ABSTRACT
This
research was carried out in order to alleviate the issues on depleting crude
oil reserves and environmental pollution by finding replacement for fossil fuel
in Nigeria. A promising way of doing this is, the production of biofuels such
as biodiesel, whose major by-product is glycerol (10% of biodiesel produced).
The by-product, glycerol, is not presently useful for any other thing, so it
will be wise to also convert it into useful energy such as hydrogen production
via reforming. The research uses pinch technology as a technique in conserving
energy in the glycerol reforming process for hydrogen production. The pinch
analysis was carried out on 3 methods of reforming namely: Aqueous phase
reforming, Steam reforming, and Auto thermal reforming. The result obtained
showed that the unit production cost ($/kmol) of H2 is 31.69 before
integration and 29.56 after integration for APR, 48.7 before integration and
36.87 after integration for SR, but the ATR showed no significant difference in
production cost before and after integration with a cost of 30.26 before and
30.06 after. Energy recovered from APR is 29, 820kW (86%) and 37,400kW (69%)
from SR and 11,559kW (68%) from ATR. This energy saving reduced the operating
cost by 92% for APR, 75% for SR and 76% for ATR, but an increased capital cost
was incurred as a result of the additional heat exchangers that were required
to achieve energy recovery. The break even analysis showed that the additional
capital cost incurred due to the additional heat exchangers would be gained
back from the savings made from the operating cost over the break even period.
The APR break even period is 0.333years with 0.131years and 0.92 years for SR
and ATR respectively.
TABLE OF CONTENTS
PAGES
Title
Page
Title Page ii
Certification iii
Letter
of Transmittal iv
Dedication v
Acknowledgment vi
Abstract vii
Table of Content ix
List of Tables x
List of
Figures xi
Nomenclature xii
CHAPTER ONE: INTRODUCTION
1.1
Background and Motivation 1
1.2
Research Objectives 2
1.3 Scope
of Study 3
1.4 Relevance
of study 3
CHAPTER TWO: LITERATURE REVIEW
2.1
Introduction 4
2.2
Hydrogen 4
2.2.1Methods of Hydrogen Production 5
2.3 Biofuel
Production 7
2.3.1 Glycerol 8
2.3.2 Properties of Glycerol 10
2.4
Reforming Techniques 12
2.4.1 Steam
Reforming. 15
2.4.2 Supercritical Water Reforming 16
2.4.3 Partial oxidation Reforming 17
2.4.4 Auto thermal Reforming 18
2.4.5 Aqueous Phase Reforming 18
2.5
Catalysis 20
2.6
Process Integration 23
2.6.1 Fundamentals of Pinch Study 25
2.6.2 Steps in carrying out pinch
analysis 25
2.7
Costing 32
2.7.1 Factorial Method 32
2.7.2 Heat Exchanger Cost 33
2.7.3 Variable Cost and Fixed Cost 33
CHAPTER THREE: METHODOLOGY
3.1
Introduction
3.2 Process
Description
3.3 Process
Simulation
3.4 Energy
Integration
3.5 Cost
Evaluation
CHAPTER FOUR:
RESULT AND DISCUSSION
4.1
Aqueous Phase Reforming. 41
4.1.1 Pinch Analysis for APR 41
4.1.2 Cost Evaluation of Base APR
Case 44
4.1.3 Cost Evaluation of Integrated
APR Case 47
4.1.4 Break Even Analysis for APR 48
4.2 Steam
Reforming 49
4.2.1 Pinch Analysis for SR 49
4.2.2 Cost Evaluation of Base SR
Case 52
4.2.3 Break Even Analysis for SR 54
4.2.4 Break Even Analysis for SR 55
4.3 Auto
thermal Reforming 56
4.3.1 Pinch Analysis for ATR 56
4.3.2 Cost Evaluation of ATR Base
Case 58
4.3.3 Cost Evaluation of Integrated
ATR Case 61
4.3.4 Break Even Analysis for ATR 61
4.4
Discussion of Results 62
CHAPTER FIVE: CONCLUSION AND RECOMMENDATION
5.1 Conclusion 64
5.2
Recommendation 64
APPENDIX 65
REFERENCES 75
LIST OF TABLES
Tab 2.1: Composition of glycerol before
and after acid washing
Tab 2.2: Common operating conditions and
result of different method of glycerol
reforming (Silvey, 2011)
Tab 2.3: Conversion over different
catalyst type
Tab 2.4: Experience DTmin values ( Mondal et al, 2013)
Tab 2.5: Typical factors for fixed
capital cost estimation (extract from Coulson and
Richardson, 1993)
Tab 2.6: Summary of production cost
(extract from Coulson and Richardson, 1999
Vol 6)
Tab 3.1: Composition of crude glycerol
Tab 4.1: Composition of glycerol before
and after pretreatment
Tab 4.2: Process stream Data
Tab 4.3: Energy Targets for APR
Tab 4.4: Heat exchanger summary for APR
Tab 4.5: Raw material specification
Tab 4.6: Equipment cost for APR
Tab 4.7: Fixed operating cost for APR
Tab 4.8: Utility rates and cost for APR
Tab 4.9: Total production cost for base
and integrated case for APR
Tab 4.10: Process stream Data for SR
Tab 4.11: Energy Targets for SR
Tab 4.12: Heat Exchanger summary for SR
Tab 4.13: Equipment cost for SR
Tab 4.14: Fixed operating cost for SR
Tab 4.15: Utility rate and cost for SR
Tab4.16: Production cost for both SR
cases
Tab 4.17: Stream Data for ATR
Tab 4.18: Energy Targets and savings for
ATR
Tab 4.19: HEN Summary
Tab 4.20: Cost of equipment for ATR
Tab 4.21: Fixed operating cost for ATR
Tab 4.22: Utility rate and cost for ATR
Tab 4.23: Production cost for both ATR
cases
LIST OF FIGURES
Fig 2.1: Rate of bio diesel
production
Fig 2.2: Derivatives of glycerol
Fig 2.3: A schematics of a typical
reforming process
Fig 2.4: Catalytic activities of
metals for; rate of C-C bond breaking (grey), water gas-shift reaction (white),
methanation reaction (black).
