Dr. Sadaf Siddiq 08F UET PHD ME 47

PhD Thesis
OPTIMAL PERFORMANCE ANALYSIS OF A SOLAR

THERMAL ENERGY STORAGE PLANT BASED ON
LIQUID AMMONIA
Submitted by
Engr. Sadaf Siddiq
(08F-UET/PhD-ME-47)
Supervised by
Prof. Dr. Shahab Khushnood
Department of Mechanical Engineering

Faculty of Mechanical and Aeronautical Engineering
University of Engineering and Technology
Taxila, Pakistan
July 2013
OPTIMAL PERFORMANCE ANALYSIS OF A SOLAR

THERMAL ENERGY STORAGE PLANT BASED ON
LIQUID AMMONIA
by
Engr. Sadaf Siddiq
(08F-UET/PhD-ME-47)
A proposal submitted for research leading to the degree of Doctor of Philosophy

in
MECHANICAL ENGINEERING
Approved by
External Examiners
________________________________
(Engr. Dr. M. Javed Hyder)
Dean of Engineering,
________________________________
(Engr. Dr. Ejaz M. Shahid)
Associate Professor,
Pakistan Institute of Engineering & Applied Sciences

Nilore, Islamabad.
Department of Mechanical Engineering,

University of Engineering & Technology, Lahore.
Internal Examiner (Research Supervisor)

________________________________
(Engr. Dr. Shahab Khushnood)
Professor,
Department of Mechanical Engineering,
University of Engineering & Technology, Taxila.

University of Engineering & Technology
Taxila, Pakistan.
ii
DECLARATION
I declare that all material in this thesis is my own work and that which is not, has been
identified and appropriately referenced. No material in this work has been submitted or
approved for the award of a degree by this or any other university.
Signature: _____________________________
Authors Name: ________________________
It is certified that the work in this thesis is carried out and completed under my supervision.
Supervisor:
Prof. Dr. Shahab Khushnood
University of Engineering and Technology
Taxila, Pakistan.
iii
ABSTRACT
This work focuses on extending the use of a solar thermal energy plant from an intermittent
energy source to a base load power plant by incorporating an efficient thermal storage feature.
A reference 10 MWe solar thermal plant design is considered with liquid ammonia as a
working fluid for energy production, in a Rankine Cycle, as well as a thermal storage
medium. During periods of no solar insolence, the recovery system, based on an industrial
ammonia synthesis system, is used to drive the power conversion unit and enable continuous
operation.
A thermofluid model, based on the continuity, momentum and energy conservation equations,
is used to carry out a numerical simulation of the plant, to determine the process variables
and subsequently carry out an integrated plant energy recovery analysis. The objective of this
work is to maximize the efficiency of the plant by a detailed consideration of the most critical
process in the plant: the energy recovery unit. This is carried out by (i) estimating the
sensitivity of non-uniform catalyst concentration in a synthesis reactor, and (ii) obtaining an
optimal configuration from a variational Lagrangian cost functional and applying
Pontryagins Maximum Principle. The optimal configuration is used to recommend a redesign of the synthesis reactor and to quantify the energy recovery benefits emanating from
such a recommendation. Industrial optimal configurations are achieved by carrying out the
analysis with the simulation code, Aspen Plus, to design a heat removal system
surrounding the catalyst beds, and incorporating the effect of standard industrial processes
iv
such as purge gas removal, quench gas recycling, and recycle ratio to achieve the optimal
temperature profile obtained for the synthesis reactor considered in this work.
This work quantifies the maximum energy recovery in a base-load solar thermal plant
utilizing the existing environment of chemical process industry. It is concluded that a onedimensional model, with mass and energy conservation equations using the Temkin-Pyzhev
activity and pressure-based kinetics rate expressions, predicted an optimal ammonia
conversion of 0.2137 with a thermal energy availability of 20 MWth. A comprehensive
process simulation using Aspen Plus predicts an optimal ammonia conversion of 0.2762
mole fraction at exit, with two inter-bed heat exchangers having optimal temperature drops of
205K and 95K respectively, and yielding a thermal availability of 45.6 MWth. The thermal
energy availability of a base-load solar thermal plant can be increased by 15% in the
ammonia conversion and over 25% in thermal energy availability for energy recovery.
To my family . . .
vi
ACKNOWLEDGEMENTS
During the development of my PhD studies at University of Engineering & Technology
Taxila, several persons and institutions collaborated directly and indirectly with my research.
Without their support it would be impossible for me to finish my work. That is why I wish to
dedicate this section to recognize their support.
I want to start expressing a sincere acknowledgement to my advisor, Prof. Dr. Shahab
Khushnood because he gave me the opportunity to research under his kind guidance and
supervision. I received motivation; encouragement and support from him during all my
studies. I owe Special thanks to Dr. Zafar Ullah Koreshi for the his support, guidance, and
transmitted knowledge for the completion of my work. With him, I have learned writing
papers for conferences and journals and sharing my ideas with the scientific community. I
also want to thank the example, motivation, inspiration and support I received from Dr.
Tasneem M. Shah, Dr. Arshad H. Qureshi and Dr. M. Bilal Khan.
The Grant from University of Engineering & Technology Taxila provided the funding and
resources for the development of this research and validation of my work. At last, but the
most important I would like to thank my family, for their unconditional support, inspiration,
love and prayers.
vii
NOMENCLATURE
A
Cross-sectional area (m2)
ANU
Austrailian National University
Cp
Specific heat at constant pressure (kJ kmol-1 K-1)
Cr
Compression Ratio
CSP
Concentrating Solar Power
Activation energy (kJ kmol-1)
Ff s
Force (external, fluid to solid)
FN0
Initial nitrogen molar flow rate (kmol h-1)
Gt
Giga-ton (109 ton)
Hamiltonian
Enthalpy per unit mass
Functional
J i , J i*
Molar Fluxes
Kinetic Energy
Ka
Equilibrium constant
KBR
Kellogg Brown and Root
Length of synthesis reactor (m)
MTD
Metric tonnes per day
Mtoe
Million ton of oil equivalent
MWe
Megawatt electric
MWth
Megawatt thermal
OEM
One Equation Model
Pressure (MPa)
Linear Momentum
PMP
Pontryagins Maximum Principle
PV
PhotoVoltaic
Heat
viii
Universal gas constant 8.3144 kJ kmol-1 K-1
RA
Reaction rate (kmol NH3 h-1 m-3 catalyst)
RK-4
4th order Runge-Kutta
Surface Area (m2)
Temperature (K)
TEM
Two Equation Model
TSP
Thermal Storage Plant
TWh
Terawatt-hours (1012 Watt-hrs)
Internal Energy (kJ)
Internal Energy per unit mass
Watts
ai
Activity for specie i
Total Molar Concentration
ci
Molar Concentration of Specie i
dp
Particle Diameter
Gravitational acceleration (9.81 ms-2)
ji , ji*
Mass Fluxes
kWe
kilowatt Electric
kWchem.
kilowatt chemical
kWth
kilowatt thermal
Mass (kg)
ni0
Initial mole flow rate of specie i (kmol h-1)
ppm
Parts per million
Molar Production
Time
Control variable
Velocity (m s-1)
Work
Distance along catalyst bed (m)
ix
Normalized Distance along catalyst bed (m)
yi
Mole fraction for specie i
yi
z, z N
Initial Mole fraction for specie i

