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Product Code: 00002614

No of Pages: 84

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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.





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




1.1 Background and Motivation                                                                            1

1.2 Research Objectives                                                                                         2

1.3 Scope of Study                                                                                                   3

1.4 Relevance of study                                                                                            3                                                                                             



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




3.1 Introduction

3.2 Process Description

3.3 Process Simulation

3.4 Energy Integration

3.5 Cost Evaluation



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




5.1 Conclusion                                                                                                         64

5.2 Recommendation                                                                                               64


APPENDIX                                                                                                               65

REFERENCES                                                                                                        75


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



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



Minimum Temperature Difference


Heat capacity flowrate


Supply Temperature


Target Temperature


Hot utility requirement


Cold utility requirement


Composite curve


Grand composite curve


Hot stream heat capacity flowrate


Cold stream heat capacity flowrate


Aqueous Phase Reforming


Steam Reforming


Auto Thermal Reforming






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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