77-9.4
     THE CONTROL  OF  HYDROCARBON EMISSIONS FROM

           GASOLINE  MARKETING OPERATIONS




              VINCENT  J.  PITRUZZELLO
       U.S.  ENVIRONMENTAL  PROTECTION AGENCY
                NEW  YORK,  NEW YORK
For Presentation at the 70th Annual Meeting of the

          Air Pollution Control Association

Toronto, Ontario, Canada    June 20-June 24,1977
                   Printed in U.S.A.

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    NOTE   TO  EDITORS
Publication  rights to  this paper  are
reserved for  the  Journal  of the Air
Pollution  Control  Association.  Any
use by other journals is limited  to
twenty per cent  of text and figures.

                 a.

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                                 -.3-                              77-9.4
The purpose of this report is to review methods currently available for
controlling hydrocarbon emissions generated during gasoline marketing
operations.  For this purpose, gasoline will be defined as a petroleum
distillate with a Reid Vapor Pressure of 4 pounds or greaterJ  The need
for controlling this source of emissions was initiated by Federal regula-
tions promulgated in November of 1973.  It was mandated that oxidant con-
centrations, in specific areas of the country, be reduced.  This was to be
achieved by limiting the amounts of oxidant-forming hydrocarbons from both
stationary and mobile sources.  The gasoline marketing network accounts for
approximately 28% of total hydrocarbons being emitted from the petroleum
industry and as such was a prime target for control.  Hydrocarbon emissions
from gasoline marketing result in about 1.4 million tons per year.2  This
paper discusses the methods of control which have been instituted within
recent years for meeting the requirements of the regulations.

NETWORK OPERATION
The gasoline marketing industry contributes hydrocarbon compounds to the
atmosphere through the mechanism of evaporation during the many handling
processes involved in transferring gasoline from the terminal to the vehicle.
If left uncontrolled, the industry would become a greater relative contributor
to hydrocarbon emissions because other emission sources are being brought into
control, because gasoline sales are increasing and because of increased reacti-
vity of non-leaded gasoline vapors.

Terminal operations are the central point of the gasoline marketing network.
Here the product is received by rail, truck, barge and pipeline and transported
to the service station by tank trucks.  Emissions are generated during the bulk
terminal loading operation, during delivery to the service station and during
vehicular refueling operations.  Regulations have been promulgated for controlling
emissions from the terminal and service station sources; regulations have been
proposed for the vehicular refueling operation.

During the year 1973 106.5 billion gallons of gasoline were consumed in the United
States.An average annual increase in consumption of about 5% is expected for
the foreseeable future.  The distribution was made through more than 25,000
bulk stations and terminals to over a quarter million service stations. Vir-
tually, all gasoline product was transported by tank truck to the retail outlet.
Because of the nature of this operation, the gasoline product can be subject to
two or three transfers before being consumed.  This factor makes the control of
this source category increasingly important.

In most terminal operations, tank trucks ranging in size from 500 to 8500 gallons
are loaded by a variety of techniques.  The method used for loading has the
greatest influence on the amount of emissions generated at the loading rack.
Product can be transferred by splash loading techniques, where the stock is dis-
charged into the upper part of the truck compartment through a short spout which
never dips below the surface.  The fall increases evaporation and can result in
the loss of liquid droplets and subsequent entrainment of vapors.  Subsurface or
submerged loading operations result in rapid evaporation loss until the end of

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                                    -f-
                                                                 77-9.4
the loading spout is covered to give  a  calm surface.   Most  loading of
this type requires that,  ideally,  the spout be within  a  few inches of
the bottom of the compartment.   However,  because of the  size and shapes
of the various transport  trucks,  this ideal  situation  can be realized in
only a certain percentage of the  delivery vessels.   Loading losses can
be kept to a minimum by the use of bottom loading techniques where the
transfer piping is connected directly to  the tank bottom.*

To insure the maximum degree of control,  regulations required that all
displaced vapors and air  be vented to a vapor collection or disposal  system.
This is accomplished by connecting a  vapor recovery arm  to  the delivery  vessel
during loading. The vapor arm is  a permanent fixture at  the rack and  allows
the vapor to be directed  to the control unit for processing.  Recently,  there
have been many advances in the  technology of controlling emissions at the ter-
minal.  To date, there are seven  different types of systems available for this
purpose.  Vapor recovery  or disposal  units are connected to the loading  rack
and process gasoline vapors into  liquid product, combust the vapors,  or  use
the vapors as a source of fuel  gas.