Fractional conversion of Nitrogen
Greek
H r
Heat of reaction (kJ kmol-1 NH3)
Extent of reaction
Potential Energy
Fugacity coefficient for specie i
Mass Flow Rate (kghr-1)

Shear Stress
Catalyst effectiveness factor
The void space of the bed
Lagrange multiplier
(x)
Catalyst spatial factor
(x)
Optimal Temperature
Density (kg m-3)
Vector containing state variables
Subscripts
eqm
Equilibrium
Species in a multi component system, i =1,2,3,4,....N
opt
Optimal
Isentropic
tot
Total amount of entity in a macroscopic system
Evaluated at a surface
1,2
Evaluated at cross sections 1 and 2
Table of Contents
ABSTRACT ....................................................................................................................................................... IV
ACKNOWLEDGEMENTS ............................................................................................................................ VII
NOMENCLATURE ...................................................................................................................................... VIII
TABLE OF CONTENTS .................................................................................................................................. XI
TABLE LIST ................................................................................................................................................... XIII
FIGURE LIST ................................................................................................................................................ XIV
1
INTRODUCTION .....................................................................................................................................1
1.1 SOLAR ENERGY: POTENTIAL AS A RENEWABLE ENERGY SOURCE ............................................................2
1.2 SOLAR POWER PLANTS IN OPERATION ......................................................................................................5
1.2.1
PV Plants ........................................................................................................................................5
1.2.2
Solar Thermal Plants ......................................................................................................................7
1.3 THERMAL ENERGY STORAGE REQUIREMENT............................................................................................9
1.4 THERMAL STORAGE MATERIALS ..............................................................................................................9
1.5 USE OF LIQUID AMMONIA AS STORAGE MATERIAL ................................................................................ 11
1.5.1
Poperties of Liquid Ammonia ....................................................................................................... 12
1.5.2
Dissociation and Synthesis of Ammonia ....................................................................................... 12
1.5.3
Commercial uses of Ammonia ...................................................................................................... 13
1.5.4
Industrial proprietary processes for Ammonia Production .......................................................... 14
1.5.4.1
1.5.4.2
1.5.4.3
1.5.4.4
1.5.4.5
1.6
1.7
1.8
1.9
1.10
2
Haldor Topsoe Ammonia Synthesis Process ........................................................................................... 15

Kellog Brown & Roots (KBR) Advanced Ammonia Process (KAPP).................................................... 15
Krupp Uhde GmbH Ammonia Process ................................................................................................... 16
ICI-Leading Concept Ammonia (LCA) Process...................................................................................... 17
The Linde Ammonia Concept (LAC) Ammonia (LCA) Process ............................................................ 17
THERMODYNAMIC CYCLES FOR SOLAR THERMAL POWER PLANTS ........................................................ 18

LITERATURE REVIEW .............................................................................................................................. 19
THESIS MOTIVATION............................................................................................................................... 22
OBJECTIVES ............................................................................................................................................ 23
SUMMARY OF FOLLOWING CHAPTERS ............................................................................................... 24
DESCRIPTION OF THE THERMAL STORAGE PLANT .............................................................. 25

2.1 PLANT FEATURES.................................................................................................................................... 25
2.1.1
Process Design ............................................................................................................................. 25
2.1.2
Opertational Parameters .............................................................................................................. 27
2.2 OVERALL PLANT LAYOUT AND DESCRIPTION ......................................................................................... 28
2.2.1
Ammonia Dissociation .................................................................................................................. 29
2.2.2
Ammonia Synthesis ....................................................................................................................... 30
2.2.3
Syn Gas and Ammonia Storage .................................................................................................... 31
2.2.4
Heat Exchangers and Transport Piping ....................................................................................... 31
2.2.5
Compressors and Pumps .............................................................................................................. 31
2.3 THERMAL STORAGE PLANT PROCESS FLOW DIAGRAM ........................................................................... 32
MODELLING & SIMULATION OF THERMAL STORAGE PLANT .......................................... 34

3.1 MATHEMATICAL MODELLING .............................................................................................................. 34
3.1.1
Review of Mathematical Models of TSP ....................................................................................... 34
3.1.2
Mathematical Models for TSP ...................................................................................................... 41
xi
3.1.2.1
3.1.2.2
TEM Model using Activity based Temkin-Pyzhev Form (TP-A): .......................................................... 43

TEM Model using Partial Pressure based Temkin-Pyzhev Form (TP-B): ............................................... 45
3.2 MODELING UNIT OPERATIONS ................................................................................................................ 48

3.2.1
Dissociation Reactor .................................................................................................................... 48
3.2.2
Synthesis Reactor-Aspen Plus Model............................................................................................ 51
3.2.3
Synthesis Reactor- HYSYS Model ................................................................................................. 53
3.2.4
Flash Tank .................................................................................................................................... 55
3.2.5
Purge Gas & Recycle.................................................................................................................... 56
3.2.6
Heat Exchangers and Waste Heat Recovery................................................................................. 57
3.2.6.1
3.2.6.2
3.2.6.3
3.3
3.4
4
Counter Flow Heat Exchanger (CF-HX): ................................................................................................ 57

