Masters Thesis

Modeling and Validation of an Automobile Evaporative
Emission Carbon Canister
A Thesis
Presented in Partial Fulfillment of the Requirements for the Degree

Master of Science in the Graduate School of The Ohio State
University
By
Anoop Sunil, B. Tech
Graduate Program in Mechanical Engineering
The Ohio State University
2019
Master’s Examination Committee:

Dr. Giorgio Rizzoni, Advisor
Dr. Yann Guezennec
© Copyright by
Anoop Sunil
2019
Abstract
The automotive carbon canister consists of activated carbon particles designed to
adsorb and desorb Volatile Organic Compounds (VOCs) that evaporate from gasoline
present in the fuel tank. This is done to both increase fuel economy and decrease fuel
emissions. Experimental tests were done on an activated carbon bed measuring the
temperature and mass change during loading and purging of the carbon canister.
Experiments were conducted using n-butane as the volatile organic compound
during the loading phase and dry air during the purging phase. A 1D model was
developed in MATLAB to predict the canister behavior during these experiments.
The model predicts the mass change in the canister which in turn estimates the
amount of fuel available in the canister.
Since adsorption and desorption are exothermic and endothermic reactions respec-
tively, the model also predicts the temperature change along the bed of the canister
to study the effect of temperature on the adsorption and desorption process. The
experiments were used to validate the model using the activated carbon present in
an automotive canister.
The model developed in this thesis can be used to predict the loading and purging
event that occurs in an ideal carbon canister. This model can be used as the foun-
dation for a more complex model in the future and provide inputs to create a more
efficient automotive canister.
ii
This is dedicated to my faculty advisor, friends and collegues who have helped me
complete this project.
iii
Acknowledgments
I would like to thank everyone who has helped me complete my project to model
automotive carbon canister which resulted in my thesis. I would like to give a special
thanks to my faculty advisor, Dr. Giorgio Rizzoni, and project teammate, Ruochen
Yang. Your guidance and support have been of tremendous help and encouragement
to me. I would also like to thank everyone from the Ohio state university who have
provided valuable feedback during my project.
Thank you Luca Romagnuolo and Brian Rahman who supported the project and
for giving me feedback on my thesis. It has been a pleasure working with everyone
at CAR and all the friends I made along the way.
I would also like to send a special thanks to my family and friends who supported
me during the course of my graduate school and helped me complete my degree.
iv
Vita
August 11, 1993 . . . . . . . . . . . . . . . . . . . . . . . . . . . . Born - Kerala, India
2011-2015 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . B.Tech. Mechanical Engineering,

National Institute of Technology
Karnataka, Surathkal
2015-2017 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Assistant Manager, Tata Motors
2017-present . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . M.S. Mechanical Engineering,

The Ohio State University.
Fields of Study
Major Field: Mechanical Engineering
v
Table of Contents
Page
Abstract . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ii
Dedication . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . iii
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . iv
Vita . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . v
List of Tables . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ix
List of Figures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . x
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.1 Problem introduction . . . . . . . . . . . . . . . . . . . . . . . . . 1

1.2 Purpose and Objectives . . . . . . . . . . . . . . . . . . . . . . . . 3
1.3 Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.4 Thesis structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2. Background . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
2.1 Effect of fuel vapor on environment . . . . . . . . . . . . . . . . . . 6

2.2 Brief overview of EVAP-system and carbon canister . . . . . . . . . 7
2.2.1 Loading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
2.2.2 Purging . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
2.3 Activated carbon . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
2.4 Literature review . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
vi
3. Theory and Modeling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
3.1 Adsorption fundamentals . . . . . . . . . . . . . . . . . . . . . . . 16

3.1.1 Effect of porosity . . . . . . . . . . . . . . . . . . . . . . . . 17
3.2 Thermal properties of adsorption . . . . . . . . . . . . . . . . . . . 17
3.3 Adsorption Isotherms . . . . . . . . . . . . . . . . . . . . . . . . . 18
3.3.1 The Langmuir Isotherm Model . . . . . . . . . . . . . . . . 19
3.3.2 Linear Driving Force . . . . . . . . . . . . . . . . . . . . . . 21
3.3.3 Adsorption Isotherm Model . . . . . . . . . . . . . . . . . . 22
3.4 Breakthrough and Bleed emissions . . . . . . . . . . . . . . . . . . 25
3.4.1 Canister Breakthrough . . . . . . . . . . . . . . . . . . . . . 25
3.4.2 Bleed emissions . . . . . . . . . . . . . . . . . . . . . . . . . 26
3.5 Model development . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
3.5.1 Mass transport equation . . . . . . . . . . . . . . . . . . . . 27
3.5.2 Thermal Transport equation . . . . . . . . . . . . . . . . . . 30
4. Experiment Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
4.1 Experimental Setup . . . . . . . . . . . . . . . . . . . . . . . . . . 34

4.1.1 Canister geometry . . . . . . . . . . . . . . . . . . . . . . . 34
4.1.2 Thermocouple connections . . . . . . . . . . . . . . . . . . . 36
4.1.3 Setup Description . . . . . . . . . . . . . . . . . . . . . . . 38
4.2 Testing Procedures . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
4.2.1 Canister loading . . . . . . . . . . . . . . . . . . . . . . . . 41
4.2.2 Canister Purging . . . . . . . . . . . . . . . . . . . . . . . . 43
5. Simulation Method and Parameters . . . . . . . . . . . . . . . . . . . . . 46
5.1 Method of solution . . . . . . . . . . . . . . . . . . . . . . . . . . . 46

5.2 Initial and boundary conditions . . . . . . . . . . . . . . . . . . . . 47
5.3 Loading and purging simulations . . . . . . . . . . . . . . . . . . . 48
5.4 Parameter Estimation . . . . . . . . . . . . . . . . . . . . . . . . . 49
6. Result and Discussions . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
6.1 Experimental results . . . . . . . . . . . . . . . . . . . . . . . . . . 52

6.1.1 Canister Loading Mass and Temperature Variation . . . . . 52
6.1.2 Canister Purging Mass and Temperature Variation . . . . . 56
6.1.3 Measurement errors and inaccuracies . . . . . . . . . . . . . 60
6.2 Model Calibration . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
6.3 Simulation and Experimental Comparison . . . . . . . . . . . . . . 66
6.3.1 Canister Loading . . . . . . . . . . . . . . . . . . . . . . . . 66
vii
6.3.2 Canister Purging . . . . . . . . . . . . . . . . . . . . . . . . 70
7. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
Appendices 76
A. Canister Dimensions for Model . . . . . . . . . . . . . . . . . . . . . . . 76
B. Thermocouple Positioning on Canister . . . . . . . . . . . . . . . . . . . 78
C. MATLAB code to calibrate model . . . . . . . . . . . . . . . . . . . . . . 79
Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
viii
List of Tables
Table Page
3.1 Adsorption Isotherm curve-fit parameters . . . . . . . . . . . . . . . . 25
3.2 Antoine equation coefficients for n-Butane . . . . . . . . . . . . . . . 28
4.1 n-Butane and Nitrogen Mixture Gas cylinder Composition . . . . . . 41
5.1 Physical Properties of carbon bed and other Model Parameters . . . . 49
5.2 Canister Geometric Properties . . . . . . . . . . . . . . . . . . . . . . 50
B.1 Thermocouple Position along Carbon bed for both Canisters . . . . . 78
ix
List of Figures
Figure Page
2.1 A simplified schematic representation of the Fuel EVAP system . . . 8
2.2 Schematic diagram of a commonly used activated carbon canister . . 8
2.3 Approximate flowchart of vapor flow during loading process . . . . . . 10
2.4 Approximate flowchart of vapor flow during purging process . . . . . 11
3.1 Adsorption Isotherm for n-Butane on BAX 950 Activated Carbon using
f and v . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
4.1 Schematic Diagram of Canister 1 . . . . . . . . . . . . . . . . . . . . 35
4.2 Schematic Diagram of Canister 2 . . . . . . . . . . . . . . . . . . . . 35
4.3 Thermocouple positions on canister 1 . . . . . . . . . . . . . . . . . . 37
4.4 Thermocouple positions on canister 2 . . . . . . . . . . . . . . . . . . 37
4.5 Rotameter used to Measure Vapor volumetric flow rate . . . . . . . . 38
4.6 Schematic Diagram of the Canister loading experiment setup . . . . . 39
4.7 Schematic Diagram of the Canister Purging experiment setup . . . . 40
4.8 Experimental setup for loading experiments . . . . . . . . . . . . . . 43
4.9 Experimental setup for Purging experiments . . . . . . . . . . . . . . 44
6.1 Canister #1 Mass Profile during Loading Experiment . . . . . . . . . 53
x
6.2 Canister #1 Temperature Profile during Loading Experiment . . . . . 54
6.5 Canister #1 Mass Profile during Purging Experiment . . . . . . . . . 57
6.6 Canister #1 Temperature Profile during Purging Experiment . . . . . 58
6.7 Canister #2 Mass Profile during Purging Experiment . . . . . . . . . 59
6.8 Canister #2 Temperature Profile during Purging Experiment . . . . . 60
6.9 Canister mass profile with small disturbance during experimental testing 61
6.10 Cooldown Experiment Results - Carbon Bed and Skin Temperatures 62
6.11 Cooldown Experiment - Calibrating dTp /dTC . . . . . . . . . . . . . . 63
6.12 Cooldown Experiment - Calibrating Uloss . . . . . . . . . . . . . . . . 64
6.13 Cooldown Experiment - Validating Calibrated values on Canister #1 65
6.14 Cooldown Experiment - Validating Calibrated values on Canister #1 65
6.15 Comparison between Simulation and experimental results - Mass pro-

file Canister #1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67

file Canister #2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
6.17 Comparison between Simulation and experimental results - Tempera-

ture profile Canister #1 . . . . . . . . . . . . . . . . . . . . . . . . . 68


file Canister #1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
xi
file Canister #2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72