TERMINAL CONTROL SYSTEMS
Each type of system will  be briefly described below:

     (a)  The operation of the cotnpression-refriqeration-absorption system
is based on absorbing vapors with cool  gasoline.   The vapors are first satu-
rated to insure that they are above the upper explosive limit (UEL), com-
pressed and then cooled before introduction into  the  absorber.   Here, the
vapors are bubbled through cold gasoline (at -10°F)  and absorbed.  Air is
vented at the top of the absorber and gasoline product,drawn from the bottom
of the absorber,is returned to storage.  As in most  recovery systems, the
efficiency of the unit is dependent on  the inlet  hydrocarbon concentration.
If necessary, booster compressors can be installed to increase  recovery effi-
ciency.

     (b)  Compress ion-refrigeration-condensation  units  recover vapor by first
saturating the vapors above the UEL and then by compressing the vapors in a
two cycle compressor equipped with an inter-cooler.   Condensate is drawn from
the inter-cooler prior to the second stage compressor.  Compressed vapors are
sent to a condenser where they are cooled and condensed.  The vapors are then
returned along with the condensate, from the inter-cooler, to storage.

     (c)  Lean-oil-absorption units operate by allowing the gasoline vapor to
flow into a packed absorption column.  The packing is continuously wetted by a
stream of lean oil, which is gasoline stripped of its light ends.  The clean
air is usually passed through a demister to remove any entrained absorbent and
the enriched gasoline is returned to storage.  Lean  or "sponge  oil" absorbent
is produced by heating gasoline from storage.  All light ends from this heating
are condensed and returned to storage.   The quantity  of lean oil is variable
and is a direct function of the quantity of vapor flow to the absorber, the
vapor temperature and the degree of vapor saturation.5

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                                                                 77-9.4
                                     -5-
     (d)  Another method used for recovering gasoline vapor is the
refrigeration system, based on condensing vapor at atmospheric pressure.
This system employs a typical cascade refrigeration operation which pro-
duces temperatures in the evaporator-interchanger in the order of -100°F.
A brine coolant is circulated through the finned tube sections of the vapor
condenser and the gasoline vapor is passed over the sections of the con-
denser.  Entrained moisture in the entering vapor condenses and collects
as frost on the cold plate fins.  Liquid hydrocarbon is collected at the
bottom of the condenser.  At periodic intervals, defrosting of the finned
surfaces is accomplished by circulating warm brine from a separate storage
reservoir.  A two-stage refrigeration unit is used to cool the stored brine
to about -120°F.  Vapor holders are not required, since the unit operates  on
demand.6

     (e)  A recent development in reducing emissions of gasoline vapor has
been the adsorption-absorption system.  This process operates by adsorbing
gasoline vapors on activated charcoal to near the saturation point of the
charcoal and follows this with absorption of the recovered vapors with liquid
gasoline.  The design includes a duel charcoal bed system which allows one
bed to operate while the other is being regenerated.  Upon completion of re-
generation, the bed operation is switched.  Vapor holder tanks are not required
since the vapor flow is directed straight to the charcoal bed.''

