An Evaluation of Evaporative Emissions of

Gasoline from Storage Sites and Service Stations

By: J.S. Razavizadeh

Supervisor: Prof. H.S. Ghaziaskar
Tuesday 88.02.22 , 11.00 am
 Displacement emissions
Introduction -1
Breathing and withdrawal emissions

Evaporative emissions -2
Filling emissions

Emission from vehicle refueling

Emissions prevention and minimization

Factors affecting evaporation -3
Collection of vapor

absorption
control of emissions-4 Vapor recovery Pressure swing and purge regeneration

Condensation

Diffusion technologies

Treatment of vapor

Legislation regarding evaporative emissions-5

 •The hydrocarbons emitted during petrol storage and distribution
can be broadly classified as volatile organic compounds (VOCs)

Pure hydrocarbons-1

VOCs Partially oxidized hydrocarbons-2

Organics containing chlorine , sulphur and nitrogen-3

Industrial and domestic solvents(40%)-1

VOCs emissions originate from
exhaust gases from motor vehicles(25%)-2
Evaporation and loses from motor vehicle(10%)-3
Petrol distribution(3%)-4
Vehicle refueling(2%)-5
Oil refining (3%)-6
from other source(17%) -7
Oxygen Molecule (O2) + NOx + VOC +

Sunlight

Ozone Molecule (O3)

 Typical petrol distribution

Products storage
At refinery

Rail car Pipe line Marine vessel

Bulk storage at
Marketing depot

Road tanker

Storage tank at
service station

Motor vehicle
Typical petrol vapor composition (only VOC)
VOLUME COMPUND
Traces Ethane
1.5% Propane
8% Isobutane
10% n-Butane
14% Pentane
5000ppm Benzene
6% Hexane and others

40% TOTAL
)voc only, remainder in air(
 EVAPORATIVE EMISSIONS

the average emission from a typical European petrol storage and distribution
system, is O.56% volume of the petrol distributed

displacement refueling
breathing and withdrawal filling

0.3 0.03 0.05 0.18

 Displacement emissions

• Displacement emissions occur from fixed roof storage facilities (bulk storage tanks), as well as
underground service station tanks due to vapor displacement by incoming petrol.

• Displacement emissions from fixed roof storage facilities account for 0,14 %

• from service station storage tanks for 0,16 %

Breathing and withdrawal emissions

• Breathing emissions are caused by variations in tank contents, temperature and by changes
in barometric pressures that cause expansion and contraction of the liquid and vapor in a
tank.

• Withdrawal emissions occur when petrol is pumped out of a storage tank resulting in the
intake of air through pressure/vacuum relief valves or vents

• Breathing and withdrawal emissions from bulk storage tanks account for 0,02% and from
service station storage tanks for 0,01% of total emission losses.
 Filling emissions

• Filling emissions occur when petrol is transferred from storage tanks to road tankers.

• two types of vapor making up filling emissions, namely preloading vapor (PLV) and
evolution vapor (Ve).
• PLV is residual vapor originating from a tank's previous contents, being displaced by
loading of the new product, and is defined as a fraction or percentage of full saturation, Cp,.

• Cp less than 1 % (Cp < 0,Ol) when the previous contents of a road tanker were a non-
volatile product.

• Cp between 10% and 20% (0,l < Cp < 0,2) when the previous contents of a tanker were
discharged completely at one point.

• Cp between 30% and 50% (0,3 < Cp < 0,5) when the previous contents were discharged at several
occasions.

• Cp between 90% and 100% (0,9 < Cp < 1,O) when the contents of a tanker were discharged
at a service station tank that allows for vapor return.
• Evolution vapour (ve) evaporates from the product itself when it is being loaded. Petrol can be loaded
into a road tanker via top splash loading, submerged top loading or bottom loading.

• In order to estimate Ve a parameter VB is used to represent the amount of splashing in a tanker during
filling.

• VB is equal to the fraction of the original tank atmosphere that is assumed to be completely saturated
during loading.

1. VB = 0,4 for top splash loading.

2. VB = 0,15 for submerged top loading.
3. VB = 0,13 for bottom loading.

Concentration of petrol vapor Parameter representing

under equilibrium conditions the amount of splashing

filling emission

liquid to vapor
volume equivalence
Average preloading
factor vapor concentration
 Emissions from vehicle refueling

•These emissions contribute to 0,18 volume % of the total emissions from petrol storage
and distribution systems

.product (liquid petrol) properties -1

FACTORS
AFFECTING
.Liquid/vapor interface areas -2
EVAPORATION
.turbulence in the relevant liquid and vapor -3
 Control of emission
• Safe operation
• Ease of operation
• Reliable operation
• Low maintenance
• Low operation costs
• Low investment costs
• Highest possible emission reduction.