A.1 Canister #2 geometry and dimensions approximation for model . . . 77
A.2 Canister #1 geometry and dimensions approximation for model . . . 77
xii
Chapter 1: Introduction
Automobiles have been expressed as one of the sources of air pollution since the
1960s. Emissions can cause harmful effects on the environment and public health.
Automotive emissions control was introduced to decrease the harmful effect of these
emissions on the environment. Automotive emissions control includes the study of re-
ducing vehicle emissions particularly vehicles with internal combustion engines. Most
of the automotive emissions control focus on tailpipe emissions such as CO and N Ox
emissions. This work is going to focus on the evaporative emissions which are caused
due to evaporation of the fuel present in the fuel tank [20].
1.1 Problem introduction
A major contributor to air pollution are hydrocarbons emissions (HC). Long ex-
posure to hydrocarbons can lead to asthma, lung disease and cancer. A subsection
of hydrocarbons that directly affects public health is the Volatile organic compounds
(VOCs). Volatile organic compounds are organic compounds whose boiling point
is below 250 ◦ C. The fuel present in internal combustion engines especially gasoline
consists of different types of hydrocarbons. The lighter hydrocarbons present in the
1
gasoline constitute the volatile organic compounds since they are likely to evapo-
rate into gaseous form. The compounds within this group contribute to the smog
formation and environmental pollution [4].
The volatile organic compounds can be exposed to high pressures while inside the
fuel tank. This increase in pressure can be caused due to two reasons: Refueling and
temperature increase. In a closed fuel tank system, while refueling the volume of liquid
gasoline present in the tank will increase compressing the gaseous gasoline present in
the tank. Another way the pressure of the gas present in the tank can increase is due
to the increase in ambient temperature as the pressure of a gas is directly proportional
to its temperature provided the volume remains a constant according to the ideal gas
law [2].
Ideally, a fuel tank should not be pressurized due to safety concerns and to prevent
back pressure inside the tank. To avoid this pressure build-up, the fuel tank is vented
to the atmosphere to get rid of the gaseous vapors and maintain atmospheric pressure
inside the fuel tank. As mentioned earlier these volatile organic compounds are major
contributors to the air pollution and the smog formation. To prevent releasing the
volatile organic compounds to the atmosphere automotive makers have introduced
an active carbon canister in between the fuel tank and the atmosphere. [16]
The activated carbon canister is used to adsorb the volatile organic compounds
on the surface of the activated carbon and expel only clean air into the atmosphere.
However due to its limited capacity, once the canister reaches saturation it will stop
adsorbing VOCs and will be released into the atmosphere. To be able to use the
canister again, the adsorbed gasoline vapors have to be purged back into the intake
manifold. The canister has to be purged regularly to maintain optimum emission
2
control. Purging involves passing air through the canister which desorbs the VOCs
and forcing them into the engine manifold. This process allows for better fuel economy
and reduces evaporative emissions.
The carbon canisters have existed for a long time but due to the new stringent
emission norms being introduced every year automotive companies are forced to im-
plement better carbon canisters with larger capacity and better-activated carbon
types. The need for efficient carbon canisters has led to the demand for canister
models which can accurately predict the amount of volatile organic compounds ad-
sorbed so that it can be used to improve the fuel economy and maintain the emission
standards.
1.2 Purpose and Objectives
The purpose of this thesis is to create a carbon canister model capable of pre-
dicting the amount of volatile organic compounds adsorbed and desorbed in a given
activated carbon canister. This model can be used by the automotive industry to run
simulations of the EVAP system and create new and improved carbon canisters to
comply with the advanced emission norms.
The goal of this project is to create a carbon canister model that can accurately
predict the amount of VOCs adsorbed in an ideal flow situation (diurnal setting) and
the amount of VOCs desorbed while purging the canister at a constant flow rate.
The model will be validated using experimental tests conducted on a canister filled
with activated carbon. Once the model is validated it can be used by an automotive
company to analyze the carbon canister inside their vehicles. The model can also
3
be used as a base to create new canister designs and help reduce the evaporative
emissions further.
1.3 Method
The project consists of two main parts to predict the behavior of an activated
carbon canister: modeling and experimental analysis. The modeling part includes
predicting the adsorption and desorption behavior of activated carbon using the car-
bon and canister properties in chemical equations. The model will predict the amount
of VOCs adsorbed or desorbed and the temperature changes in the canister during
this process. The experimental part consists of building a test rig of an activated
carbon canister with a weighing scale and thermocouples to studying the mass and
temperature changes of the canister as it is being loaded with VOCs.
The model is implemented in MATLAB to simulate the mass and temperature
change of the canister during the adsorption and desorption phases. The MATLAB
model will simultaneously solve the mass and temperature partial differential equa-
tions to model the carbon adsorption properties.
1.4 Thesis structure
This thesis will first give a background on the EVAP system and carbon canister.
The thesis then explains the theory behind the canister model and the equations
used to model the carbon canister. In chapter 4 the thesis describes the experimental
setup and analysis done to compare the model. In chapter 6 the thesis will provide
the results and discussions based on the findings of the experimental setup and the
4
accuracy of the model. Finally, the thesis will conclude with the use of the model
and any future work remaining.
5
Chapter 2: Background
This chapter will provide a background on the problem considered in this thesis.
First, it will explain the effect of fuel vapor on the environment and then provide
a brief overview of the EVAP system and carbon canister. Finally, it will discuss
various methods used by other authors to model the activated carbon canister.
2.1 Effect of fuel vapor on environment
Volatile organic compounds (VOCs) are a group of gaseous compounds containing
carbon that exist in the atmosphere, not including carbon monoxide, carbon dioxide
or carbonic acid. VOCs as pollutants have a major impact on the environment and
human health. VOCs at the ground level react with oxides of nitrogen in the presence
of sunlight in a photochemical reaction to create ozone in the ground levels. Ozone at
the ground level is the main ingredient in smog formation. Ozone can also be toxic to
humans and cause various health issues. VOCs are also responsible for its destruction
of the ozone layer at the stratosphere level and the role it plays in the greenhouse
effect [6]. Given the harmful effects of VOCs in the atmosphere, its release should be
minimized as much as possible.
As mentioned in the previous section, evaporative emissions from fuel present in
automobiles is a major source of VOCs. Increasing ambient temperature or heat from
6
the engine can cause the volatile compounds present in the fuel to evaporate inside
the fuel tank. In the absence of a carbon canister, the vapor build-up inside the fuel
tank is released directly into the atmosphere. To avoid releasing these harmful vapors
in the atmosphere, a carbon canister is introduced into the fuel system in between the
fuel tank and the vent to the atmosphere. Even with the carbon canister installed,
the built-up vapor in the fuel tank can leak into the atmosphere when the canister is
saturated. Therefore an accurate model of the carbon canister is required so that the
canister can be purged before it reaches saturation.
2.2 Brief overview of EVAP-system and carbon canister
The evaporative emission control system or EVAP for short is used to control
the amount of evaporative gasoline vapor escaping into the atmosphere from the fuel
system. The OBD II EVAP monitor on vehicles runs a self-diagnostics check on the
fuel system to detect any fuel vapor leaks. If the system finds a leak, it will turn
on the check engine light indicating a leak in the EVAP system to the owner of the
vehicle.
Figure 2.1 shows a simplified sketch of the main components of the EVAP system
which include the fuel tank, gas cap and EVAP canister. The fuel tank usually
is equipped with some expansion volume at the top to accommodate for the fuel
expansion during a hot day without overflowing or causing the EVAP system to leak.
The gas cap helps to seal the system from the atmosphere and allows the filling of
the fuel tank.
7
Figure 2.1: A simplified schematic representation of the Fuel EVAP system
Figure 2.2: Schematic diagram of a commonly used activated carbon canister
The main component of the EVAP system is the carbon canister. The location
of the activated carbon canister varies from vehicle to vehicle. Figure 2.2 shows
a schematic diagram of a commonly used activated carbon canister. The carbon
8
canister consists of a carbon bed placed inside a plastic housing with some filler and
protection to keep the carbon bed secured inside the housing. The canister has 3
main valves on the outside named the load valve, purge valve and atmosphere valve.
These valves allow the flow of air and gasoline vapors to and from the canister. The
load valve serves as a connection between the fuel tank and the carbon bed inside
the canister. The purge valve connects the carbon bed to the vehicle intake manifold
and finally, the atmosphere valve connects the carbon bed to the atmosphere.
2.2.1 Loading
The event where hydrocarbons are adsorbed on the carbon bed is known as load-
ing. For the loading event, the load valve and atmosphere valve remain open while
the purge valve remains closed. During the event, gasoline vapors flow through the
carbon bed in the canister through the load valve and out the atmosphere valve. The
loading event occurs due to two main reasons: an increase in ambient temperature or
a sudden increase in fuel vapors inside the fuel tank.
The first reason for loading is the increase in ambient temperature around the fuel
tank. This increase in temperature will cause the volatile compounds present in the
fuel to evaporate into gases. As a result of this evaporation, the air inside the tank is
concentrated with hydrocarbons present in the fuel vapors. To prevent damage to the
fuel tank by the increase in pressure and temperature the fuel vapors must be vented
away from the tank. As mentioned in the previous section we cannot vent this fuel
vapor into the atmosphere to avoid pollution. The canister is placed in between the
tank and the atmosphere so that all vented air from the fuel tank must pass through
the canister before it can pass to the atmosphere. As the mixture of air and fuel pass
9
Figure 2.3: Approximate flowchart of vapor flow during loading process
through the canister from the loading port, the fuel vapors adsorb on the carbon bed
of the canister and clean air is released into the atmosphere through the atmospheric
port.
Another reason canister loading may occur is during a refueling event. During
the refueling process, there is a sudden increase in the liquid fuel level inside the
fuel tank. This sudden liquid volume increase causes the fuel vapor present inside
the fuel tank to be pushed into the canister and the carbon bed is loaded with fuel
vapors during this process. During the refueling event, a lot of vapor is loaded into the
canister quickly it is known as a fast loading event and the loading due to temperature
changes is a slow loading event since the gasoline vapors are loaded on the carbon
bed at a much slower rate.
Figure 2.3 shows an approximate flow diagram of the gasoline vapors during the
adsorption or loading process. The gasoline vapors from the fuel tank flow through
the carbon canister and clean air is released into the atmosphere.
10
Some markets, like in the US, require the canister to adsorb all the vapor released
during the refueling event whereas in other markets such as Europe the fuel pump
will take in the majority of the fuel vapors released during the refueling event. This
is also a major factor involved in the canister design stage. US market canisters have
larger canisters with more activated carbon volume as compared to their European
counterparts [14].
2.2.2 Purging
The event where hydrocarbon vapors are desorbed from the carbon bed by passing
air inside the canister is called purging. During the purging event, the atmosphere
and purge valve remain open while the load valve remains closed. This event occurs
when the engine is running. Figure 2.4 shows an approximate flow diagram of the
airflow through the EVAP system during the purging process.
Figure 2.4: Approximate flowchart of vapor flow during purging process
11
Air is drawn into the canister with the help of the low pressure created during the
engine intake stroke. As air rushes into the canister through the atmosphere valve
the hydrocarbons adsorbed on the carbon bed get desorbed and are pushed into the
engine intake manifold through the purge valve and used for engine combustion. The
pressure created by the engine suction varies depends on the driving cycle and this
can affect the mass flow of air through the canister. The mass flow rate of air decides
the amount of fuel that will be desorbed from the carbon canister. The purge valve is
also a one-way check valve which is used to control the flow and avoid any backflow
into the canister. [22]
2.3 Activated carbon
Activated carbon is a form of carbon which has been processed to increase its
surface area to make it more susceptible to adsorption. The carbon bed inside the
canister consists of activated carbon. Activated carbon used in automotive appli-
cations is usually produced in very small sizes of granules or pellets. The carbon
is obtained from biomass and coal. The carbon is mixed with a binder and passes
through several processing techniques such as pelletizing, heat treatment and condi-
tioning. During this process, the carbon becomes porous and will lead to a larger
surface area allowing higher adsorption. This process is known as activating the
carbon particles [11].
2.4 Literature review
Studies have been conducted by various authors to understand canister perfor-
mance during the adsorption and desorption process. Various authors have used
12
experimental and modeling methods to find factors that affect canister loading and
purging events. A model is presented by Lavoie et al. in 1996 who used experimental
results to predict the behavior of the activated carbon canister. The authors col-
lected data from loading a wood-based activated carbon and predicted the 1D mass
and thermal transient behavior of the carbon canister. The model is written in FOR-
TRAN and was created to run on an IBM-compatible PC. The model still predicts
the canister behavior pretty well and is being used as a base for the model for this
project [12].
Fiani et al. created a model to describe experiments using both heat and mass
transfer. This paper does not handle canister purging but provides good insight
and discussion about conductive and convective heat transfer around a small carbon
sample [8].
Bai et al. developed a 2D model to simulate the adsorption and desorption of n-
butane over an activated carbon bed. They described that the Linear Driving Force
model accurately predicted the mass loading of butane on carbon. Since they created
a 2D model they were able to predict the temperature variation of carbon bed along
the sides of the plastic wall and found that the heat transfer to ambient created a
low-temperature region near the canister walls and in turn lead to better adsorption.
This shows that radial effects do play a part in the adsorption of gasoline vapors on
the canister. The only drawback of this study is the fact that it only used results
and parameters from other studies hence a strong validation could not be done by
the authors [1].
Sato et al. created a 3D CFD model which took twice the amount of time as a
real-time experiment to run the model even with lower resolution. The model was
13
later simplified using a Linear Driving Force model which significantly improved the
model prediction speed and still predicted the results quite accurately. This paper
also inspects the effect of time step which will be useful while modeling in MATLAB
[17].
Smith et al. used a 1D model calibrated using enthalpy of formation and Langmuir
model adsorption and desorption reaction rate ratio. This model was then later used
to simulate a purge valve [19].
Williams et al. studied the effect of canister geometry in bleed emissions and
breakthrough. These authors did a canister design study which helped to understand
how the shape of the canister affects the gas flow and various efforts taken to minimize
the bleed emissions from canisters [21].
Bergaoui et al. studied how different alkanes adsorb on the surface of BAX 1100
carbon and created a model to predict the isotherm for the same. They started
with data collected from C1 - C7 n-alkanes adsorbed on the surface of a Westvaco
BAX-1100 activated carbon. Then they used a statistical physics model to predict
the adsorption behavior of these alkanes on the activated carbon. This isotherm
prediction model can be used to predict the isotherm for n-butane over a wide range
of temperatures [3].
Yoo et al. explored the control-oriented modeling of the canister purging sys-
tem and on-line estimation of fuel loading on the canister. This model created an
analytical expression for the evaporative fuel using only the sensors available in the
production vehicle. This paper allows modeling the canister loading to be versatile
and used in any vehicle just by using the fuel trim value. The model was helpful to
14
understand the need for modeling the canister to be used in different types of vehicle
[22].
This section provided various models created by various authors to predict the
adsorption and desorption on activated carbon in one-, two- and three- dimensional
models. However, none of these models have been created in MATLAB and involve a
large simulation time. This provides the motivation for carrying out this project and
create a fully functional carbon canister model.
15
Chapter 3: Theory and Modeling
This chapter will discuss the fundamental theory behind the modeling of the
carbon canister. It will also discuss the adsorption process and the physical behavior
of the canister at the time of loading and purging.
3.1 Adsorption fundamentals
Adsorption is a surface phenomenon where the molecules of a gas or liquid adhere
on the surface of an insoluble solid. The gas molecules being adsorbed on the surface
is called adsorbate and the surface itself is called adsorbent. For this project, the
adsorbate is the gaseous vapor of fuel and the adsorbent is the activated carbon bed
inside the canister. Since the adsorbent and adsorbate are present in different states
(solid and gas respectively) this process is an example of heterogeneous adsorption.
[2]
The loading event in the carbon canister is an example of physical adsorption or
physisorption where the gas vapor molecules are held in the vacant spots in the acti-
vated carbon by Van Der Waal forces. Physisorption is a relatively weak interaction
as the Van Der Waal forces have weak interaction energy. This allows the adsorbed
particles to be removed quite easily in the case of the carbon canister. [2]
16
3.1.1 Effect of porosity
As mentioned in the previous chapter, the carbon bed is activated by various
processes that increase the carbon porosity and surface area. In the case of adsorption,
high porosity and large surface area of adsorbent are favorable for efficient loading of
adsorbate particles on the adsorbent [18].
An activated carbon adsorbent has different sizes of pores after the activation
process and each pore size plays a different role in the adsorption and desorption
process. Pore sizes larger than 500 Å called macro-pores are inefficient for adsorption
but they transport the hydrocarbon molecules into the smaller pores. Mesopores,
pores ranging from 20-500 Å in size, are the most important pores on the activated
carbon because they effectively adsorb the hydrocarbon vapor molecules and release
them quite easily during the purging process. The smallest pores, micropores, of sizes
less than 20 Å are highly effective for adsorption but are not very effective during
desorption. Due to the high efficiency of the mesopores activated carbon used in
automobile applications contain a large number of mesopores [15].
3.2 Thermal properties of adsorption
Physical adsorption, or physisorption, occurs when the intermolecular forces be-
tween the adsorbate molecules are lesser than that between the adsorbent and adsor-
bate. This makes physisorption an exothermic process as heat is released when the
adsorbate adsorbs on the adsorbent similar to condensation. The enthalpy change of
a reaction is given by:
∆H = ∆G + T ∆S (3.1)
17
Since the adsorbate molecules are more ordered in the adsorbed state the entropy
change, ∆S, of the system will be negative. Also since the adsorption process is
spontaneous the change in Gibbs Free Energy, ∆G, is also negative. Using this in
equation (3.1) shows that the enthalpy change is always negative (exothermic). This
shows that the temperature of the carbon bed will increase during adsorption and
decrease during desorption. Higher temperatures cause unfavorable conditions for the
adsorption process meaning the exothermic adsorption process will act against more
adsorption into the carbon bed [7].
As the adsorption process progresses the thermal properties of the carbon bed will
keep changing throughout the duration of the adsorption. This model will assume a
fixed average of these thermal properties to reduce the complexity of the mathematical
model and faster processing.
3.3 Adsorption Isotherms
Adsorption equilibrium describes the ratio of the amount of adsorbate adsorbed
to the amount remaining in the solution. The adsorption equilibrium is dependent
on the temperature and partial pressure of the adsorbate. The equilibrium will not
provide any information on the rate of the adsorption.
For gaseous adsorbates, the adsorption process is usually described using adsorp-
tion isotherms. An isotherm is a curve which indicates the amount of adsorbate
adsorbed on an adsorbent (adsorption equilibrium) as a function of the partial pres-
sure of the gaseous adsorbate at a constant temperature. The amount of adsorbate
adsorbed is normalized per unit mass of adsorbent so that it can be compared to
different adsorbate-adsorbent combinations [9].
18
Loading is expressed in an isotherm as, θ, a fraction of the maximum amount of
adsorbate that can possibly be loaded on the adsorbent.
Amount of adsorbate loaded