Thermal Heat Exchanger (SRIN-HX): .................................................................................................... 58
Thermal Heat Exchanger (SROUT-HX): ................................................................................................ 58
MODELING THE INTEGRATED PLANT ...................................................................................................... 59

TWO EQUATION MODEL (TEM) VALIDATION: ....................................................................................... 59
PLANT OPTIMIZATION...................................................................................................................... 62
4.1 REVIEW OF OPTIMIZATION TECHNIQUES ............................................................................................. 62
4.2 OPTIMAL ANALYSIS USING VARIATIONAL CALCULUS ........................................................................ 72
4.3 PARAMETRIC SENSITIVITY ANALYSIS .................................................................................................... 78
4.3.1
Effect of Temperature on Dissociation ......................................................................................... 78
4.3.2
Effect of Flow Rate on Dissociation ............................................................................................. 79
4.3.3
Effect of Pressure on Synthesis ..................................................................................................... 80
4.3.4
Effect of Temperature on Synthesis .............................................................................................. 80
4.3.5
Effect of Flash Temperature on Liquid Ammonia Separation ...................................................... 82
4.3.6
Effect of Purge Fraction on Ammonia Liquification .................................................................... 83
4.3.7
Effect of Recycle Stream on Synthesis .......................................................................................... 84
AN OPTIMAL STORAGE PLANT ...................................................................................................... 85

5.1 PROCESS MODIFICATIONS ..................................................................................................................... 85
5.1.1
Optimal Analysis Problem Formulation- Process Modifications ................................................. 85
5.1.2
OEM using Activity based Temkin-Pehzev form (OEM-TPA) ...................................................... 86
5.1.3
OEM using Partial Pressure based Temkin-Pehzev form (OEM-TPB) ........................................ 89
5.1.4
Process Modifications Validation: ............................................................................................... 94
5.2 DESIGN MODIFICATIONS ....................................................................................................................... 97
5.2.1
The Proposed Design .................................................................................................................... 99
5.2.2
Design Modifications Validation: ............................................................................................... 101
CONCLUSIONS AND FUTURE WORK ......................................................................................... 103
REFERENCES .................................................................................................................................................. 106

APPENDIX A.
AMMONIA 3D PHASE DIAGRAMS ...................................................................... 121
APPENDIX B
MATLAB PROGRAMS FOR AMMONIA SIMULATION ............................... 122
APPENDIX B1: MATLAB PROGRAM FOR OUTPUT OF STEADY STATE SYNTHESIS REACTOR ....................... 123
APPENDIX B2: MATLAB PROGRAM FOR FINDING EQUILIBRIUM CONCENTRATIONS ................................... 149
APPENDIX B3: MATLAB PROGRAM FOR FINDING OUTPUT OF COUNTER-FLOW SYNTHESIS REACTOR....... 153
APPENDIX B4: MATLAB PROGRAM FOR FINDING OUTPUT OF STEADY STATE SYNTHESIS REACTOR WITH 3
CATALYST ZONES .......................................................................................................................................... 157
xii
Table List
Tables
Page
TABLE 1.1: Worlds Largest (25MWe or above) PV Plants in Operation .............................. 6

TABLE 1.2: Solar Themal Plants in Operation ........................................................................ 7
TABLE 1.3: Haldor Topsoe Ammonia Converter Features ................................................... 15
TABLE 2.1: Overall Plant Design for a 10 MW(e) Baseload Plant ....................................... 26
TABLE 3.1: Equations of change of Multi-component Mixtures in terms of the Molecular
Fluxes .............................................................................................................................. 35
TABLE 3.2: Coefficients of the correction factor polynomial in terms of pressure .............. 38
TABLE 3.3: Input Data for Dissociation Reactor .................................................................. 49
TABLE 3.4: Input Data for Synthesis Reactor ....................................................................... 51
TABLE 3.5: Reaction Input for Temkin-Pyzhev Power-Law Expression in Aspen Plus .. 52
TABLE 3.6: Flash Tank Output.............................................................................................. 56
TABLE 3.7: Molar Flow Rates of Components in and out of Splitter ................................... 56
TABLE 3.8: Percentage errors in 1-D Models compared with HYSYS and Aspen Plus61
TABLE 4.1: Optimal solution for the exit conditions ............................................................ 67
xiii
Figure List
Figures
Page
Figure 1.1 Volume Reduction with Phase Change Materials ................................................. 10

Figure 1.2 Materials for medium and high heat storage ......................................................... 10
Figure 1.3 Energy densities for different energy carriers ....................................................... 12
Figure 2.1: Thermal Storage Plant Schematic ........................................................................ 29
Figure 2.2: Array of 400 m2 Paraboloidal Solar Collectors [3] .............................................. 30
Figure 2.3: TSP Process Flow Diagram .................................................................................. 32
Figure 3.1 : Conversion of Nitrogen along a single-bed catalyst ........................................... 39
Figure 3.2 : Syngas temperature in converter ......................................................................... 39
Figure 3.3 : Molar flow rate in converter ................................................................................ 40
Figure 3.4 : Syngas compression requirement ........................................................................ 40
Figure 3.5 : 3-Bed Homogeneous Reactor with TP-A Kinetics ............................................. 45
Figure 3.6 : 3-Bed Homogeneous Reactor with TP-B Kinetics .............................................. 47
Figure 3.7 : PFR Dissociation Reactor in Aspen Plus ........................................................ 49
Figure 3.8 : Dissociation Reactor Exit Composition .............................................................. 50
Figure 3.9 : Dissociation Reactor Temperature Profile .......................................................... 50
Figure 3.10 : PFR Synthesis Reactor in Aspen Plus ........................................................... 51
Figure 3.11 : Synthesis Reactor Exit Composition (Aspen Plus) ....................................... 52
Figure 3.12 : Synthesis Reactor Temperature Profile (Aspen Plus) ................................... 53
Figure 3.13 : Plug Flow Reactor in HYSYS ....................................................................... 53
Figure 3.14 : Synthesis Reactor Temperature Profile (HYSYS) ........................................ 54
Figure 3.15 : Synthesis Reactor Exit Composition (HYSYS) ............................................ 55
Figure 3.16 : Flash Tank in Aspen Plus .............................................................................. 55
Figure 3.17 : Splitter in Aspen Plus .................................................................................... 56
Figure 3.18 : Mixer in Aspen Plus ...................................................................................... 57
Figure 3.19 : Counter Flow Heat Exchanger (CF-HX)........................................................... 57
Figure 3.20 : Thermal Heat Exchanger (SRIN-HX) ............................................................... 58
Figure 3.21 : Thermal Heat Exchanger (SROUT-HX) ........................................................... 58
Figure 3.22 : Integrated Plant.................................................................................................. 59
Figure 3.23 : Comparison of 1-D (TP-B) model, HYSYS, and Aspen Plus results ....... 60
Figure 4.1 : Optimization Process ........................................................................................... 63
Figure 4.2 : Mathematical Methodology to solve governing equations ................................. 64
Figure 4.3 : Counter-Flow Ammonia Synthesis Reactor ........................................................ 66
Figure 4.4 : Temperature & Concentration Profiles along Converter Length ........................ 66
Figure 4.5 : GA Search Algorithm .......................................................................................... 67
Figure 4.6 : Four-Bed Synthesis Reactor ................................................................................ 68
Figure 4.7 : Effect of Quench gas on conversion efficiency................................................... 69
Figure 4.8 : GA Algorithm for obtaining optimal temperature distribution ........................... 70
xiv
Figure 4.9 : Optimal and Normal Ammonia Production Rates .............................................. 71