Emissions prevention and minimization

Collection of vapor

absorption
control of emissions-4 Vapor recovery Pressure swing and purge regeneration

Condensation

Diffusion technologies

Treatment of vapor
 Emission prevention and minimisatim
• decreasing the volatility of petrol
• vapor balancing
• minimizing the liquid/vapour interface area
• reducing turbulence.
Typical construction of a modern day tanker
Tanker at Terminal
(No Vapor Recovery)
Tanker at Service Station
(No Vapor Recovery)
Bottom Loading at Terminal
(With Vapor Recovery)
Fuel Drop at Service Station
(With Vapor Recovery)
API to Drop Hose Connection
(At Service Station)
 Vapour recovery
Step 1 collection of VOCs/air mixture
Step 2 separation of VOCs from air
Step 3 the recovery of the separated VOCs into liquid state.
 Once the vapor has been collected, various processes or combinations of
processes can be used to separate and recover the vapor. These include condensation,
.absorption, diffusion and adsorption

Condensation: by compression or cooling

Condensation is most efficient for VOC recovery at relatively high VOC
concentration (above 5000 ppm)
Air

Step2 and 3
VOC/air Step1 Separation and Condensed
mixture collection Recovery via VOCs
condensation

.Flow diagram for condensation as vapor recovery process

 Advantage and disadvantage of condensation

Disadvantage Advantage
Energy requirements of Mechanical Moderate efficiencies, 50-90%
refrigeration are high

Nitrogen source needed for cryogenic Simple, flexible, safe process

condensation

May result in the generation of a Can handle wide range of products

wastewater stream
Absorption : absorbed in to liquid due to molecular force.
depends of vapor pressure and the temperature of the absorbent.

Low boiling point hydrocarbon liquid( like crude oil or kerosene) are
often used for VOC separation from air via absorption.
air

Step2 Absorbent
VOC /air Step1 Separation from
/)kerosene(
mixture collection Air via absorption
)with kerosene(
VOC mixture

Recycling of
Absorbent (kerosene) Separation from
Absorbent via
distillation
Step3
Absorbent Recovery via
VOC/)petrol( Absorption VOC
mixture )with petrol(
• Absorption can be used for high vapor flows and VOC concentration ranging
between 500 ppm to 5000 ppm.

Advantage and disadvantage of absorption

Disadvantage Advantage
Liquid absorbent may be transferred Good for high humidity streams
to the exit gas
(relative humidity < 50%)
High efficiencies, 95_98%

Wide range of vapor flow rates and

VOC concentration
Diffusion technologies: such as membrane is relatively new
Two types of membrane namely diffusion membrane and solubility
membrane.
air

VOC /air Step2

Step1
mixture Separation via
collection
diffusion

Step3 Step3
Recovery via Recovery via
absorption condensation

VOC /absorbent Condensed

mixture VOCs
 Advantage and disadvantage of diffusion technology

Disadvantage
Constant vapor flow rate are Necessary,
but buffer tanks are a major safety
concern
High power consumption
Advantage
Recovery of between 95 and 99%
Safe process and operational flexibility

Post treatment system needed in The Very wide range of products handling,
case of very high emission standards. for example ,hydrogen, Sulphide ,
acetone , MTBA, ethyl acetate
Adsorption: most effective methods and most economical.
the adsorption medium most generally used is activated carbon and hydrophobic
zeolites.
two regeneration technologies are currently in use, namely: thermal regeneration
and pressure swing and purge regeneration.
air

VOC /air Step1 Step2

mixture collection Separation via
adsorption

Step3 Step3
Recovery via Recovery via
absorption condensation

VOC /absorbent Condensed

mixture VOCs
 Advantages and disadvantages of adsorption

disadvantages advantages
Hydrogen sulphide from crude oil Wide range of vapor and vapor
vapor poison the carbon. concentration can be handled .

organic compounds like ketones, Efficient, relatively simple process

aldehydes and organic acids can
causes localised hot spots or bedfires
in carbon beds.
Light hydrocarbon fraction such as Flexible and inexpensive to
methane are very poorly adsorbed operate

Carbon performance decreases with

high humidity vapor streams (ralative
humidity <50%)
 1. References:
2. MEMBRANES FOR VAPOR/GAS SEPARATION Richard W. Baker Membrane
Technology and Research, Inc. 1360 Willow Road, Suite 103, Menlo Park, CA 94025

3. NEW TECHNOLOGY FOR EMISSION REDUCTION AT PETROL STATIONS OHLROGGE

K., WIND J. GKSS-Forschungszentrum Geesthacht GmbH, Institut für Chemie, Max-Planck-Strasse, D-
21502 Geesthacht, Germany

4. Safety design of a petrol pump attendant robot Francesco Becchi, Rezia M. Molfino and
Roberto P. Razzoli University of Genova, Genova, Italy

5. The Problem of Volatile Organic Compound (VOC) Emissionsfrom Petrol in

Lithuania and Methodological Aspects of Emission Reduction Viktoras Doroševas, Vitalijus
Volkovas, Ramūnas Gulbinas Technological Systems Diagostics Institute, Kaunas University of
Technology

6. Membrane Based Vapor Recovery at Petrol Stations Klaus Ohlrogge and Jan Wind

7. A policy instrument for the reduction of greenhouse gas emissions An Interim Report to
the Tyndall Centre for Climate Change Research 7th |January 2004 Dr Kevin Anderson,
Tyndall North, UMIST Kevin.anderson@umist.ac.uk Tel. 0161 200 3715 Dr Richard
Starkey, Tyndall North, UMIST
?Questions