θ= (3.2)
Maximum number of vacant sites available
The loading fraction is a unitless variable and can take any value between 0
and 1. θ = 0 indicates that the system is empty and θ = 1 indicates that the
system is saturated and the adsorbent has no more vacant sites available for loading.
Each isotherm is unique for an adsorbate-adsorbent system but most isotherms follow
that lower temperature and higher partial pressure lead to a higher concentration of
adsorbate loading.
3.3.1 The Langmuir Isotherm Model
A large number of models have been developed to mathematically describe adsorp-
tion isotherms. The models help explain the interactions between the components in
the adsorption system. They are used to design and scale up the adsorption process.
Using the kinetic energy of gases and few assumptions Langmuir was able to
predict a type I isotherm (mono-layer adsorption). The assumptions for the Langmuir
model are:
• The adsorption was limited to a single layer of adsorbate
• The surface of the adsorbent was considered flat
• Each vacant site on the adsorbent surface has an equal probability of adsorbing
an adsorbate molecule.
19
• The adsorbate molecules do not interact with each other or any other molecule
on the site
Using these assumptions, the rate of adsorption and desorption for a molecule of
adsorbate X adsorbing on a vacant site on adsorbent S and forming the adsorbed
state SX can be written as follows:
ads r
S+X (−
−−− SX
+ (3.3)
rdes
The forward reaction is the adsorption reaction occurring at a rate of rads given
by
rads = kads pi (1 − θ) (3.4)
where θ is the fraction of adsorbate molecules that have occupied from the max-
imum available vacant sites, pi is the partial pressure of the adsorbate gas and kads
√
is a constant rate multiplier given by the expression kads = Navo / 2πMw RT . Navo
is the Avogadro’s number, Mw is the adsorbate molecular weight, R is the universal
gas constant and T is the temperature in Kelvin.
The reverse reaction is the desorption occurring at a rate of rdes given by
rdes = kdes e(−EA /(RT )) θ (3.5)
where kdes is constant rate multiplier given by the expression kdes = nm v1 . nm is
the number of adsorbate molecules to complete a monolayer and v1 is the vibration
frequency of the adsorbate particles. The term e(−EA /(RT )) represents the probability
20
of the adsorbate particle to overcome potential energy at the surface of the adsorbent
where EA represents the activation energy [7].
As mentioned in the earlier section, adsorption isotherms are expressed during
adsorption equilibrium where the rate of adsorption is equal to the rate of desorption.
Using this and solving for the amount of adsorbate loaded, θ,
rads = rdes
kads pi (1 − θ) = kdes e(−EA /(RT )) θ (3.6)

Kpi
θ=
1 + Kpi
where the K is a constant and is defined,
kads (EA /(RT ))

K= e (3.7)
kdes
Equations (3.6) and (3.7) show the simplicity and ease of use of the Langmuir
model. The model has only two unknown variables, the activation energy EA and the
kads
ratio of the reaction rate multipliers kdes
. This model shows that as the temperature
increases the loading will decrease. Higher temperature leads to a lower K value and
therefore a lower θ [7].
3.3.2 Linear Driving Force
Isotherms are used to determine the amount of adsorbate present on adsorbent
at equilibrium but they lack the information regarding the speed of the reaction.
Consider the adsorption reaction S + X *