     (f)  One of the most direct vapor control systems is the flame oxidation
method.  Vapor emissions are controlled by combusting the vapor rather than
recovering it.  Gasoline vapor, displaced from the loading operation, is sent
to a holder tank, which is used to reduce surging to the system and allow  for
an even air flow.  Vapor is then drawn from the tank by a blower, compressed
and fed to the oxidizer.  A propane pilot light is used for oxidizer ignition
and thus, a source of propane must be made available.  The oxidizer operation
is controlled by the gas volume in the vapor holder tank and starts at about
30% capacity and shuts down at about 10%capacity.  Because of the nature of the
operation, no recovered product tanks or lines are necessary.  Capital and
operating costs for these units are usually lower than that required for recovery
units, but this can be offset by the economic loss of combusting the vapor rather
than recovering it.5,8

     (g)  Another method of vapor disposal, by combustion, uses the heat genera-
ted by the operation as a source of space or process heat.  Gasoline vapors are
conducted to a saturator to obtain concentrations above the UEL.  The enriched
vapor is then sent to a vapor-holder tank, which is fitted with an internal
diaphragm.  When a preset level is approached, a negative pressure pump is acti-
vated and the vapors are sent to a standard burner.  If the burner is oil-fired,
a dual-burner system is needed to allow for proper combustion of the vapor feed.
The capital expenditure necessary for this system includes ductwork, the vapor-
holder tank and burner adjustment.  However, this can be offset by savings in
fuel  oil consumption.  High levels of burner efficiency must be maintained for
compliance with Federal, State, or local regulations.

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                                                                 77-9.4
COST DATA

Table I depicts actual  installed costs  for a  variety of systems  presently
in operation in New Jersey.   Column I  represents  the cost of the unit and
Column II shows an installed cost which includes  all associated  terminal
work such as loading rack retrofit  piping, electrical  work, etc.   Column
III gives gasoline throughput at the rack to describe the units'  work load.
This data has been presented to illustrate the  range of costs that may be
encountered when installing  a vapor recovery  unit.   Expenditures for each
type of unit will fluctuate  with the work load  but  not  necessarily in arith-
metic proportion.  Most terminal units  have been  oversized to compensate  for
expected growth in gasoline  consumption.  Where cost data were available  for
more than one installation of a particular type unit, a range of costs and
throughputs are supplied.  It is difficult to  generalize and use  these
figures for cost estimation  at other terminals  since different parameters
will be encountered at each  facility.   For example, it  may be desirable to
retrofit an existing rack instead of demolishing  it and rebuilding a new  one.
Piping costs will be dependent on diameter and  lengths  of pipe required.
Labor costs will differ with geographical areas.  The desired quality of
the completed terminal  will  affect overall costs; resurfacing costs and
quality of equipment must also be considered.

Table II presents an analysis of the actual associated  costs for retrofitting
a two-rack top loading operation to bottom loading.  When considering annual-
ized cost for the various types of units, utility and maintenance  costs must
be included in the estimates.  Depending on the type and size of the unit,  these
costs can range from 2-5% of capital cost. Annualized  costs for oxidation
systems are dependent on the pilot light propane  requirements.

Operating costs can be offset by the recovery of saleable product.  For example,
a 500,000 gallon/day terminal can recover about 600 gallons of gasoline product
per day if all the displaced vapor is  sent to the recovery unit  and if the  unit
is operating at 90% efficiency.  This  also assumes  bottom or submerged loading
into trucks used exclusively for gasoline delivery  to service stations equipped
with vapor recovery.  The recovered product consists of light ends, and is  mixed
in storage, usually with regular grades of gasoline. Thus, this product  can be
worth several hundred dollars per day,  based  on current resale value of gasoline.
A typical calculation is shown in Figure I.

The reliability of vapor recovery systems must also be  considered.  For example,
in New Jersey there are 26 terminals equipped with  vapor recovery systems.   As
of March, 1977 there have been 257 total operating  months, with  a  reported  down-
time of 10 months or 4%.  Thus, reliability of operation is 96%.  Most units are
automated and require very little maintenance except for daily checks on  operating
parameters which are usually displayed on a control board for easy access.   In
the event of a system or component failure, the manufacturer will  supply  the re-
quired technical assistance.  Units are commercially available for terminals
with daily throughputs as low as 70,000 gallons and as  high as one million  gallons

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                                                                77-9.4
                                -7-
SERVICE STATION CONTROLS