Figure 4.10 : Optimal and Normal Nitrogen Conversion and Reaction rates ......................... 71
Figure 4.11 : Effect of Temperature on Dissociation ............................................................. 79
Figure 4.12 : Effect of Flow Rate on Dissociation ................................................................. 79
Figure 4.13 : Effect of Pressure on Synthesis ......................................................................... 80
Figure 4.14 : Effect of Temperature on Synthesis .................................................................. 81
Figure 4.15 :Temperature & Pressure Parametric Sensitivity for Synthesis .......................... 81
Figure 4.16 :Effect of Flash Temperature on Ammonia Flow Rate ....................................... 82
Figure 4.17 :Effect of Flash Temperature on Ammonia Mole Fraction ................................. 83
Figure 4.18 :Effect of Purge Fraction on Ammonia Liquification ......................................... 83
Figure 5.1 : Homogeneous reactor with 1-D Model (TEM-TPA) showing gas temperature T ,
equilibrium temperature Teqm , and optimal temeprature Topt ............................................ 87
Figure 5.2 : Temperature in homogeneous reactor compared with one-equation optimal
temperature Topt and equilibrium temperature Teqm . ......................................................... 91
Figure 5.3 : Homogeneous reactor: (a) ammonia mole fraction, (b) temperature profile, and (c)
hydrogen/nitrogen/ammonia mole fractions. .................................................................. 92
Figure 5.4 : Homogeneous reactor with OEM-TPA, showing gas temperature T , equilibrium
temperature Teqm , and optimal temperature Topt . .............................................................. 93
Figure 5.5 : The Proposed Energy Recovery Plant with Process Modifications ................... 93
Figure 5.6 : PFR reactor beds with cooling between beds 1 and 2 ......................................... 94
Figure 5.7 : PFR reactor beds with cooling between beds ...................................................... 95
Figure 5.8 : Effect of temperature drop in the inter-bed heat exchanger, after the first bed, on
the ammonia mole fraction at reactor outlet. .................................................................. 95
Figure 5.9 : Effect of temperature drop in the inter-bed heat exchangers, after the first and
second beds, on the ammonia mole fraction at reactor outlet. ........................................ 96
Figure 5.10 : Homogeneous reactor: Nitrogen conversion in catalyst bed. ............................ 98
Figure 5.11 : Effect of varying spatial composition in reactor beds on the mole fraction of
ammonia in the reactor compared with the reference (homogeneous) design with spatial
concentration [1.00, 1.00, 1.00] ...................................................................................... 99
Figure 5.12 : Effect of varying spatial composition in reactor beds (1.50, 1.25, 1.00); a)
nitrogen conversion, b) actual, optimal and equilibrium temperatures, c) hydrogen,
nitrogen and ammonia mole fractions........................................................................... 100
Figure 5.13 : Bed1: Temperature Profile with different Catalyst Distribution ..................... 101
Figure 5.14 : Bed2: Temperature Profile with different Catalyst Distribution ..................... 102
Figure A.1 Ammonia 3D Phase Diagram ............................................................................. 121
xv
Engr. Sadaf Siddiq (08F-UET/PhD-ME-47)
1 INTRODUCTION
In the coming centuries of the decline of the worlds fossil energy stocks, an electricity
production mix will establish which will be inevitably dominated increasingly by alternate &
renewable energies.
The alternate energy sources are available in form of solar energy, wind energy,
hydroelectric, geothermal, wave and tidal power etc. The current global energy consumption
is 15TWe per year while the solar energy potential is estimated to be 86000 TWe per year
[46].
Solar energy can be utilized either as a direct photovoltaic (PV) source, where the light is
converted directly into electrical energy or as concentrated solar power where a fluid is
heated by concentrating the solar thermal energy to produce electricity in a thermal power
plant. Solar thermal energy is concentrated using different techniques, such as, Parabolic
Trough, dish System and power tower etc.
The success of solar thermal systems for electricity production hinges very crucially on the
selection, mechanical design and optimal operation of an energy storage system which can
enable the continuous operation of a power plant. The energy storage systems being
investigated include solid graphite, encapsulated Phase Change Materials (PCMs) in a
graphite matrix, and liquid ammonia [72].
This work focuses on extending the use of a solar thermal energy plant from an intermittent
energy source to a base load power plant by incorporating an efficient thermal storage feature.
A reference 10 MWe solar thermal plant design is considered with liquid ammonia as a
working fluid for energy production in a Rankine Cycle as well as a thermal storage medium.
During periods of no solar insolence, the recovery system, based on an industrial ammonia
synthesis system, is used to drive the power conversion unit and enable continuous operation.
The objective of this work is to increase the efficiency of ammonia synthesis process for
maximum heat recovery and hence to improve the performance of Solar Thermal Storage
plant.
1.1 Solar Energy: Potential as a Renewable Energy Source