) SX, where a molecule of adsorbate S
adsorbs on the vacant site in adsorbent X to form adsorbed state SX. This reaction is
21
a reversible reaction where the molecule S can be desorbed from the adsorbed state
resulting in a vacant spot and adsorbate molecule.
This reaction can be written in two ways - one with two counter-acting reactions
with their own reaction rates or as one reaction with one reversible reaction rate.
Equations (3.4) and (3.5) are examples of counteracting reactions. The same reaction
can be rewritten with only one reaction rate as
r
S+X ←
→ SX (3.8)
This is achieved by having the reaction rate as the driving force between the
current state and the equilibrium state of the reaction. The most simple reaction
rate is given by the linear driving force (LDF) which is written as:
r = k(θeqm − θ) (3.9)
where r is the reaction rate for (3.8), k is a time constant, θeqm is the loading level
at equilibrium and θ is the current local loading level of the adsorbate. Equation (3.9)
will be positive for an adsorption reaction and negative for a desorption reaction. The
LDF model can be used to display any isotherm with a reaction rate expression [5].
3.3.3 Adsorption Isotherm Model
For a particular family of adsorbates, the adsorption isotherms can be defined
using the relative volume of adsorbate adsorbed and the differential free energy of
adsorption normalized to a unit volume of liquid.
22
The relative volume of adsorbate adsorbed, v (unitless), is defined as the ratio
of the volume of adsorbate adsorbed per unit mass of carbon, V (m3 /kgC), to the
saturation volume of the carbon, V0 (m3 /kgC),
V
v= (3.10)
V0
The differential free energy of adsorption per unit volume, f (J/m3 ), can be written
as:
ρL RT psat
f= ln (3.11)
W pi
where ρL (kg/m3 ) is the liquid density of the adsorbate , R = 8.314 (JK −1 mol−1 )
is the universal gas constant, W (kg/mol) is the molecular mass of adsorbate, T (K)
is the absolute temperature, pi (P a) is the partial pressure of adsorbate and psat (P a)
is the saturation pressure of adsorbate at T [12].
Figure 3.1 shows an isotherm for n-butane (adsorbate) adsorbed on activated
carbon BAX 950 (adsorbent) plotted in terms of parameters v and f. This curve
has been plotted by curve fitting data collected of n-butane adsorbed on BAX950
activated carbon by Westvaco Company. The curve fit was identified by Lavoie [12]
using equations (3.12) and (3.13). For computational convenience, the data is divided
into two segments by breakpoints v ∗ and f ∗ . The breakpoint is the point where the
curve is continuous on both sides v ∗ = 0.9 and f ∗ = 4 J/ml. The curve fit parameters
are described in table 3.1.
Below the breakpoint, v ∗
∗ 1/n
A
f (v) = f1 ln v ≤ v∗ (3.12)
v
23
Figure 3.1: Adsorption Isotherm for n-Butane on BAX 950 Activated Carbon using
f and v
Above the breakpoint, v ∗
f0
f (v) = v v > v∗ (3.13)
B∗
−1
This plot only shows one hydrocarbon adsorbate but studies have shown that
hydrocarbons ranging from methane to hexane can be plotted on the same curve.
This allows adsorption curves to be created for hydrocarbons in the same family as
long as one curve is available [10].
24
Curve parameter Value Unit
6
f1 85 ∗ 10 J/m3
f0 0.5 ∗ 106 J/m3
n 1.2 -
v∗ 0.9 -
∗
A 0.9233 -
∗
B 0.8 -
− 3
V0 8.3 ∗ 10 4 m /kgC
Table 3.1: Adsorption Isotherm curve-fit parameters
3.4 Breakthrough and Bleed emissions
The carbon canister has a limited capacity based on the type of activated carbon
present inside the canister. The size of the canister and the type of activated carbon
used must meet the required minimum emission standards.
3.4.1 Canister Breakthrough
The carbon bed inside the canister has a limited number of vacant sites avail-
able for adsorption. While the canister is being loaded with hydrocarbons it will
eventually run out of vacant spots. This leads to canister saturation when all the
vacant spots are filled and further loading of the canister will lead to the hydrocar-
bon molecules escaping into the atmosphere. This phenomenon is known as canister
breakthrough. Lavoie (1996) shows data collected from canister loading to follow
a non-linear behavior with effective adsorption at low vapor pressures. This non-
linearity of the activated carbon leads to complete saturation of the carbon canister
before appreciable breakthrough occurs to the atmosphere [12].
25
An ideal canister would have a unit step function for canister breakthrough where
the concentration of hydrocarbons leaving the canister would be equal to the hydro-
carbons entering the canister. A non-ideal canister would have non-isothermal effects
and non-ideal geometry leading to a slightly earlier breakthrough as compared to an
ideal canister. For emission purposes, a canister is considered saturated when 2.0g of
hydrocarbon is released from the canister atmosphere port [21].
3.4.2 Bleed emissions
The carbon canister is loaded from one end to another. This tends to cause a
concentration gradient in the carbon bed after loading. This concentration gradient
can lead to diffusion of adsorbate particles within the canister even if there is no
convective flow inside the canister. As mentioned in the earlier section, non-ideal
canisters tend to have breakthrough slightly before the carbon bed is saturated. The
diffusion phenomenon can lead to breakthrough if the canister is left for a while, this
event is called bleed emissions.
Diffusion bleed emissions can be reduced efficiently by making the carbon beds
longer, having air pockets in between carbon beds or by using an auxiliary chamber
with another carbon bed since it will lead to lower pressure drops [21].
3.5 Model development
The adsorption and desorption process inside the canister can be simplified as a
flow inside a tube. To accurately model the adsorption and desorption the carbon
canister model is developed by discretizing the carbon bed inside the canister in
one axis and calculating the mass loading along this axis. As mentioned in the
earlier sections adsorption and desorption are exothermic and endothermic processes,
26
therefore, the corresponding temperature change accompanied by the mass loading
at each section also needs to be modeled for better accuracy.
3.5.1 Mass transport equation
To model the carbon canister, we consider a 1-D bed of activated carbon (ad-
sorbent) along a coordinate axis, x, of length L. The mass of the carbon bed inside
the canister is given by mcarbon and the canister has a uniform cross-sectional area of
Ax . The carbon bed is assumed to have an initial arbitrary loading of butane vapors
given by mini . The mass of butane loaded on the carbon bed will be defined by m1 .
A molar flow along the axis of the canister containing a mixture of butane and air is
introduced to change the distribution of the vapor loading inside the canister. The
mass transport equation will determine the mass loading of butane on the carbon bed
with time along the length of the bed with time t, m1 (x, t), given an initial loading
of m1 (x, 0) = mini .
Using equation (3.10) we can calculate the relative volume of adsorption for each
point along the length of the carbon bed. Once relative volume of adsorption is
calculated equations (3.12) or (3.13) can be used to calculate the differential free
energy of adsorption. At equilibrium the partial pressure of butane vapor is a function
of the loading of butane on the carbon bed and the temperature, T. Rearranging
equation (3.11) we can calculate the partial pressure of butane in the carbon bed.
fW
p1 = psat e ρL RT (3.14)
Saturation pressure for butane for a given temperature T can be calculated using
the Antoine equation:
27
B
log10 (psat ) = A − (3.15)
T −C
where A, B, C are empirical coefficients and T is the absolute temperature. An-
toine coefficients for n-butane at relevant temperatures are presented in table 3.2.
The parameters are based on pressure in bar and absolute temperature [13].
Temperature Range (K) A B C

195.11-272.81 3.85002 909.65 -36.146
272.66-425.00 4.35576 1175.581 -2.071
Table 3.2: Antoine equation coefficients for n-Butane
Using the partial pressure of the butane vapor in the canister and the total pressure
the local mole fraction can be calculated and similarly the mole fraction of air in the
system:
p1
y1 =
pt (3.16)
ya = 1 − y1
Convective term
The mixture of butane and airflow can be assumed to be uniform and equal to
the inlet along the length of the canister bed. The flow of butane due to convection
can be written as:
y1
Q1 conv = Qt y1 = Qa (3.17)
ya
28
where Qt is the total convective flow inside the canister and Qa is the convective
flow of air.
Diffusive term
The vapors that have loaded on the carbon bed can also diffuse within the canister
over time. This diffusion primarily occurs in the gas phase and is given by:
∂n1
Q1 dif f = −Ax βD1 (3.18)
∂x
where D1 is the diffusion coefficient and n1 is the molar concentration of butane
vapor in the carbon bed while β is a dimensionless factor to take into account changes
in cross-sectional area and longer flow length due to void space. For the simplified
model we can assume β = 1.
The molar concentration of butane can be written as the product of total molar
concentration and mole fraction of butane, n1 = nt .y1 . Using ideal gas law, nt =
pt /RT .
Simplifying equation (3.18) we get,
pt ∂y1
Q1 dif f = −Ax βD1 (3.19)
RT ∂x
Overall mass transport equation
Considering a small element, ∆x, of carbon bed with a cross-sectional area, Ax ,
the rate of change of adsorbed butane can be written by using continuity of moles:
∂N ∆[Ax n1 ] ∆(Q1 + Q1
conv dif f )
≡ =− (3.20)
∂t ∆t ∆x
Substituting equations (3.17) and (3.19)
29

∂n1 Qa ∂(y1 /ya ) βD1 pt ∂ ∂y1
=− + Ax (3.21)
∂t Ax ∂x Ax RT ∂x ∂x
Using ρapp to denote the apparent density of the carbon bed, D1 in terms of
p
diffusion coefficient of air D1 = Da WA /W1 , replacing Qa with ma /Wa and rewriting
the equation in terms of mass loading we get:
r
∂m1 ṁa W1 ∂(y1 /ya ) ρa βDa W1 ∂ ∂y1
=− + Ax (3.22)
∂t ρapp Ax Wa ∂x ρa pp Ax Wa ∂x ∂x
where m1 is the specific mass loading of butane per unit mass of carbon, ρa is the
density of air, Wa is molecular weight of air, W1 is molecular weight of butane.
3.5.2 Thermal Transport equation
During the loading of canister the local carbon bed temperatures have seen to
go as high as 90◦ C and during purging the temperatures have dropped to as low as
−10◦ C. These high transients bring the need to model the thermal effects of the
carbon bed during these processes. The thermal effects of the carbon bed can be
modeled using the conservation of energy equation [12].
Energy conservation equation
Similar to the mass transport equation we consider a small element of the canister,
∆X along the flow direction. Conservation of energy states that:
∂E ∂QEconv ∂QEcond dQloss

=− − − (3.23)
∂t ∂x ∂x dt
where E is the total energy in the system, QEconv is the energy flux due to con-
vection in the x-direction, QEcond is the conductive energy flux and dQloss /dt is the
heat loss to and from the canister to the ambient air through the plastic wall.
30
Expanding on equation (3.23) we have:
∂E ∂
= [ρapp Ax {ec + mp ep + ma ea + m1 e1 + Es (m1 , T )}] (3.24)
∂t ∂t
where ρapp is the apparent density of the carbon bed (prior to adsorption), Ax is
the cross-sectional area of the canister, ec , ep , ea and e1 are the mass-specific internal
energy of carbon, plastic wall, air and butane respectively. mp , ma , m1v , m1 are the
mass quantities relative to the mass of carbon for plastic, air, butane vapor and
adsorbed butane respectively. The energy of the adsorbed material, Es is a function
of the total volume adsorbed.
Convection
The energy flux due to convection of butane vapor along the carbon bed is given
by:
∂QEconv ∂
= [Qt (h1 W1 y1 + ha Wa ya )] (3.25)
∂x ∂x
where Qt is the total molar flow given in (3.17), h is the mass-specific enthalpies,
W is the molecular weight of and y is the mole fraction.
Conduction
The energy flux due to conduction is given by:

∂QEcond ∂ ∂T
=− Ax kapp (3.26)
∂x ∂x ∂x
where kapp is the apparent effective thermal conductivity of the carbon bed. The
thermal transport due to the diffusion of butane vapor is expected to be small as
31
compared to the conductive term and can therefore be ignored in the overall thermal
transport equation [12].
Heat Loss
The energy loss through the plastic container of the canister is given by,
dQloss
= Pext (x)Uext (T − Tamb ) (3.27)
dt
where Pext (x) is the perimeter of the canister at point x, Uext is the overall external
heat transfer coefficient between the ambient air and carbon bed and Tamb is the
absolute ambient temperature.
The overall external heat loss transfer coefficient can be expressed in terms of
heat transfer conductance through the plastic wall to ambient air, Uloss , apparent
conductivity of the activated carbon, kapp and cross-sectional area as:
1
Uext = √ (3.28)
1/Uloss + Ax /3kapp
Energy properties
Assuming constant specific heats, the mass-specific internal energy can be written
as:
ec = Cvc T
ep = Cvp Tp
(3.29)
ea = Cva T
e1 = Cv1 T
The energy of the adsorbed phase can be written in the form [12]:
32
Zm1
f (v)
Es (m1 , T ) = Cp1 T − ∆hvap1 (T ) − dm1
ρL
0 (3.30)
d f (v) dm1
Es (m1 , T ) = Cp1 T − ∆hvap1 (T ) −
dt ρL dt
Overall Thermal Energy Release Equation
Using equations from (3.24) to (3.30) to substitute into equation (3.23) and noting
that the gaseous energy terms ma ea andm1 e1 are smaller compared to the carbon
energy term we get,

dTp ∂∆hvap ∂T
CV C + mp CP P + m1 CP − =
dTC ∂T ∂t

f (v) ∂m1
− CP T − ∆hvap −
ρL ∂t

1 ∂ ṁa T Cp W1 y1 + CPa Wa ya kapp ∂T
(3.31)
− − Ax
Ax ∂x ρapp Wa ya ρapp ∂x
Pext 1
− √ (T − Tamb )
ρapp Ax 1 + Ax
Uloss 3 kapp
The mass and temperature terms have been separated to obtain the temperature
equation.
dTp
The first two terms on the LHS of the equation CV C and mp CP P dT C
represent the

thermal inertia of the carbon and the canister wall. The next term, m1 CP − ∂∆h ∂T
vap
,
represents the thermal inertia of the adsorbed mass of butane vapor.