Recovery of vapor generated during bulk delivery at the service station
can be accomplished by a closed loop balance system which simply returns
the displaced vapors to the delivery vessel.  The liquid gasoline acts
as a driving force sending the vapors back to the tank truck.  Some im-
portant factors in designing an efficient balance system are the type of
loading technique, vapor and liquid line fitting, vent pipe restrictions
and vapor-tight delivery vessels.  Design criteria calls for loading to
be done with the use of a submerged fill pipe to keep splash effects at
a minimum.  Systems will also include dry-break or cam-lock fittings on
the product and vapor return lines, to insure a tight fit and eliminate
leaks.  A restriction on the underground tank "breathing" vent line is
necessary to establish a path of least resistance thus assuring a high
percentage return to the tank truck.

Also, the tightness of the delivery vessel is extremely important.  The
trucks should be kept vapor-tight so that a maximum amount of recycled
vapor can be returned to the terminal for processing through the recovery
or disposal unit.  Systems currently available on the market, include a
two-point system (separate vapor and product line) and one-point or co-
axial system where the liquid line is surrounded by an outer annular space
for vapor return to the truck.

Recovery of vapors from vehicle refueling operations has generated much
disagreement among the participating interests.  It is uncertain whether
balance-type systems can meet the requirements of the various codes.  Effi-
cient gasoline dispensing nozzle designs have been questionable.  Vacuum-
assisted systems, which create a negative pressure at the pump to capture
the expelled vapors, are not desireable to the industry because of the high
capital cost and questionable dependability.  The vacuum-assist systems must
be equipped with a secondary recovery or disposal unit to control the excess
emissions generated by the evaporation of additional hydrocarbons in the
additional ingested air.  The main processing systems used in conjunction
with vacuum assist are refrigeration, absorption, compression and oxidation.
Some recent technology has sought to combine balance and vacuum-assist systems
into a "hybrid" system which uses gasoline circulated through the dispensing
nozzle as a source of vacuum.  Hopefully, technology will soon be developed
to satisfy both industrial and regulatory interests.  Some typical cost data
for retrofitting a service station for compliance with the bulk delivery and
vehicular refueling regulations are given in Table III.9>10

SECONDARY BENEFITS

There are some ancillary benefits to be derived from controlling vapors generated
during gasoline marketing operations.  These will be considered below:

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                                                                 77-9.4
 (1)  Bottom loading techniques reduce the amount  of vapor generated since
 there  is less splashing of product.  This is  a  direct  saving of a valuable
 fuel.  Tight fitting systems decrease the occurrence of  spillage and thus,
 make the terminal area a safer place to work.   Since bottom loading does
 not require the driver to load from the top of  the  truck,  the incidence of
 falls will be eliminated.  Bottom loading allows  the operator to fill  several
 compartments simultaneously and reduces overall fill time.   The loading racks
 are equipped with automatic sensors to terminate  loading  and prevent compart-
 ment overfill.

 (2)  The gasoline fraction that is recycled results  in  a  direct conservation
 of a valuable resource.  It has been estimated  that  about  9  million gallons
 per year of gasoline fractions can be recycled  in N.J., based on 1973  con-
 sumption.  Resale of the recovered fraction will assist in  recouping capital
 and operating expenses.

 (3)  By returning service station losses to the delivery  trucks, a  level
 above the UEL is constantly maintained in tight trucks, thus,  eliminating
 any explosion hazard.   Vapor concentration in retrofitted  trucks is about
 15-20? and does not approach the UEL of 7.6%.  Criteria require  that delivery
 vessels are to  be inspected at least semi-annually by leak testing  procedures
 to insure vapor tightness.

 (4)  Systems that use  the captured vapor as a source of fuel  result in  a
 saving of valuable fuel oil  and utilize an energy source that would have
been wasted.