Solar energy currently accounts for an installed capacity of about 23 GWe, compared with
geothermal (installed capacity 10.7 GW), and wind (160 GW) [8]. This is insignificant in the
global scenario where in 2010, the total primary energy consumption was 12002.4 Mtoe [8]
consisting of oil (33.8%), coal (29.6%), natural gas (23.8%), hydroelectric (6.5%) and
nuclear (5.6%). Even though renewable sources such as solar, geothermal and wind are not
presently significant, they offer the promise of providing clean and sustainable energy by
mitigating the effect of the carbon release from fossil fuels, in the form of greenhouse gases
[8], [14]. Such reductions are necessary for the environment and are binding on states
signatory to the Kyoto Protocol [117]. Emission of greenhouse gases (carbon dioxide,
methane, nitrous oxide, hydrofluorocarbons, perfluorocarbons and sulphur hexafluoride) as
well as toxic and pollutant gases, also have a harmful effect on people.
The Kyoto Protocol of 1997 [117] came into force on 16th February 2005 and establishes
quantified limitations on greenhouse gases, to promote sustainable development and calls for
member states to develop new forms of renewable energy and innovative environmentally
sound technologies.
According to a study by the World Energy Outlook [14] a Reference Scenario studies the
period 2006-2030 and estimates an increase in world primary energy demand of 45% from an
annual of 11730 Mtoe to over 17010 Mtoe at 1.6% increase per year. While oil remains the
dominant fuel, its share decreases from 34% to 30% over this period. In the same period, gas
rises at 1.8% per year to 22% while coal, at an annual increase of 2% rises from 26% to 29%.
Thus the fossil fuels contribute to 81% of the total primary energy demand by 2030.
Notwithstanding the impact of a nuclear renaissance, the contribution of nuclear power to
primary energy drops from 6% to 5%; this is an electricity generation share from 15% to 10%
by 2030.
In this period, renewable energy sources take second place after coal for electricity
generation. The contribution of hydropower drops from 16% to 14% while non-hydro
renewables, growing at an average annual rate of 7.2% increase from less than 1% to 4%.
The absolute magnitude of the non-hydro renewables increases from 66 Mtoe in 2006 to 350
Mtoe by 2030.
The power outlook has coal contribution to electricity generation increasing from 41% in
2006 to 44% in 2030, while the share of renewable grows from 18% to 23% in the same
period. The worlds final electricity consumption grows from 15665 TWh to 28141 TWh at
an average annual growth of 2.5%. This corresponds, in the Reference Scenario, to an
electricity generation of 18921 TWh in 2006 to 33265 TWh in 2030.
The factors accelerating the share of renewables are climate change, to attain the CO2 ppm
goal, the higher cost of oil and gas and energy security. Among the renewables, hydropower
will continue to be the dominant while others will include wind, solar, biomass and
geothermal energy.
The sun, as the primary source of energy for the solar system, supplies over 30,000 TWyr/yr
which, compared with the global energy requirement of the order of 20 TWyr/yr over the
next generation, may be considered to be a virtually inexhaustible source [46]. Solar energy
is useable as thermal energy, bioenergy from photosynthesis, and as a source for photovoltaic
conversion. Solar energy is truly renewable and sustainable as it is non-depletable, carbon
emission free, scalable, readily accessible, robust and flexible. The issues which will ensure
its place in the future energy scenario is its economic competitiveness in comparison with
existing technologies. A key technological issue that lies at the core of economic
competitiveness of solar energy -- thermal energy storage, is the focus of this thesis.
For electricity generation, the solar energy options available are photovoltaic (PV)
technology and concentrated solar power (CSP) technology. PV technology is based on the
direct conversion of photon energy from the Sun to electricity. Since the energy from the sun
is spread over a large range of wavelengths, a PV collector is designed to utilize as much of
the available spectrum as possible. The primary limitation is the detection window of the
sensor material forming the collector. The efficiency of a PV collector has remained low
(about 20%) and thus its application has been generally limited to mini-power requirements
such as off-grid homes [168][175]. However, larger PV plants have been built and the total
PV technology had a global installed capacity of 6 GWe in 2006, growing by 2009 to
15GWe and by the end of 2009 to 23 GWe, but had the disadvantage of having the highest
generating cost (US$ 5500-9000 per kWh in 2007) compared to all renewable technologies.
The Reference Scenario estimates the cost to reduce to US$ 2600 per kWh by 2030. CSP
technology uses optics to focus sunlight to a small receiver where the energy can be utilized
to convert water to superheated steam for electricity generation in a turbine. The total
installed capacity of CSP was 354 MWe in 2006. This technology is expected to be
comparable in cost (US$ 2-3 per kW: 2007) with gas-fired, but generally more expensive
than coal-fired generation, wind and nuclear.
1.2 Solar Power Plants in Operation

1.2.1 PV Plants
Though PV technology is considered to be of use for small off-grid locations, large plants
have been built and are currently in operation [46]. The PV power generation technology saw
a 70% increase in 2008 alone, to 13GWe. Two notable areas of growth witnessed in 2008
were the Building Integrated PV Plants (BIPV) in Europe, and the utility-scaled PV plants (>
200 kWe), By the end of 2008, over 1800 such plants were in operation worldwide. Several
of these plants can be considered to be large, with the 200 MWe Huanghe Hydropower
Golmud Solar Park plant, completed in China in 2011, to be the largest PV plant in the world.
Plants of this magnitude are currently under development in Europe, China, India, Japan, the
United States of America and other countries. Table 1.1 presents Worlds largest PV plants in
operation while 38 more plants with a cumulative nominal power of about 13000 MWe are
planned or under construction and are expected to complete by 2019.
TABLE 1.1: Worlds Largest (25MWe or above) PV Plants in Operation

S.No.
1
2
3
4
Name
Country
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
Huanghe Hydropower Golmud Solar Park

Perovo Solar Park
Sarnia Photovoltaic Power Plan
Montalto di Castro Photovoltaic Power
Station
Solarpark Senftenberg
Finsterwalde Solar Park
Okhotnykovo Solar Park
Lopburi Solar Farm
Lieberose Photovoltaic Park
San Bellino Photovoltaic Power Plant
Le Gabardan Solar Park
Olmedilla Photovoltaic Park
Sault Ste Marie Solar Park
Strasskirchen Solar Park
Tutow Solar Park
Waldpolenz Solar Park
Longyuan Golmud Solar Park
Hongsibao Solar Park
Serenissima Solar Park
Copper Mountain Solar Facility
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
Puertollano Photovoltaic Park