h i
The first term on the RHS, CP T − ∆hvap − fρ(v) L
∂m1
∂t
, represents the energy
added to the system by adsorption of butane on the carbon bed. The next two
h i
1 ∂ ṁa T Cp W1 y1 +CPa Wa ya kapp ∂T
terms, Ax ∂x ρapp W a ya
− Ax ρapp ∂x , represent the energy added to the
system through convection and conduction along the bed. The last term, − Pext
ρapp
(x)
,
represents the heat loss from the system to ambient through the internal boundary.
33
Chapter 4: Experiment Analysis
This chapter describes the experimental setup to collect data required to calibrate
and validate the canister model described in chapter 3.
4.1 Experimental Setup
In order to collect reliable data, an automotive canister from two different vehicles
were used. The canisters were fitted with multiple thermocouples along the length to
measure the temperature changes on the activated carbon bed.
4.1.1 Canister geometry
Two canisters of different sizes and geometry were used to get a wide range of
model validation. The first canister, taken from a mid-size pickup truck, consists
of BAX-1100 activated carbon bed arranged in a straight line. Figure 4.1 shows a
sketch of the canister. The canister contains 1270 g of activated carbon encompassing
a volume of 3.5 L. The load valve and purge valve are on the one end of the canister
and the atmosphere valve is placed on the opposite end of the canister. During the
loading phase, the purge valve will be sealed off with sealant caps provided with the
canister and air will flow from the load valve to the atmosphere valve. The cross-
sectional area of the airflow path can be approximated to around 81.5cm2 .
34
Figure 4.1: Schematic Diagram of Canister 1
The second canister, taken from an SUV, consists of BAX-1100 activated carbon
bed arranged in a U-shape inside a rectangular casing. Figure 4.2 shows a sketch of
the canister. This canister contains 1000 g of carbon encompassing a volume of 2.7L
inside the canister. The cross-sectional area of the airflow path can be approximated
to around 67cm2 .
Figure 4.2: Schematic Diagram of Canister 2
35
The reason for using two different types of canisters is to validate the model as
long as the geometry of the canister is provided.
4.1.2 Thermocouple connections
The aim of the experiment is to observe the changes in carbon bed temperature
as the activated carbon is adsorbing butane vapors and while it is being purged with
clean air. Since activated carbon has a non-linear behavior when it comes to vapor
loading, the carbon bed will have different concentrations of butane vapor during the
course of the experiment. Different rates of loading along the length of the bed lead
to different temperatures along the length of the carbon bed. To account for this
thermocouples have to be placed at different sections of the carbon bed to observe an
accurate temperature variation at different points along the length of the bed.
To place a thermocouple first a hole the size of the thermocouple was drilled
on the plastic casing of the canister. After drilling, the canister was prepared by
inserting K-type thermocouples into the carbon bed to ensure that the thermocouple
will be able to accurately measure the bed temperature. Along with the K-type
thermocouples, T-type thermocouples were also used on the body of the canister to
measure the temperature variation on the walls of the canister during loading and
purging experiments. Another T-type thermocouple was used to measure the ambient
air during the experimental process.
The first canister was prepared with 5 K-type thermocouples placed along the
length of the carbon bed and 1 T-type thermocouple on the canister wall. The second
canister was prepared with 4 K-type thermocouples with 2 placed on one edge of the
U-shape and the 2 more placed on the other edge of the U-shape. The second canister
36
Figure 4.3: Thermocouple positions on canister 1
was also fitted with 1 T-type thermocouple to measure the temperature changes to
the wall of the canister. Figures 4.3 and 4.4 show the sketches of the thermocouple
position on each canister.
Figure 4.4: Thermocouple positions on canister 2
37
4.1.3 Setup Description
During the experimental testing, the canister under testing will be placed on top
of an Adam Equipment GFK 165ah weighing scale with a capacity of 75 kg and
readability of 1g. This weighing scale is used to measure the mass change of the
canister during the loading and purging process. The thermocouples attached on the
canister are connected to an ETAS ES650.1 A/D and Thermo module to observe the
temperature changes in the carbon bed and plastic wall. Data is acquired from the
ETAS module with the help of a software named INCA which is published by ETAS
for data measurement and calibration. The data collected from INCA is converted
to an m-file readable in MATLAB and the data is plotted.
To allow for the flow of gas the canister is connected to other components in the
experimental setup with the help of rubber tubes and brass connectors.
Figure 4.5: Rotameter used to Measure Vapor volumetric flow rate
38
During the loading phase, the butane gas is provided from a cylinder that contains
a mixture of n-butane and nitrogen mixed in a 50/50 volume mix. The butane
nitrogen mixture is usually used in testing to avoid errors from using different gasoline
types with different composition of volatile compounds. The cylinder is controlled
using a regulator which measures the cylinder pressure and allows the user to control
the exit pressure of the mixture from the cylinder. This regulator is connected to a
Praxair PRS3002-FL3-CGA rotameter which allows the user to control the volumetric
flow rate of the gas mixture coming out the cylinder. Figure 4.5 shows a picture of
the flowmeter used to measure the flow rate of gas into the carbon canister.
Figure 4.6: Schematic Diagram of the Canister loading experiment setup
In real-life conditions, the flow rate of gasoline vapors into the carbon canister
is very slow. The flow-meter was selected such that it can measure a flow range of
39
94.8 - 948 sccm of air. The flow-meter is connected to the inlet port (load valve) of
the canister. The exit port (atmosphere valve) is connected to another spare canister
on a weighing scale to measure 2g breakthrough from the test canister. The setup
is kept near a shop ventilation pipe to avoid any butane leak into the ambient air.
Figure 4.6 shows a schematic diagram of the canister loading setup for experimental
analysis.
Figure 4.7: Schematic Diagram of the Canister Purging experiment setup
During the purging phase, air to purge the canister is provided by an air com-
pressor. The air compressor is connected to an Omega Engineering FMA1845A mass
flow meter which displays the flow rate of air in LPM using an LCD display. The flow
is manually controlled by increasing or decreasing the pressure of air exiting the air
compressor. The flow-meter is connected to the atmosphere valve port of the canister.
40
The reverse airflow through the canister desorbs the adsorbed n-butane and purges
it out the canister purge valve. Figure 4.7 shows a schematic diagram of the canister
purging setup.
4.2 Testing Procedures
A number of tests with varying conditions have been conducted to obtain data
required to validate the carbon canister model.
4.2.1 Canister loading
In order to maintain similar initial conditions for all experiments, before each
loading experiment the canister is purged with air at a constant rate of 50 L/min till
the canister displayed a weight reduction of 0.5g in 10 minutes which is the equivalent
to 7x10−4 exit hydrocarbon concentration.
n-Butane vapor is loaded into the canister using a cylinder and flow-meter. The
cylinder contains a mixture of butane and nitrogen in 50/50 ratio by volume. The
composition of the cylinder is shown in table 4.1. To simulate real-time loading
conditions as in a vehicle, n-butane is loaded into the canister at a rate of 50 g/hr.
Gas Pressure Volume Mass Moles

(Psig) (m3 ) (g) (mol)
Butane 4.92 0.059 145.79 2.5085
Nitrogen 25.00 0.059 70.26 2.5085
◦
Totals @70 F 0.119 216.05 5.0169
Table 4.1: n-Butane and Nitrogen Mixture Gas cylinder Composition
41
Since the flow-meter only measures the volumetric flow of air we need to apply a
correction factor and calculate the required flow of the n-butane and nitrogen mixture
to obtain 40 g/hr of n-butane. To calculate the correction factor, we need to calculate
the specific gravity of the mixture:
molecular weight of gas mixture

SG =
molecular weight of air
(% of N2 ∗ mol. wt of N2 + % of C4 H10 ∗ mol. wt. of C4 H10 )
SG =
mol. wt. of air (4.1)
0.5 ∗ 27 + 0.5 ∗ 58.12
SG =
28.97
SG = 1.486
The correction factor of a rotameter flowmeter is given by:
r
1
CF =
SG (4.2)
CF = 0.8202
Using the correction factor the new flowmeter range is calculated for a mixture of
n-butane and nitrogen in a 50/50 ratio by volume. Range of flow meter for n-butane
and nitrogen mixture = Range of flowmeter for air * correction factor = 94.8*0.8202
- 948 *0.8202 = 77.755 - 777.550 cc/min of n-butane and nitrogen mixture at 50/50
by volume.
Table 4.1 is used to calculate the required flow of the mixture required to obtain
40 g/hr of n-butane in the following steps.
• Weight fraction of n-butane in the mixture = mass of n-butane in mixture

Total mass of mixture
145.79 g
= 216.05 g
= 0.6748
• 1 g of mixture contains 0.6748 g of n-butane
42
• To get 50 g/hr of n-butane we will need 50
0.6748
= 74.10 g/hr of mixture
• 0.119 m3 volume contains 216.05 g of n-butane and nitrogen mixture.
0.119m3
• Volume containing 74.1 g/hr of mixture = 216.05g
∗ 74.1 g/hr
= 0.04081 m3 /hr = 680.2 cc/min
Therefore the required flow rate of the mixture to obtain 50 g/hr of n-butane is
544.19 cc/min. Figure 4.8 shows a picture of the setup used to load the canister.
Figure 4.8: Experimental setup for loading experiments
4.2.2 Canister Purging
Once the carbon canister is completely loaded with 2g breakthrough the canister
is said to be saturated. This canister is now ready to be purged. Once the canister
is saturated it is allowed to cool down to room temperature. To purge the canister,
43
Figure 4.9: Experimental setup for Purging experiments
the air is passed through the canister from the atmosphere vent and adsorbed butane
vapors are desorbed from the pores present in the activated carbon bed. Figure 4.9
shows the picture of the experimental setup for purging experiments.
Before the experiment begins all connections are sealed using vacuum tape to
prevent any gas leaks and the flowmeter is switched on. Since the flowmeter measures
flow by introducing a heat flux into the gas flow and measuring the amount of heat
carried by the gas, the flowmeter takes around 15 minutes to warm up after initial
powering up. Once a flowmeter is warmed up the experiment is ready to collect data.
The data acquisition system is powered on and INCA starts recording data collected
by the ETAS equipment.
44
To start the airflow, the air compressor is switched on and the pressure is varied
till the Omega Engineering flowmeter reading reads 50 LPM. Once the air is flowing
through the canister the ETAS equipment will measure the changes in the carbon bed
temperature and the weighing scale will measure the canister mass changes during
the desorption process. To ensure that inflammable butane vapor is not released into
the lab, the pipe from the purge valve is placed near the lab exhaust pipe.
45
Chapter 5: Simulation Method and Parameters
5.1 Method of solution
The partial differential equations of mass and temperature can be solved by dis-
cretization of the PDE into sections. For an initial condition ordinary differential
equation, the value of the first differential is given. Using this initial condition the
subsequent states of the equation are determined using a finite difference scheme.
Similarly, for a boundary value problem with a second-order ordinary differential
equation the boundary conditions reduce the degree of freedom of the system by the
number of boundary conditions available. The idea for a partial differential equation
is similar to the ordinary differential equation.
The equations (3.22) and (3.31) show that the equations are a 1st order PDE in
time and a 2nd order PDE in space. The system is discretized on a two-dimensional
grid for space, length of the carbon bed x, and time, t, using the notation mi,j ≡
m(i∆x, j∆t). Here ∆x refers to the size of nodes or discretization length of the carbon
bed and ∆t refers to the time step of the simulation. The domain for the PDE along
x is bounded by the boundary conditions and the domain for t is semi-infinite with
an initial condition and run till the simulation is stopped.
46
To perform the integration in t, the PDE is discretized by approximating ∂m/∂t
with the forward difference method and ∂m/∂x with the central difference method
as shown in equations (5.1) and (5.2).

