that are time
averages over about 15 minutes to 1 hour. If the odor problem is not constant, one may need to consider much shorter
concentration averaging times. The technology to predict these very short average time concentrations, however, is still
developing. An approximation may be made by multiplying the concentration predicted by the standard models by a factor of 3
to 6 to obtain a short averaging time “peak" concentration prediction.
When conducting the impact analysis, it may be useful to include nearby emission sources that are not within the plant
boundary. Although the plant sources may result in a predicted concentration that is well below the odor threshold, the
combined sources may be sufficient at times of specific wind direction or plant operations to result in odor complaints from the
surrounding community.
Application of the modeling approach is limited to cases where sufficient information to quantify the source emissions and
atmospheric dispersion is available. In some cases, there may not be a clear indication of either the chemical causing the odor
or the potential sources. Modeling in these situations is inappropriate and can result in the use of unrealistic assumptions
leading to a poor choice of emission reduction and control.
Additional details on the use of dispersion models can be found in Section XVIII-A1.
Step 4: Reduce or Eliminate the Odor Problem
This step includes a determination of the amount of emission reduction required and the choice of reduction or control
alternatives. In some cases, it can be beneficial to prioritize the emission source list based on the contribution to the odor, the
cost to control, or other factors. A preliminary step in determining acceptable control options is to determine the amount of
emission reduction required to eliminate or reduce the odor problem. A 50 percent decrease in emission and, therefore,
equivalent reduction in ambient concentration, will usually result in less than a 50 percent perceived reduction in the odor
intensity. The perceived odor intensity is related to the ambient concentration of the odorous compound by Stevens' Law.
The value of the exponent in Stevens' Law ranges from about 0.2 to 0.6 with most sulfur compounds in the 0.3 range. Thus, for
example, a reduction of 50 percent in the ambient concentration for a compound with a Stevens' Law exponent of 0.3 will result
in only a perceived odor reduction of less than 20 percent. Thus, much more source reduction is required than if the odor
problem was just proportional to ambient concentration.
Stevens' Law exponents are presently available for only a limited number of chemicals. A list of the exponents is provided in
EE.72E.94. These exponents have been developed through the use of test subjects in groups called odor panels. Since there
have been different protocols and panels used in the various studies, the actual reported values of the exponent tend to vary.
As indicated above, however, a reasonable approach is to use a value of 0.3 if data are not available.
In choosing a mitigation approach, consideration must focus on what will satisfy the local community and regulatory authorities.
It may be important to balance reductions in odor intensity with frequency of occurrence. In some cases there is an advantage
to reducing the frequency rather than the magnitude of an odor problem since the former may involve operations and
housekeeping while the later is likely to involve some investment.

TABLE 12
STEPS FOR ADDRESSING ODOR PROBLEMS
Step 1: Establish the Need for Further Action
• Is the action required because of a community complaint? How frequent are the complaints and what percentage of the
community is complaining? Are the complaints mostly from a single geographic location or are they wide spread?
• Has worker concern about safety or health initiated the action? Has an industrial hygienist been included in the problem
solving group? Are the potential odor causing chemicals a safety or health problem?
• Are there local nuisance or odor regulations? Have there been any complaints from the community to the local regulatory
agencies? Have the local regulatory authorities contacted the facility and are there time limits or other requirements that
they have established for solving the odor problem? Has the facility previously had discussions with the local regulatory
agency about other odor problems?
• Is the control of odors driven by an internal initiative for safety, health or general housekeeping? Identify the initiative.
• Are there any health concerns for either the community or plant personnel based on the chemicals involved? Are these
based on immediate or longer term effects of exposure to the chemical?