 (5)  The use of vapor  recovery  and disposal systems can reduce the emissions
 os suspected carcinogenic compounds  of gasoline.  Benzene and associated
 aromatic components constitute  the largest percentage of suspected carcino-
 genic agents in the stock.   The liquid phase content of benzene can range
 from 0.5% to 2.0% by liquid  volume percent for regular and premium grades.
 For purposes of maintaining  octane ratings, unleaded gasolines contain a
 higher benzene  content, usually about 2.5% liquid volume percentage.   With
 the increased use of unleaded fuels, (projected as a 10% increase per year)
 this problem will  grow. More data must be compiled to adequately determine
 the magnitude of the problem.

 (6)  It is  also possible  that lead particles may be transported and emitted
 in the vapor phase.  However, due to the lack of available data, this state-
ment cannot be  made with a  high level of confidence.  Further studies into
 this area are necessary.

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                                                                 77-9.4
CONCLUSIONS

Systems are currently available  for  meeting  requirements of regulations
controlling vapor emissions generated  during the gasoline marketing opera-
tion.  Technology has been developed to  recover or dispose of 90% of vapors
displaced during truck loading operations  at the bulk terminal.   Service
station control systems can also effectively recover 90% of normal  vapor
loss during delivery operations.  A  cost-effective technology for vehicular
refueling control is still in the development stage.   The available control
systems have been found to be reliable and will  aid in the achievement and
maintenance of the national ambient  air  quality standard for oxidants  by
reducing the emissions of precursor  hydrocarbons.

Secondary benefits will also be realized by  the  implementation of these
controls.  Gasoline product will be  recovered and  recycled,  the  terminal
and service station environment will be  a  safer  and more pleasant area to
work.  Valuable fuel will be conserved and emissions  of suspected carcino-
genic agents will be reduced.

FUTURE CONSIDERATIONS

It is not yet known to what geographical extent  these  regulations will  be
applied.   Presently, there are portions  of seven states  and  Washington,  D.C.
where gasoline marketing controls have been  required.   Since  technology  is
proven and available, this source of emissions can  readily be controlled.

Vapor balance systems can be used at bulk loading stations  which are secondary
distribution facilities that receive gasoline from  larger terminals by tank
truck.  Recovery and disposal  systems can be  sized  for controlling emissions
generated during marine loading operations.  Losses from this  source can be
significant because of the large volumes  handled.  Marine controls should be
considered for transporting the new sources.of oil  from the Alaska North Slope
to the West Coast and for similar oil discoveries off  the East Coast.  Marine
controls are being contemplated for the Houston-Galveston Area.  In some cases,
product is stored in underground tanks  in waterfront terminal  operations.
Breathing and working losses, from these  tanks, can also be controlled  in
conjunction with barge loading.

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                                                              77-9.4
                                  Table I
      Type Unit
Compression-Refrigeration
Absorption (range)
Compression-Refrigeration
Condensation
Lean-Oi1-Absorpti on
Refrigeration (range)
Adsorption-Absorption
Flame Oxidation
Fuel Disposal System
ire Vapor
Column
Unit Cost
60-80
250
140
50-155
80
90
—
A
Recovery at the Terminal
I Column II
Associated [
($103) Installed Cost ($10J)
70-90
125
Not Available (N.A.)
N.A. 500
50
300
350D

Column III
j Product
Throughput
80,000-
325,000 gal /day
385,000 gal/day
500,000 gal /day
70,000-
1 ,000,000 gal/day
70,000 gal/day
200,000 gal/day
820,000 gal/day
A
 Data supplied is in 1974-76 dollars.
D
 Assume, two gasoline loading racks with a total  of 12 loading arms.
 It is believed that this type of system has been removed from the market.
 Cost is $100,000 for saturator and vapor holder; $100,000 for piping
 (1300 ft.) and $150,000 for rack retrofit.
D

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                                                        77-9,4
                            Table II
                 Associated Capital Expenditures
     Item
               A
Rack Conversion^
Combined Piping
Labor .
MetersL         _
Land Improvement
Truck Retrofit (Bottom Load)
 80,000 (2 racks,  4 positions)
125,000
 42,000
 25,000
 33,000
 1500-2500 per compartment
 Includes reworking of rack from top splash to bottom load.
 (Cost of a top submerged arm   $3500; cost of bottom load
 arm = $1100)
D
 Dependent on distance from loading rack to vapor recovery unit.
P
 Includes electrical meters and pre-set shut off switches.