∂m mi,j+1 − mi,j
≈ (5.1)
∂t i,j ∆t

∂m mi+1,j − mi−1,j
≈ (5.2)
∂x i,j 2∆x
The second partial derivatives in the PDE are approximated by the 2nd order
central difference method as shown in equation (5.3).
∂ 2m

mi−1,j − 2mi,j + mi+1,j
≈ (5.3)
∂x2 i,j (∆x)2
5.2 Initial and boundary conditions
The state variables in the equations are the mass of adsorbate adsorbed per mass
of carbon and the temperature of the carbon bed. The partial differential equations
(3.22) and (3.31) are single derivatives in time and their solution in the time domain
require an initial condition given by:
m1 (x, 0) = m1 init (x) (5.4)
and
T (x, 0) = Tinit (x) (5.5)
47
The carbon bed is assumed to have an initial adsorbed mass loading of 0.35 g/gC
and the initial temperature of the system is taken as average room temperature of
21 ◦ C. Using the initial mass condition, m1 init , the mole fraction of the butane
vapor, y1 init , at each point on the carbon bed is calculated to get the initial loading
condition for equation (3.22).
The partial differential equations are second derivatives in space and therefore
need two boundary conditions for the solution. The boundary conditions at the inlet
(at x=0) for positive flow are given by:
m1 (0, t) = m10 (t)

(5.6)
T (0, t) = T0 (t)
At the outlet of the canister (x=L) we can neglect all heat and mass transport
except convection thus giving a constant gradient:
∂m1
(L, t) = 0
∂x (5.7)
∂T
(L, t) = 0
∂x
For purging condition, the flow is reversed and the boundary conditions are also
reversed. At x=L the boundary conditions are set by the flow rate of gas and at x=0
the gradients are set to 0. The purging experiment is conducted with a completed
saturated carbon canister, therefore, the initial conditions of the canister will include
saturated canister.
5.3 Loading and purging simulations
The simulations are set up to replicate the environmental and physical conditions
of the experimental setup to accurately predict the behavior of the carbon canister.
48
Solving the partial differential equations occurs in two steps. In the first step, using
the initial and boundary conditions the equation for the mass transport (equation
3.22) is used to advance the mass loading on butane along the carbon bed in time.
In the second step, the updated mass loading of butane, gas concentrations along
the bed and energy flux terms are calculated using the first step and the temperature
along the bed is updated using equation (3.31). Due to the coupling between the mass
and temperature equations some instabilities may arise during this two-step solution
process.
The physical properties of the carbon bed, plastic canister and other model pa-
rameters are mentioned in table 5.1 and 5.2.
Property Symbol Value Unit

Apparent Density of Activated Carbon ρapp 345 kg/m3
Ratio of plastic mass to carbon mass mp 0.5 -
Specific Heat of Carbon CvC 700 J/(kg K)
Specific Heat of Butane Cp1 1600 J/(kg K)
Specific Heat of Plastic Cpp 1900 J/(kg K)
Apparent Thermal Conductivity of Carbon bed kapp 0.13 W/(m K)
Self Diffusion Coefficient of air Da 1.5 ∗ 103 m2 /s
Axial Diffusivity Factor in Carbon Bed β 1 -
Table 5.1: Physical Properties of carbon bed and other Model Parameters
5.4 Parameter Estimation
In equations (3.22) and (3.31) all parameters are properties of the carbon bed,
plastic canister or the gas flowing inside the canister except for the ratio of change of
49
Property Unit Canister 1 Canister 2
Length cm 53 46
2
Cross-Sectional Area cm 81 70
Canister Volume L 3.5 2.7
Carbon Mass g 1270 1000
Activated Carbon Type - BAX 1100 BAX 1100
Discretization Length mm 5 5
Table 5.2: Canister Geometric Properties
plastic wall temperature with respect to carbon bed (dTp /dTC ) and the heat loss con-
ductance through the wall (Uloss ). These parameters are calibrated from experimental
data before they can be used in the model.
A canister cool down experiment is conducted to estimate these parameters. This
experiment is done by loading the carbon canister till the part of the canister under
consideration reaches its maximum temperature and then the butane flow into the
canister is shut off. Since there is no flow and no new butane being added to the
canister the temperature of the canister will begin to cool down to room temperature.
The stagnant air will prevent heat loss through the ends of the canister and heat loss
will only occur through the plastic walls of the canister [12].
To calibrate the two parameters canister 1 is loaded with butane till thermocouple
1 (figure 4.3) reaches its maximum temperature and starts to cool down. This indi-
cated that this area of the carbon bed is saturated. Once saturated the temperature
of the carbon bed and the skin thermocouple is collected. Since there is only heat loss
across the walls of the canister and very little heat loss across the ends, the equation
(3.31) can be modified to get:
50
" Pext √1
#
∂T ρapp A (1/Uloss + A/(3 kapp ))
= (T − Tamb ) (5.8)
∂t CvC + mp Cpp dTdT
p
+ m 1 (C p1 − ∂∆hvap
∂T
)
The value of dTp /dTC can be determined by studying the decrease in temperature
of the plastic wall with respect to the decrease in temperature of the carbon bed.
Using this value, equation (5.8) is modeled in MATLAB and the values for Uloss is
varied until the equation fit matches the data for the cooldown experiment.
Once the values are calibrated the cool down test is done once more to validate
the calibrated values. The values are also validated by modeling the cool down test
for canister 2 and predicting the heat loss in the canister bed after saturation.
51
Chapter 6: Result and Discussions
6.1 Experimental results
This section will present the experimental results of canister testing. First, the
experimental results for loading the two canisters are presented and then the results
for purging the canister is presented. The end of the section will discuss a few mea-
surement errors and inaccuracies present in the data collection for this project.
6.1.1 Canister Loading Mass and Temperature Variation
As described in section 4.2.1 to study the effect of vapor loading on canister mass
change and carbon bed temperature, a constant flow of n-butane is provided to the
canister through the load valve. Figures 4.3 and 4.4 show the positions of the ther-
mocouples in two canister under testing. These thermocouples are positioned in the
radial center of the carbon bed to obtain a good measure of the bed temperature.
A problem that can arise with this method is that the thermocouples can only pro-
vide temperature information at discrete points on the carbon bed, thus limiting the
information available.
Figure 6.1 and 6.2 mass and temperature profiles as the canister is loaded with
n-butane at a constant flow. The experiment lasted 6 hours and 20 minutes before
52
Figure 6.1: Canister #1 Mass Profile during Loading Experiment
the 2g breakthrough was observed in the spare canister. The mass of the canister
increased by 321g showing that the canister adsorbed 321 grams of n-butane. Since
the n-butane was flowing at a constant flow the mass of the canister also increased
linearly at the same constant rate.
Figure 6.2 shows the temperature profile as the adsorption moves across the can-
ister bed. As explained in 3 adsorption is an exothermic process and the temperature
of the carbon bed increases as the carbon adsorbs n-butane. Once a portion of the
carbon bed is saturated no more butane can be adsorbed and the temperature of
the carbon bed decreases to room temperature. At the end of 6 hours and 20 min-
utes, the concentration wave of butane has moved completely across the bed. Before
thermocouple 4, the area of canister #1 changes which account for the difference in
53
Figure 6.2: Canister #1 Temperature Profile during Loading Experiment
temperature rise of the canister at this position. The cross-sectional area of the can-
ister decreases before thermocouple 4 and leads to an uneven temperature increase.
The temperature at the center of the carbon bed, where the thermocouples are fitted,
is higher than the temperature at the ends of the canister as seen by the difference
in temperature increase between the normal thermocouple and skin thermocouples.
Figure 6.3 shows the mass increase as canister #2 is loaded with n-butane at a
constant flow rate. Canister #2 has a smaller cross-section and shorter carbon bed
length as compared to canister #1. This leads to canister #2 reaching 2g break-
through earlier than canister #1 as seen in the figure. The experiment lasted 4 hours
and 50 minutes and the mass of the canister increased by 253g. Similar to the pre-
vious experiment, the mass of the canister increased in the same linear rate as the
butane gas was loaded into the canister.
54
Figure 6.4 shows the temperature profile of canister #2 as it is loaded with butane
gas at a constant rate. The concentration wave moves along the length of the carbon
bed and the temperature in each portion of the bed increases until it is saturated.
Once a section of the bed is saturated no more butane vapor can be adsorbed on the
carbon bed and the concentration wave of butane will move ahead. As mentioned
earlier, the cross-sectional area of canister #2 is smaller than canister #1 and this
causes a larger increase in temperature at each section in the canister as compared
to canister #1. This is evidenced in equation (3.31) where a larger area leads to a
smaller increase in carbon bed temperature due to better convection and heat loss
to the environment. The heat generated by the adsorption is dissipated easily when
the cross-sectional area of the carbon bed is larger. Due to this factor, the carbon
bed temperature of canister #2 increases higher than canister #1. This factor is
55
also the reason why the temperature measured by thermocouple 4 rises to a higher
temperature as compared to the temperature at the previous thermocouples.
6.1.2 Canister Purging Mass and Temperature Variation
To study the effect of purging on a saturated canister, the mass change and tem-
perature change along the carbon bed of the canister is recorded as the canister is
purged with 50 LPM of air through the atmosphere vent. Once a fully saturated
canister has cooled down to close to room temperature the canister is purged with
air from an air compressor. The flow is controlled by changing the output pressure
out of the compressor and the flowmeter provides a reading of the airflow rate.
Figure 6.5 shows the mass loss in canister #1 as it is being purged with 50 LPM of
air through the vent port. The first few minutes are very critical to canister purging
56
Figure 6.5: Canister #1 Mass Profile during Purging Experiment
as the canister releases a lot of butane during this time period. The figure shows a
steep decrease in the canister mass which then reduces to a gradual decrease in mass.
The mass flow rate of air is much higher than the rate at which the canister is being
loaded which leads to a much faster decrease in canister mass as compared to the
increase in mass during loading experiment.
Figure 6.6 shows the temperature profile of canister #1 as it is being purged with
50 LPM of air. Since purging through the atmosphere port, the thermocouple closest
to the inlet air is thermocouple 5. As mentioned earlier, since purging is a much faster
process than loading, desorption occurs in all parts of the canister simultaneously.
This leads to the sudden decrease in temperature at all parts of the canister as
evidenced in the figure. Once the canister has been completely purged of butane
vapors, the temperature of the carbon bed returns to ambient temperature. The
57
Figure 6.6: Canister #1 Temperature Profile during Purging Experiment
end of the carbon bed closest to the atmosphere vent reaches ambient temperature
first due to its proximity to the incoming air and faster heat loss due to convection.
Positions on carbon bed further down will reach ambient temperature slower since
the butane vapor from the atmosphere vent end flow along the carbon bed to the
purge vent and may get adsorbed along the way. The plastic wall of the canister
also experiences a decrease in temperature similar to the carbon bed as seen by the
reading from the skin thermocouple.
Figure 6.7 shows the mass profile of canister #2 during the purging experiment.
Similar to canister #1, most of the butane is removed from canister 2 in the first 10
minutes of the experiment. The experiment lasted 75 minutes after which the mass
of the canister decreased by less than 0.5g every 10 minutes.
58
Figure 6.7: Canister #2 Mass Profile during Purging Experiment
Figure 6.8 shows the temperature profile of canister #2 as it is being purged with
50 LPM of air. The n-butane starts to desorb from the carbon bed quickly once the
inlet air is introduced into the canister and this causes a decrease in the carbon bed
temperature. In canister 2, thermocouple 4 was placed too close to the atmosphere
port which did not allow the thermocouple to get an accurate reading of the carbon
bed temperature and instead was only able to read the incoming air temperature.
The remaining three thermocouples displayed an accurate reading of the carbon bed
as it was being purged. Thermocouples 2 and 3 started at a higher temperature than
thermocouple 1. Similar to canister 1 the last thermocouple along the carbon bed
(thermocouple 1) took the longest to return to ambient temperature as butane vapor
was desorbed from this section of the canister last.
59
Figure 6.8: Canister #2 Temperature Profile during Purging Experiment
6.1.3 Measurement errors and inaccuracies
The experiments in this project were conducted in non-ideal conditions. The flow
of butane into the canister is controlled by using the manually operated rotameter
which is mainly used to indicate the flow rate of gas. This can cause a small dis-
crepancy in the flow meter readings which adjusting the flow. The flowmeter used to
measure the flow of air for purging experiments has an accuracy of ±10 LPM. This
can cause a variation in the airflow while purging the canister. To verify this flow an
anemometer was used to make sure that the airflow was constant.
The weighing scales used to measure the weight of the canister as it is being loaded
or purged are very sensitive. Any small changes to the experimental setup caused a
sudden increase or decrease to the weighing scale and rendering the data collected
60
for that experiment unusable. The pipes that were used to flow gas in and out of the
canisters must be kept stationary and fixed in order to avoid them influencing the
weighing scale. Figure 6.9 shows an experiment where the test setup was disturbed
during purging canister 2. Any changes to the setup can cause a sudden change
in the weighing scale and it may not return to the previous reading corrupting the
experimental data.
Figure 6.9: Canister mass profile with small disturbance during experimental testing
The temperature sensors in the carbon bed are placed in the center of the carbon
bed assuming a perfectly cylindrical carbon shape with equal amounts of activated
carbon on each side of the thermocouple. This assumption may not always be true
as the carbon inside the canister may be shaped differently and the thermocouples
may not always get the accurate average temperature reading of the carbon bed.
61
One way to avoid this inaccuracy is to include more thermocouples to get a better
understanding of the activated carbon bed temperature.
6.2 Model Calibration
Observer design and parameter estimation are used to identify the parameters of
the model which are not directly measurable. A cooldown test is used to estimate
these parameters and calibrate the carbon canister model as explained in chapter 5.
Figure 6.10: Cooldown Experiment Results - Carbon Bed and Skin Temperatures
Figure 6.10 shows the results of a cooldown test conducted on canister #1. The
canister is loaded with butane vapor and once a section of the canister has been
saturated the butane flow into the canister is cut off and the temperature of the
carbon bed and plastic wall is recorded as they cool to ambient temperature.
62
Figure 6.11: Cooldown Experiment - Calibrating dTp /dTC
To determine the rate of change of plastic wall temperature with respect to the
carbon bed, the temperature of the plastic wall is plotted vs the temperature of the
carbon bed as seen on figure 6.11 and a linear approximation of the curve is calculated.
The slope of this curve will give the rate of change of plastic wall temperature with
respect to the carbon bed. From the graph the value of dTp /dTC is estimated to be
0.2078.
Once the value of dTp /dTC is estimated this value can be used in equation (5.8) to
determine the value of heat loss conductance through the walls of the plastic canister.
Equation (5.8) is modeled in MATLAB and different values of Uloss are considered
and the cooldown of the carbon bed temperature is calculated. The value for Uloss
that predicts the carbon bed temperature most accurately is selected as the parameter
63
Figure 6.12: Cooldown Experiment - Calibrating Uloss
value as seen in figure 6.12. From the figure, the best value for Uloss to predict the
carbon bed temperature is 0.05 W/(m2 K).
Once both the parameters have been estimated these values are used in equa-
tion (5.8) to predict the carbon bed temperature for a different cooldown experiment
on canister 1 and 2 (figures 6.13 and 6.14). These figures show that the parame-
ter estimation has been successful and the model is able to predict the carbon bed
temperature with very good accuracy.
64
Figure 6.13: Cooldown Experiment - Validating Calibrated values on Canister #1
Figure 6.14: Cooldown Experiment - Validating Calibrated values on Canister #1
65
6.3 Simulation and Experimental Comparison
Once the parameters of the model are estimated the model is used to predict the
mass of butane vapor that has been adsorbed and desorbed by the activated carbon
bed during the loading and purging experiments. Once the simulations are run the
prediction is compared against experimental values to determine the accuracy of the
model. Since the model is aimed to be used in an automotive ECU to predict the
amount of gasoline vapor inside the carbon canister, an assumption of a uniform
cross-sectional area across the length of the canister is made on the model to reduce
its complexity. The main priority of the model is to predict the mass loading and
purging of the canister and only secondary importance is given to the temperature
of the carbon bed. For the comparison, the simulation and experimental results are
plotted on the same graph and compared.
The experimental results are presented in the solid lines and the simulation results
are presented in the same graph with dotted lines. Since the experimental results
include temperature plots from different sections on the canister the temperature
measurement and predictions have been color-coded for ease of understanding.
6.3.1 Canister Loading
The loading the canister was modeled using equations (3.22) and (3.31). The
canister loading is simulated for both canisters at 50 g/hr loading of n-butane to
match the loading rate of butane in the experimental results.
66
Figure 6.15: Comparison between Simulation and experimental results - Mass profile
Canister #1
Canister #2
67
Figures 6.15 and 6.16 shows the comparison between the model prediction of
the canister mass increase as the canister is being loaded with butane vapor. The
figure shows that the model is able to predict the amount of butane adsorbed on the
activated carbon inside the canister quite accurately. The larger canister #1 is able
to store more butane vapors due to the larger volume and greater amount of activated
carbon inside the canister. Since the adsorption process prefers a cooler environment
the larger canister provides better heat transfer away from the carbon loading sites
and allow for better adsorption inside the carbon bed.
Figure 6.17: Comparison between Simulation and experimental results - Temperature