Moura photovoltaic power station
Kothen Solar Park
Avenal Solar Facility
Cellino San Marco Solar Park
Bitta Solar Park
Frstenwalde Solar Park
Ralsko Solar Park Ra 1
Reckahn Solar Park
Alfonsine Solar Park
Vepek Solar Park
San Luis Valley Solar Ranch
Sant'Alberto Solar Park
Planta Solar La Magascona & La Magasquila
Ernsthof Solar Park
Arnedo Solar Plant
Parc Solaire Curbans
China
Ukraine
Canada
Italy
Nominal
Power(MWe)
200
100
97
84.2
Germany
Germany
Ukraine
Thailand
Germany
Italy
France
Spain
Canada
Germany
Germany
Germany
China
China
Italy
USA
82
80.7
80
73
71.8
70
67.2
60
60
54
52
50
50
48
48
47.6
Spain
Portugal
Germany
USA
Italy
India
Germany
Czech Republic
Germany
Italy
Czech Republic
USA
Spain
Italy
Germany
Spain
USA
46
45
45
42.7
40
39.5
38.3
38
36.2
35.1
35
34.4
34
33
32
31.8
30.2
38
39
40
41
42
43
44
45
46
47
48
49
Long Island Solar Farm

Planta Solar Dulcinea
Cottbus Drewitz Solar Park
Agua Caliente Solar Project
Gunthawad Solar Farm
Cimarron Solar Farm
Merida/Don Alvaro Solar Park
Planta Solar Ose de la Vega
Webberville Solar Park
evtn Solar Park
Solarpark Heideblick
Solarpark Eiche
USA
Spain
Germany
USA
India
USA
Spain
Spain
USA
Czech Republic
Germany
Germany
30
30
30
30
30
30
29.9
27.5
26.4
26
25.7
25
1.2.2 Solar Thermal Plants

The CSP technology showed a small generation increase by 0.06GWe to 0.5GWe by the end
of 2008. The worlds largest solar site is in California, owned by NextEra Energy Resources
[45] The power produced is 354 MWe, which is purchased by Southern California Edison
and provides to more than 230,000 homes at peak power during the day. It is thus as large as
a nuclear reactor such as CHASNUPP, and would be sufficient for a city of the size of
Islamabad. The site is spread over 1500 acres, and has more than 900,000 mirrors.
Other large CSP plants in the range of 30-150 MWe are also located in the United States and
Spain [21],[47]. Several other countries including Abu Dhabi, Algeria, Egypt, Israel,
Portugal and Morocco have projects underway [45]. One of the plants, a 20MWe CSP is
integrated with a 450MWe natural-gas combined-cycle plant in Morocco. Table 1.2 lists
solar thermal power plants in operation in different parts of the world with total capacity
amounting to 1702.65 MWe. The total capacity of under construction (to be completed by
2014) solar thermal plants is 2106.9 MWe.
TABLE 1.2: Solar Themal Plants in Operation
Serial
#
1
2
3
Name
Country
USA
Capacity
(MWe)
354
Solar Energy Generating

Systems
Solnova Solar Power Station
Andasol solar power station
parabolic trough
Spain
Spain
150
150
parabolic trough
parabolic trough
Technology
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
Extresol Solar Power Station

Palma del Rio Solar Power
Station
Manchasol Power Station
Valle Solar Power Station
Martin Next Generation Solar
Energy Center
Nevada Solar One
Ibersol Ciudad Real
Alvarado I
La Florida
Majadas de Titar
La Dehesa
Helioenergy 1
Lebrija-1
Solacor 1
Puerto Errado 1+2
Hassi R'mel integrated solar
combined cycle power station
PS20 solar power tower
Kuraymat Plant
Beni Mathar Plant
Yazd integrated solar combined
cycle power station
24
Gemasolar
25
PS10 solar power tower
26
Kimberlina Solar Thermal
Energy Plant
27
Sierra SunTower
28
Archimede solar power plant
29
Thai Solar Energy (TSE) 1
30
Liddell Power Station Solar
Steam Generator
31
Keahole Solar Power
32
Maricopa Solar
33
Jlich Solar Tower
34
Saguaro Solar Power Station
35
Shiraz solar power plant
Overall Capacity
Spain
Spain
100
100
parabolic trough
parabolic trough
Spain
Spain
USA
100
100
75
parabolic trough
parabolic trough
ISCC
USA
Spain
Spain
Spain
Spain
Spain
Spain
Spain
Spain
Spain
Algeria
64
50
50
50
50
50
50
50
50
31.4
25
parabolic trough
parabolic trough
parabolic trough
parabolic trough
parabolic trough
parabolic trough
parabolic trough
parabolic trough
parabolic trough
fresnel reflector
ISCC
Spain
20
solar power tower
Egypt
Morocco
Iran
20
20
17
ISCC
ISCC
parabolic trough
Spain
Spain
USA
17
11
5
solar power tower

solar power tower
fresnel reflector
USA
Italy
Thailand
Australia
5
5
5
2
solar power tower

parabolic trough
parabolic trough
fresnel reflector
USA
USA
Germany
USA
Iran
1702.65
2
1.5
1.5
1
0.25
parabolic trough
dish stirling
solar power tower
parabolic trough
parabolic trough
1.3 Thermal Energy Storage Requirement

The major drawback of CSPs at the moment is the lack of thermal storage due to which
operation is only possible when daylight is available. Only two plants have storage viz the
Andasol-1 [48] plant in Spain which has more than seven hours of full-load thermal storage
capability, and a 280 MWe plant planned in Arizona which will also have a six-hour storage
capacity.
1.4 Thermal Storage Materials