 Includes unit foundation, area resurfacing, drainage system.
 Dependent on desired quality of completed retrofit terminal.
Note:  The above represents actual on-site costs incurred by terminal
operators throughputting 500,000 gallons/day.

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                                                         77-9.4
                            Table III
                     Costs   Service Station
A.  Delivery Controls Only

Two-Point System      $3100
Co-Axial System       $2000
Component Estimates   Excavation       42%
                      Labor            32%
                      Piping           20%
                      Valve Fittings    6%
 Assume balance system for a station equipped with four underground
 tanks.
B.  Delivery and Vehicular Refueling Controls

Drybreak fittings            $ 320
Excavation                   $ 600
Vapor pipes from dispenser   $1350 (assume 450 ft. total)
Installation of pipes        $1300
Nozzles and hoses            $ 870
Installation of nozzles      $ 240
Trucks, compressor and
 misc. piping              - $ 300
                     TOTAL - $4,980

Vacuum assist unit   $3000- $5800
Total cost   $8000   $10,800 (approximate)
 Costs include total service station retrofit for a station with a
 throughput of 30,000 gal. per month using six nozzles.

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                                                         77-9.4


Example Calculation
Assume gasoline product throughput of 500,000 gallon/day with  an
RVP=10.  Product temperature is 60°F and is loaded into trucks
returning from service stations equipped for vapor recovery.

Uncontrolled Emission Factor for Gasoline   8 lb/1000 gallons
transferred


     500'00° ^T X fool gallons  ^ 90% control   3600 lo/day
Liquid density   6.2 Ib/gaTlon

Thus,

     3600 Ib  ;6.21b        581   „
          day       gallon        3


Net price; ex-tax of gasoline (1/76) - 35.2£/gallon

Dollar value of recovered product is:

                              $204.51/day

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                                                          77-9.4
 References


 1.   Environmental  Protection Agency   "New Jersey Transportation Control
     Plans: Approval  and Promulgation of Implementation Plans."
     Federal  Register 38 (218),  31399, November 13, 1973

 2.   Environmental  Protection Agency   Office of Air Quality Planning and
     Standards Revision of Evaporative Hydrocarbon Emission Factors
     EPA-450/3-76-039 August, 1976

 3.   National  Petroleum News   Mid-May Factbook 1974

 4.   American  Petroleum Institute, Evaporation Loss Committee,  Evaporation
     Loss From Tank Cars,  Tank Trucks, and Marine Vessels.
     Bulletin  2514  N.Y. 1959

 5.   Environmental  Protection Agency   Office of Air Quality Planning and
     Standards A Study of Vapor  Control  Methods for Gasoline Marketing
     Operations: Volume I  - Industry Survey and Control  Techniques
     EPA-450/3-75-046-a, Research  Triangle Park, N.C.  April  1975

 6.   Edwards  Engineering Corporation   Hydrocarbon Vapor Recovery Unit
     May 1976

 7.   Hydrotech Engineering Incorporated    Vacuum Stripping,  Water
     Deaerating, Odor Control, B.O.D.  Reduction, Hydrocarbon Removal
     1976

 8.   Environmental  Protection Agency   Office of Research and Development
     Demonstration  of Reduced Hydrocarbon Emissions From Gasoline Loading
     Terminals EPA-650/2-75-042, Washington, D.C.  June 1975

 9.   Environmental  Protection Agency   "Stage II Gasoline Vapor Recovery:
     Proposed   Decisions,  Amendments,: Test Procedures," Federal Register
     40 (197)  47670 October 9, 1975

10.   Cost Data   Vapor Recovery  Systems  at Service Stations    Pacific
     Environmental  Services Incorporated, September 1975 (Prepared
     under Environmental Protection Agency contract #68-02-1405)

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