ExxonMobil Research and Engineering Company – Fairfax, VA

ExxonMobil Proprietary
Section Page AIR POLLUTION CONTROL
XVIII-A2 42 of 42
CONTROL OF HYDROCARBONS, VOC
December, 2001 AND AIR TOXICS EMISSIONS DESIGN PRACTICES

RESPONDING TO ODOR COMPLAINTS (Cont)

Step 2: Identify the Cause
• Can the type of odor be identified? Is it generally pleasant or objectionable? Is it being detected inside as well as outside
the facility? In what locations is it being detected most frequently?
• When and how frequently do the odors occur? Does the occurrence of the odor correlate with any specific plant operation
(e.g., start-ups, tank or vessel loading, etc.)? Does the occurrence of the odor correlate with any specific meteorological
condition (i.e., wind speed or direction)?
• What are the likely chemicals that are causing the odor? Are those chemicals normally handled in the facility? Where in the
facility are those chemicals present? Are those chemicals also handled in adjacent or near by facilities that could be the
cause or could be contributing to the odor complaints?
• What are the potential plant sources for the chemicals causing the odor problem? Are they from specific units in a small
area or are the sources wide spread? Does the location, timing of the complaints, wind direction, or other factors suggest a
specific plant area that may be the source of the odorous chemical?
• If sources outside the facility are contributing to the odor problem, can this be well documented based on their typical
emissions of the suspect chemical? Are these outside facilities likely to be cooperative in solving the odor problem? Have
these outside facilities been contacted previously?
Step 3: Quantify the Ambient Concentration
• Has ambient monitoring been conducted to confirm the presence of the odorous compound? Is the detection threshold
concentration below the instrument detection limit? Are the concentrations near or above the odor threshold? Have
monitors been placed so as to capture the likely path of the concentration plume based on the potential emission sources
and local meteorology?
• What are the emissions rates from the likely sources of the odorous compounds? Are all potential sources being included?
Include all fugitive (valve, pump, compressor, flange, etc.), tank, loading, vent, and wastewater air emissions. Are
combustion sources a likely contributor to the odor problem and should they be included in the analysis? Can the emission
rates be monitored? What is the variability and uncertainty in the estimated emissions both because of operations changes
and because of assumptions used for the input data and calculation method?
• Have predicted concentration isopleths (lines of constant concentration) been plotted based on the estimated emissions of
the odorous chemical? Have the sources been modeled appropriately and do they realistically represent the physical
situation? Concentrations predicted by standard dispersion models (15 minute to 1 hour concentration averaging time)
should be increased 3 to 6 fold to correct for the shorter concentration averaging time for transient odors.
• Do the predicted ambient concentrations from emissions and dispersion modeling exceed the odor detection threshold?
How conservative are the predicted concentrations? At the highest likely emission rate and worst dispersion conditions
(e.g., highest ambient concentration) are the predicted concentrations below the odor detection threshold? How close to
the detection thresholds are the predicted ambient concentrations?
• Are the predicted concentrations near the short or long term health exposure limits for any of the compounds being
modeled? Has an industrial hygienist reviewed the results? Is any immediate action required?
• Can some of the sources or chemicals be eliminated as potential contributors to the odor problem based on the monitoring
and/or modeling? Can this be fully and defensibly documented?
• Based on the emissions and dispersion modeling are sources outside the facility the most likely cause or are they major
contributors to the odor problem? Can perimeter monitoring be used to establish a high “up-wind" concentration of the
odorous compound? Have these sources outside the facility been the cause of previous odor problems?
Step 4: Reduce or Eliminate the Odor Problem
• How much emission reduction is required to lower the perceived odor concentration to acceptable levels (Use Stevens'
Law)? If the Stevens' law exponent is unknown, use n = 0.3. Is the reduction requirement being set by a regulatory
agency or to meet some ambient concentration related to the odor threshold? Is the reduction requirement being set by a
health based standard?
• Have all source reduction opportunities been considered? Are there some low cost equipment retrofits, operational
changes, housekeeping, or materials changes, that can be implemented to reduce emissions? Can on-going emission
reduction efforts be focused on the more likely areas where the odorous compounds are most likely to be emitted?
• Are emissions source control actions required? What are the most applicable (technical / economic) recovery or
destruction options to be considered? Is there a regulatory requirement for a particular type of control device or efficiency?

ExxonMobil Research and Engineering Company – Fairfax, VA