The thermal energy storage technologies can be classified [72] by the mechanism of heat viz
(i) sensible, (ii) latent, (iii) sorptive, and (iv) chemical. In the sensible heat storage systems,
there is the possibility of liquid (water tank, aquifier, thermal oil) and solid systems (building
mass, concrete, and ground etc.) [5]. In the latent heat storage systems, both organic
(parrafins) and inorganic (hydrate salts) compounds can be used. In the sorptive, both
absorption and adsorption systems can be used. Finally, in the chemical storage, energy can
be stored in chemical bonds which can be broken endothermically and recovered in a
synthesis exothermically.
When single-phase heat transfer fluids such as thermal oil or pressurized water are used, a
sensible heat storage system using concrete has been developed and experimentally tested
[51] in the temperature range 300-400 oC and found to be an attractive options for CSPs.
Storage materials and technology will also depend on the temperatures in the plant [66]. For
domestic hot water and space heating, the temperatures will be less than 100 oC; for process
heat, 100-250 oC; for electricity generation 250-1000 oC, while for hydrogen production they
Engr. Sadaf Siddiq (08F-UET/PhD-ME

ME-47)
phase
se change materials is shown
will be in excess of 1000 oC. The storage capacity of some pha
below [66].. It can be seen that the highest storage capacity is for salts.
Figure 1.1 Volume Reduction with Phase Change Materials
Figure 1.2 Materials for medium and high heat storage
10
Salts freeze 350-500 oC and boil at ~1000 oC. They have a high volumetric heat capacity and
may be used, even in graphite blocks. Liquid fluoride salts are also widely available, as they
are used in aluminium metal extraction Hall electrolysis process in which aluminium oxide
is dissolved in cryolite which is a sodium-aluminium fluoride salt. Fluoride salts are
compatible with graphite upto 1400 oC [176].
1.5 Use of Liquid Ammonia as Storage Material

Liquid ammonia is a candidate for large solar-thermal systems due to the storage of thermal
energy in its chemical bonds during, for example, solar insolation and recovery from
subsequent exothermic synthesis. To compare different storage opportunities, the energy
storage density is a value which is useful to determine the required size of storage for a
required amount of energy. With the kind of energy carrier, the amount of stored energy
varies strongly. A comparison between different energy carriers is presented in Figure 1.3
[79]. It is clear that thermo-chemical energy carriers offer the suitable most energy densities
i.e. of the order of 10 MJ/kg.
Ammonia is an abundantly produced chemical, globally and in Pakistan. It has an important

use as a fertilizer to boost agricultural production. Thus it is used in a synthesis process of
natural gas with carbon dioxide resulting in the formation of urea fertilizer, or carbamide
(NH2)2CO. In Pakistan, there are eight large urea fertilizer plants based on the reforming and
synthesis of natural gas mainly from the Sui and Marri gas fields. At an international price of
US$ 300/tonne, this represents an annual sales value of US$1,500 million. This amounts to
an average production of about 1600 tonnes per day (TPD) per plant [25].
11
Figure 1.3 Energy densities for different energy carriers
1.5.1 Poperties of Liquid Ammonia

Ammonia (NH3) stays in the liquid form at temperatures higher than its melting point
o
77 .73 C and has a density of 681.9 kg/m at its boiling point -33.34 C ; it must thus be
kept at very low temperature or stored at very high pressure [165]. Liquid ammonia was first
produced on an industrial scale in Germany, during the First World War, by the Haber Bosch process [110].
1.5.2 Dissociation and Synthesis of Ammonia

The dissociation of ammonia
2 NH3 N 2 + 3H 2 (H = 66.9 kJ/mol)
12
is an endothermic reaction that can be carried out by thermo-catalytic decomposition using

catalysts: ruthenium, indium, nickel, Fe-Al-L, Fe-Cr. Typical temperatures are in the range of
850 1000 oC. Approximately 1.4 kW power per cubic meter of hydrogen is typically used.
Conversely, the synthesis of ammonia from nitrogen and hydrogen reactant gases
N 2 + 3H 2 2 NH 3
(H = -92.22 kJ/mol)
is an exothermic reaction for which the pressure required is in the range 130 250 bar, and
the temperature required is in the range 250 600 oC. High temperature gives higher reaction
rate, but as reaction is exothermic, higher temperature according to Le Chateliers principle
causes the reaction to move in the reverse direction hence a reduction in product. Similarly,
higher Temperature reduces the equilibrium constant and hence the amount of product
decreases; this is the Vant Hoff equation
ln K =
H o S o
+
RT
R
An increase in pressure, however, causes a forward reaction and is thus favorable. Synthesis
is achieved by using catalysts such as osmium, ruthenium, and iron-based catalysts [110].
1.5.3 Commercial uses of Ammonia

Ammonia is one of the most widely produced chemicals, amounting to over 15 million tones
in 2009. Its major uses are as fertilizer and for production of nitrogen containing compounds
such as nitric acid. It is used as a refrigerant and in textile processing. A very important
emerging use of ammonia is Hydrogen production, by its decomposition, to be used in
Hydrogen Fuel cells.
13
1.5.4 Industrial proprietary processes for Ammonia Production

Global fertilizer industry produces about 170 million tones of fertilizer nutrients every year
[42] for boosting agricultural output. Fertilizers are based on nitrogen, phosphorus or
potassium. Nitrogen accounts for 78% of the earths atmosphere. Since plants can not breathe
nitrogen, it must be converted to a suitable form such as ammonia. The Haber-Bosch process,
first demonstrated by Fritz Haber in 1909 and scaled up to an industrial process by Carl
Bosch in 1913. Both Haber and Bosch were awarded Nobel Prizes for their inventions, and
ammonia was used in Germany in the First World War for the manufacture of explosives. A
greater use of the Haber-Bosch process was in the manufacture of fertilizers such as urea and
ammonium nitrate. About 70% of the ammonia produced is from natural gas as feedstock
and the rest is mainly from coal. The Haber-Bosch process, involving the steam reforming of
methane to produce hydrogen is used with nitrogen taken from the air, to produce ammonia.
The typical size of urea plants is 1000 MeT per day with a capital cost of US$ 150 million.
The total production of ammonia was 130 million tones in 2000, produced in 80 countries
and 85% of which was used for nitrogen fertilizer production. The largest chemical industry
in the world is in the U.S. [19], with ammonia being the most important intermediate
chemical compound produced in 41 plants. The energy intensity for ammonia manufacture in
the U.S. is 39.3 GJ/tonne (including feedstocks HHV). The theoretical minimum for
ammonia production by steam reforming is 21.6 GJ/tonne which represents the ideal goal.
The technology is now mature, with the market dominated by five licensers-Haldor Topse,
M.W. Kellogg, Uhde, ICI, and Brown & Root, of which Haldor Topse has a 50 per cent
world market share as supplier of the technology [42].
14
1.5.4.1 Haldor Topsoe Ammonia Synthesis Process