Fig 2.5: Typical composite curve
Fig 2.6: Typical heat cascade diagram
Fig 3.1: Crude glycerol pre-treatment
Fig 3.2: Aqueous phase glycerol
reforming
Fig 3.3: Steam Reforming
Fig 3.4: Autothermal Reforming
Fig 4.1: APR Optimum plot DTmin
Fig 4.2: Composite curve for APR
Fig 4.3: GCC for APR
Fig 4.4: Optimum DTmin for
SR
Fig 4.5: Composite curve for SR
Fig 4.6: Grand composite curve for SR
Fig 4.7: Optimum DTmin
for ATR
Fig 4.8: Composite curve for ATR
Fig 4.9: Grand composite curve for
ATR
NOMENCLATURE
|
DTmin
|
Minimum
Temperature Difference
|
|
CP
|
Heat
capacity flowrate
|
|
Ts
|
Supply
Temperature
|
|
Tt
|
Target
Temperature
|
|
Qhmin
|
Hot
utility requirement
|
|
Qcmin
|
Cold
utility requirement
|
|
CC
|
Composite
curve
|
|
GCC
|
Grand
composite curve
|
|
CPh
|
Hot
stream heat capacity flowrate
|
|
CPc
|
Cold
stream heat capacity flowrate
|
|
APR
|
Aqueous
Phase Reforming
|
|
SR
|
Steam
Reforming
|
|
ATR
|
Auto
Thermal Reforming
|
CHAPTER ONE
INTRODUCTION
1.1
Background and Motivation
The search and increasing demand for renewable and
sustainable clean energy source due to the diminishing crude oil reserves and
concern on environmental pollution has led to the various researches on
alternatives such as biomass derived fuel and hydrogen, which would be cheaper,
efficient and causing less pollution. As
a result, new technologies requiring the use of renewable feedstock have been
the focus of intense process development within the past few decade. Renewable
feed stocks derived from biomass is been used in production of fuel and
presently about 2% of diesel used in the
United State is produced from biomass,
although these biomass derived fuel cannot compete economically with fossil
fuel.
Hydrogen on the other hand is one of
the most attractive form of energy because it is efficient, renewable, and a
clean energy source. Combustion of hydrogen produces heat and water only, it
does not produce greenhouse gases. Although, hydrogen can be produced using
different methods which will be discussed later, for this research we are
looking at hydrogen production from glycerol reforming.
Why the choice of
glycerol?
As earlier stated, the search for
alternative energy sources has led to the advancement in the biofuel technology
and an increased production of biodiesel from biomass. This advancement has
also led to an increase in glycerol production since it is a major by-
product of biodiesel production (10%
per unit mass of total biodiesel produced). Although glycerol has been useful
in other industries such as; food, beverages, body care, pharmaceutical etc.,
its rate of production is far greater than the demand for it in these
industries. For this reasons, there is a need to develop other uses for
glycerol. One of the ways of putting glycerol to good and profitable use in the
bio-fuel industry is the production of hydrogen (fuel) from glycerol through
reforming.
For the past 2 decade, the major and
most cost effective method for hydrogen production was the reforming of
hydrocarbon specifically natural gas, but with the new development natural gas
will be replaced with oxygenated
hydrocarbon (glycerol) which is preferable because; it is from a
renewable source, it avoid waste of burning natural gas (a fuel) from
non-renewable sources to produce hydrogen
(another fuel) and also provides an avenue for putting the byproduct of
the biodiesel production to good and effective use.
1.2
Research Objectives
The research objectives are as follows;
1.
Optimize hydrogen
production from renewable energy sources
2.
To
develop a cost effective method for hydrogen production from glycerol thereby
improving the overall economy of the biodiesel production.
3.
Integrating
energy in the glycerol reforming process to minimize hydrogen production cost
over a period of time.
1.3 Scope of Study
• Aqueous phase
glycerol reforming process design simulation using software.
•
SR
process design simulation
•
ATR
process design simulation
•
Heat
integration of the process by designing heat exchange networks using pinch
analysis.
1.4 Relevance of study
Nigeria
presently has a policy on biofuels titled Nigerian Biofuel Policy and
Incentives (2007) which was approved by the Federal Executive Council in 2007.
This policy aims at developing the
biofuel production in Nigeria which will
start by the importation of biodiesel and then blending with automotive gas
oil(AGO) at a 20 % ratio also known as B-20. These blends are to be
used in automobiles for a period of three years and by 2015 local production of
biodiesel will be used rather than imports.
A biofuel production programme has been put in place to
achieve 100% domestic production by 2020. (Nigerian biofuel policy and incentives 2007)
A
900 million litre production of biodiesel has been estimated by the year 2020,
with this rate of production, the amount of the byproduct glycerol that will be
produced will be about 90 million litres/133.4millionkg (10% of bio-diesel produced) that could be
diverted for hydrogen production by reforming.
In 2003, the Federal Executive
Council (FEC) approved a National Energy Policy (NEP), which articulates the
use of all viable energy sources in Nigeria, in order to diversify the energy
supply mix of the country for enhanced energy security, and provisions has been
made to include hydrogen as an energy source in the energy mix for the country.
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