profile Canister #1
68
profile Canister #2
Figures 6.17 and 6.18 show the comparison between the simulation and experi-
mental results temperature profile of each canister during the loading phase.
The model predicts the homogeneous temperature at each section of the canister.
In the experiments, the thermocouple measures the temperature of the carbon bed
at the axially central position. Due to this, there is a small discrepancy between the
simulation temperature measurement and the experimental measurement. Also, an-
other factor contributing to the different temperature prediction and actual readings
is due to the assumption made in the simulation where the cross-section area of the
canister is assumed to be constant along the length of the carbon bed. This is not
true in the case of both canisters as the cross-sectional area of canister 1 decreases
as we reach the position of thermocouple 4 and 5 and similarly, the cross-sectional
area of canister 2 is smaller at the locations of thermocouples 4 and 5. The small
69
increase in temperature at thermocouple 4 of canister #2 is due to the shape of the
canister. As seen in figure 4.4 once the position of thermocouple 1 is loaded heat is
released and this heat is dissipated in all directions. Since thermocouple 4 is very
close by the carbon bed temperature at thermocouple 4 also increases due to cross
bed conduction. This conduction term has not been included in the simulation model
hence the model does not predict this small increase in carbon bed temperature.
A comparison between the mass and temperature profiles show that the change in
cross-sectional area of the canisters does not have a significant enough change in the
loading rate or the amount of butane adsorbed on the activated carbon. Therefore
the assumption of a uniform cross-sectional area across the carbon bed is justified
and will make the model less complex and easier to use.
6.3.2 Canister Purging
Canister purging was simulated using the equations (3.22) and (3.31) similar to the
loading simulation but for the purging simulation the initial and boundary conditions
of the simulation have been reversed.
Figures 6.19 and 6.20 present the comparison between the simulation prediction
and experimental results of purging the canister at 50 LPM. Similar to canister loading
the model is able to predict the mass loss in both the canisters. The larger canister
#1 has stored a larger amount of butane vapors due to the larger volume of activated
carbon. The larger canister cross-sectional area also allows for faster desorption of
butane vapor from the activated carbon bed as seen in the figures. Once the majority
of the carbon bed has been desorbed the temperature of the carbon bed decreases
70
Canister #1
significantly which creates an unfavorable condition for desorption and therefore the
amount of butane desorbed decreases.
Figures 6.21 and 6.22 present the comparison between the temperature profiles of
the canister as they are being purged of n-butane vapors adsorbed on the activated
carbon bed. The simulation model is able to predict the temperature drop in the
carbon beds fairly accurately.
Similar to the loading phase the simulation model predicts the homogeneous tem-
perature of the carbon bed at each position in the carbon bed and the experiment
results present the carbon bed temperature at the axial center of the carbon bed.
This leads to small variations between the simulation and experimental results. Due
to the assumption of a uniform cross-sectional area the model does not predict the
71
Canister #2
larger drops in carbon bed temperature as well. The thermocouples 2, 3 and 4 in
canister #2 started at a higher temperature than thermocouple 1 and the model has
been adjusted to this starting temperature to get an accurate representation of the
experimental results.
72
profile Canister #1

profile Canister #1
73
Chapter 7: Conclusions
This project investigated and developed a simplified one-dimensional physics-
based model of the automotive evaporative emission activated carbon canister. The
model was simulated in MATLAB and was validated using experimental results on
two activated carbon canisters. The objective of this thesis was to create a model
for the automotive industry that can accurately predict the amount of gasoline va-
por adsorbed and desorbed by the carbon canister during normal stopped vehicle
conditions.
The model predicts the amount of vapor adsorbed on the activated carbon bed
during slow-loading conditions such as a diurnal stopped vehicle. The model is devel-
oped by discretizing the carbon bed into small areas and assuming a local equilibrium
of adsorption in these areas. The model also assumes a local heat source at the car-
bon bed to include the effects of the heat of adsorption released during the loading
of vapor.
The model predicts the amount of vapor desorbed from the activated carbon bed
during normal purging conditions such as engine ignition. Similar to the loading case
the model is discretized and a local heat sink is used to include the effects of the
endothermic desorption process.
74
Experimental results were conducted on two different shaped EVAP carbon can-
isters to validate the model prediction of the amount of vapor adsorbed and desorbed
by the canister during the loading and purging phases. By comparing the experimen-
tal results with the simulation results the model successfully predicted the amount of
vapor adsorbed and desorbed from the activated carbon canister during loading and
purging phases respectively. The main goal of the project was to create a model that
can predict the vapor loading in the carbon canister with a small number of inputs
so that the model can be used for different vehicles by the automotive manufacturer
in the vehicle modeling phase.
Future work in this project can include predicting the vapor loading in the carbon
canister at higher load rates such as Onboard Refueling Vapor Recovery (ORVR)
and validate the model using further experimental results. The model can be further
refined by including two-dimensional thermal effects on the carbon bed. As seen in
the experimental results the temperature of the carbon bed near the plastic wall is
lesser than the temperature of the carbon bed at the center of the canister.
A more accurate model of the carbon canister can be modeled for future work
where loading of gasoline vapor due to diffusion effects and cross-bed heat conduction
are also considered as part of the 2D or 3D canister model.
75
Appendix A: Canister Dimensions for Model
Figures A.2 and A.1 shows the approximation made to the geometry of the canister
#2 and canister #1 respectively while modeling to create a uniform cross-sectional
area across the carbon bed.
76
Figure A.1: Canister #2 geometry and dimensions approximation for model
Figure A.2: Canister #1 geometry and dimensions approximation for model
77
Appendix B: Thermocouple Positioning on Canister
Tables B.1 presents the position of the thermocouples along the length of the
canister bed. The end of the load valve is considered as x=0 and measurements are
taken from this point towards the atmosphere valve of the canister. In the case of
canister #2 the whole bed of the canister is assumed to be in a straight line and
measurements are made accordingly.
Canister # Thermocouple Number Position along Carbon bed (cm)

TC 1 6
TC 2 14
1 TC 3 20
TC 4 30
TC 5 40
TC 1 5
TC 2 18
2
TC 3 23
TC 4 41
Table B.1: Thermocouple Position along Carbon bed for both Canisters
78
Appendix C: MATLAB code to calibrate model
1
2 clc;
3 clear;
4 close all;
5
6 % ETAS output showing the number of samples collected and the ...
data points
7 % corresponding to thermocouple outputs.
8 % sampleCnt = 24985 ;
9 % recordFormat = 'f8 f8 f8 f8 f8 f8 f8 f8 '
10 % time = 1 ;
11 % TC 1qiES650qNqrqNADqrThermoqj1 = 2 ;
16 % SkinTCqiES650qNqrqNADqrThermoqj1 = 7 ;
17 % AmbTqiES650qNqrqNADqrThermoqj1 = 8 ;
18
19 %% data points
20
21 data=data points; % function to load values from data collected ...

by ETAS DAQ
22
23 %% temperature plots
24
25 time2=data(:,1)/60;
26 TC 1=data(:,2);
27 TC 2=data(:,3);
28 TC 3=data(:,4);
29 TC 4=data(:,5);
30 TC 5=data(:,6);
31 skinTC=data(:,7);
32 ambT=data(:,8);
33
34 % plot temperature variation for loading experiment
79
35 figure
36 plot(time2,TC 1,'linewidth',2);
37 hold all
38 grid on
43 plot(time2,skinTC,'linewidth',2);
44 plot(time2,ambT);
45 xlabel('Time [min]')
46 ylabel('Temperature [ôC]');
47 title({'Canister 1';' Temperature Variation during Loading ...
Experiment'});
48 legend('TC1','TC2','TC3','TC4','TC5','skin TC','Ambient');
49 set(gca,'fontsize',15)
50
51 %% weight data points and plots
52
53
54 can m start=2869; % canister start weight

55 can m end=3190; % canister end weight
56
57 % collect mass data
58 data1=xlsread("Experiment 5 weight calculations 061619.xlsx");
59
60 can m=data1(:,2)-can m start; % to measure change in mass

61 time1=data1(:,1);
62
63 % Plot mass profile of canister during loading
64 figure
65 plot(time1,can m,'linewidth',2);
66 grid on;
67 hold all;
68 xlabel('Time [min]');
69 ylabel('Canister Mass [g]');
70 title({'Canister 1';' Mass Variation during Loading Experiment'});
72
73
74
75
76 %% cooldown plots
77
78 % clear;
79 % clc;
80 % close all;
81
82 % to find start point and 1 hour after start
83 temp1=find(TC 1>40,1,'last');
84 temp2=find(time2<time2(temp1)*60+3600,1,'last');
80
85
86 % cooldown plot from experiment
87 figure
88 plot((time2(temp1:temp2)*60)-time2(temp1)*60,TC 1(temp1:temp2),...
89 'linewidth',2);
90 hold all;
91 grid on;
92 plot((time2(temp1:temp2)*60)-time2(temp1)*60,skinTC(temp1:temp2),...
93 'linewidth',2);
94 xlabel('Time [s]');
96 grid on;
98 title('Cooldown Experiment Plots - For Calibration');
99 xlim([0 3600]);
100 ylim([20 50]);
101 legend('TC 1','Skin TC');
102
103 % % to find rate of change of plastic body
104 p=polyfit(TC 1(temp1:temp2),skinTC(temp1:temp2),1);
105 x1=linspace(TC 1(temp1),TC 1(temp2));
106 y1=polyval(p,x1);
107 dT p=p(1);
108
109 figure
110 plot(TC 1(temp1:temp2),skinTC(temp1:temp2));
111 hold all;
112 grid on;
113 plot(x1,y1);
114 xlabel('Carbon Temperature [ôC]');
115 ylabel('Plastic Temperature [ôC]');
117 title({'Cooldown Experiment Plots - For Calibration';'Determine ...
dT p/dT'});
118 legend('Experimental Data','Linear Approximation');
119
120 % canister properties
121 A=99; % Cross sectional area [cmˆ2]
122 % r=sqrt(A/pi); % assuming cylinderical canister, radius [cm]
123 P ext=40; % exterior perimeter at x
124 rho app=0.345; % apparent density of the carbon canister [g/ml]
125 m p=0.5; % mass of plastic to mass of carbon ...
(m plastic/m carbon)
126 C vc=0.7; % specific heat of carbon [kJ/kg/C]
127 C p1=1.6; % specific heat of species 1 [kJ/kg/C]
128 C pp=1.9; % specific heat of plastic wall [kJ/kg/C]
129 k app=0.13; % Apparent thermal conductivity of carbon bed ...
[W/m/C]
130 U loss=13; % Wall-air heat conductance [W/mˆ2/C]
131 m s1=0.35; % adsorbed mass of species 1 [g/gC)
132 dh vap=-0.2; % heat of vaporization [J/g]
81
133 T amb=mean(ambT); % Ambient temperature [C]
134 T0=TC 1(temp1); % Initial ccarbon ...
temperature [C]
135 t=100; % time for simulation
136 % dT p=0.2078;
137 sim('Temperatureparameters model');
138
139 figure
140 plot(time*100,T,'linewidth',2);
141 hold on;
142 plot((time2(temp1:temp2)*60)-time2(temp1)*60,TC 1(temp1:temp2),'--r',...
143 'linewidth',2);
146 grid on;
148
149 title('Plot of experimental cooldown data - Lavoie values');
150 % set(gca,'fontsize',15);
151 xlim([0 3600]);
152 ylim([20 50]);
153 legend('Model','Experiment');
154
155 % changing uloss
156 figure
157 plot((time2(temp1:temp2)*60)-time2(temp1)*60,TC 1(temp1:temp2)...
158 ,'--r','linewidth',2,'DisplayName','Exp data');
159 hold all;
160 for i=1:10
161 U loss=i*0.01;
163
164 % figure
165 plot(time*100,T,'linewidth',1,'DisplayName',num2str(U loss));
166 hold on;
167
168 end
171 grid on;
172 legend('show','fontsize',10,'Orientation','horizontal','NumColumns',2)
173 title({'Cooldown Experiment Plots- For Calibration';'Determine ...
U {loss}'});
174 set(gca,'fontsize',14);
175 xlim([0 3600]);
176 ylim([20 50]);
177
178 % Final plot with correct uloss and dTp
179 U loss=0.045;
180 dT p=0.2078;
82
182
183 figure
184 plot(time*100,T,'linewidth',2);
185 hold on;
186 plot((time2(temp1:temp2)*60)-time2(temp1)*60,TC 1(temp1:temp2),'--r',...
187 'linewidth',2);
190 grid on;
192
193 title({'Cooldown Experiment Plots';'Experiment5- Validation'});
194 set(gca,'fontsize',15);
195 xlim([0 3600]);
196 ylim([20 50]);
197 legend('Model','Experiment');
83
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85

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Modeling and Validation of an Automobile Evaporative

Emission Carbon Canister

Presented in Partial Fulfillment of the Requirements for the Degree

Anoop Sunil, B. Tech

Graduate Program in Mechanical Engineering

The Ohio State University

Master’s Examination Committee:

The automotive carbon canister consists of activated carbon particles designed to

Experiments were conducted using n-butane as the volatile organic compound

developed in MATLAB to predict the canister behavior during these experiments.

amount of fuel available in the canister.

efficient automotive canister.

complete this project.

provided valuable feedback during my project.

at CAR and all the friends I made along the way.

me during the course of my graduate school and helped me complete my degree.

August 11, 1993 . . . . . . . . . . . . . . . . . . . . . . . . . . . . Born - Kerala, India

2011-2015 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . B.Tech. Mechanical Engineering,

2017-present . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . M.S. Mechanical Engineering,

Major Field: Mechanical Engineering

1.1 Problem introduction . . . . . . . . . . . . . . . . . . . . . . . . . 1

2.1 Effect of fuel vapor on environment . . . . . . . . . . . . . . . . . . 6

3.1 Adsorption fundamentals . . . . . . . . . . . . . . . . . . . . . . . 16

4.1 Experimental Setup . . . . . . . . . . . . . . . . . . . . . . . . . . 34

5. Simulation Method and Parameters . . . . . . . . . . . . . . . . . . . . . 46

5.1 Method of solution . . . . . . . . . . . . . . . . . . . . . . . . . . . 46

6. Result and Discussions . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52

6.1 Experimental results . . . . . . . . . . . . . . . . . . . . . . . . . . 52

A. Canister Dimensions for Model . . . . . . . . . . . . . . . . . . . . . . . 76

B. Thermocouple Positioning on Canister . . . . . . . . . . . . . . . . . . . 78

C. MATLAB code to calibrate model . . . . . . . . . . . . . . . . . . . . . . 79

3.1 Adsorption Isotherm curve-fit parameters . . . . . . . . . . . . . . . . 25

3.2 Antoine equation coefficients for n-Butane . . . . . . . . . . . . . . . 28

4.1 n-Butane and Nitrogen Mixture Gas cylinder Composition . . . . . . 41

5.1 Physical Properties of carbon bed and other Model Parameters . . . . 49

5.2 Canister Geometric Properties . . . . . . . . . . . . . . . . . . . . . . 50

B.1 Thermocouple Position along Carbon bed for both Canisters . . . . . 78

2.1 A simplified schematic representation of the Fuel EVAP system . . . 8

2.2 Schematic diagram of a commonly used activated carbon canister . . 8

2.3 Approximate flowchart of vapor flow during loading process . . . . . . 10

2.4 Approximate flowchart of vapor flow during purging process . . . . . 11

4.1 Schematic Diagram of Canister 1 . . . . . . . . . . . . . . . . . . . . 35

4.2 Schematic Diagram of Canister 2 . . . . . . . . . . . . . . . . . . . . 35

4.3 Thermocouple positions on canister 1 . . . . . . . . . . . . . . . . . . 37

4.4 Thermocouple positions on canister 2 . . . . . . . . . . . . . . . . . . 37

4.5 Rotameter used to Measure Vapor volumetric flow rate . . . . . . . . 38

4.6 Schematic Diagram of the Canister loading experiment setup . . . . . 39

4.7 Schematic Diagram of the Canister Purging experiment setup . . . . 40

4.8 Experimental setup for loading experiments . . . . . . . . . . . . . . 43

4.9 Experimental setup for Purging experiments . . . . . . . . . . . . . . 44

6.1 Canister #1 Mass Profile during Loading Experiment . . . . . . . . . 53

6.3 Canister #2 Mass Profile during Loading Experiment . . . . . . . . . 55

6.4 Canister #2 Mass Profile during Loading Experiment . . . . . . . . . 56

6.5 Canister #1 Mass Profile during Purging Experiment . . . . . . . . . 57

6.6 Canister #1 Temperature Profile during Purging Experiment . . . . . 58

6.7 Canister #2 Mass Profile during Purging Experiment . . . . . . . . . 59

6.8 Canister #2 Temperature Profile during Purging Experiment . . . . . 60

6.10 Cooldown Experiment Results - Carbon Bed and Skin Temperatures 62

6.11 Cooldown Experiment - Calibrating dTp /dTC . . . . . . . . . . . . . . 63

6.12 Cooldown Experiment - Calibrating Uloss . . . . . . . . . . . . . . . . 64