The conventional sequence of process steps are optimized by the introduction of improved
catalysts (KM high strength, versatile, stable and poison-resistant catalyst, mainly magnetite
Fe3O4 with promoters mainly oxides of calcium, aluminum and potassium, operating
temperatures 340-550
C [21]), new equipment design (such as improved synthesis
converters), and process optimization studies. The carbon monoxide concentrations have
been minimized at the exit of the shift converters, and a low-energy carbon dioxide removal
process (such as selexol) has been used. New syn converters S-250 and S-300 are improved
versions of the previous single bed S-50 and two-bed S-200 radial flow converters. Topsoe
recommends S-300, developed in 1999, for all new plants [[21], [24].
TABLE 1.3: Haldor Topsoe Ammonia Converter Features

Type
S-50
S-200
S-250
S-300
Basic Design
One catalyst bed
Two catalyst beds and one interbed
heat exchanger
Combination of the S-200 followed
by the S-50
Three catalyst beds with two
interbed heat exchangers
Comments
Simplest and cheapest
Commissioned in 1979; 130
units installed
Higher conversion for same

catalyst volume of S-250;
installed first in 1991.
1.5.4.2 Kellog Brown & Roots (KBR) Advanced Ammonia Process (KAPP)
KAAP uses a traditional high-pressure heat exchange based steam reforming process
integrated with a low-pressure advanced ammonia synthesis process. The steam reforming of
hydrocarbon based on Kellogg Brown and Root Reforming Exchange System (KRES) is
15
carried out which reduces energy consumption and capital cost besides reduced emissions
and enhanced reliability.
After reforming, carbon monoxide is removed from the shift converter, and carbon dioxide is
removed from the process gas using hot potassium carbonate solution, methyl diethanol
amine (MDEA) etc.
KAAP uses a high activity graphite supported ruthenium catalyst, typically three stages, after
one stage of traditional iron catalyst. This is claimed to increase the activity 10 to 20 times
enabling very high conversion at a lower pressure of 90 bar [10].
KBR is a large player in the ammonia and urea industry. It has been involved in the licensing,
design, engineering and/or construction of more than 200 ammonia plants and 62 urea
projects in the range of 600 to 3500 MTPD worldwide, representing approximately half of
current global ammonia production [23].
1.5.4.3 Krupp Uhde GmbH Ammonia Process

The Krupp Uhde Gmbh process uses the traditional reforming process followed by a
medium-pressure ammonia synthesis loop[86].
The primary reforming is carried out at a pressure of 40 bar and temperature range of 800850 oC. Enhanced reliability is attained by using a top-fired steam reformer with high alloy
steel tubes. Process air is added in the secondary reformer through nozzles installed in the
wall of vessel thus providing proper mixing of the air and reformer gas. This also provides
high energy efficiency in high pressure steam generation and superheating. As in other
processes, carbon monoxide is converted to carbon dioxide in HT and LT shift converters,
and the MDEA or Benfield system is used for carbon dioxide removal.
16
The ammonia synthesis loop uses two radial flow ammonia converters with three catalyst
beds, containing iron catalyst, and waste heat boiler located downstream of each reactor. The
converters have small grain iron catalyst.
Since 1994, Uhde has built 15 new ammonia and 13 new urea plants with annual production
capacities of more than 8 million tonnes of ammonia and 10 million tonnes of urea with
individual capacities ranging from 600 to 3,300 mtpd of ammonia and from 1,050 to 3,500
mtpd of urea [36]. Uhde has also been awarded a contract to build a 3300 MTPD Uhde
Dual-Pressure Process ammonia plant for Saudi Arabian Fertilizer Company (SAFCO) in
Al Jubail, Saudi Arabia [78].
1.5.4.4 ICI-Leading Concept Ammonia (LCA) Process

In this process, ammonia synthesis takes place at low pressure of below 100 kg/cm2g
(approximately 100 bar) using ICIs highly active cobalt promoted catalyst. This process has
an energy consumption of approximately 7.2 Gcal/ MeT (30.1 GJ/MeT) ammonia for a 450
MeT per day plant [19].
1.5.4.5 The Linde Ammonia Concept (LAC) Ammonia (LCA) Process
The LAC process consists essentially of a modern hydrogen plant and a standard nitrogen
unit with a third-party license from Casale for a high efficiency ammonia synthesis loop [34].
Ammonia Casale [16] is one of the oldest companies in the business of synthetic ammonia
production, having been founded in Switzerland in 1921. To date it has been active in the
design of over 150 ammonia synthesis reactors and in the constructionof several new plants.
17
The CO shift conversion is carried out in a single stage in the tube cooled isothermal shift
converter and gas is sent to pressure swing absorption (PSA) unit wherein the process gas is
purified to 99.99 mole % hydrogen . A low temperature air separation in cold box is used to
produce pure nitrogen. BASFs MDEA process is also eliminated in this process used for
CO2 removal.
The ammonia synthesis loop is based on Casale axial-radial three-bed converter with internal
heat exchanger giving a high conversion. The energy consumption for ammonia production
is about 29.3 GJ/ MeT [16].
Thus far, four plants based on the relatively new Linde Ammonia Concept have been
constructed with capacities of between 230 to 1,350 MTPD of ammonia.
1.6 Thermodynamic Cycles for Solar Thermal Power Plants

The two commonly used thermodynamic cycles for solar plants are the Brayton and Rankine
Cycles depending on the temperatures of the working fluid. Power towers employing PCM
salts are able to achieve very high temperatures, typically in excess of 1000 oC which transfer
heat to inert gases such as helium, and at a lower temperature, water is converted to
superheated steam. Such plants draw heavily from the experience and resources available
with high temperature gas reactors in the nuclear industry. While the thermodynamic
efficiency of such systems is high, special materials and high safety features are required for
this technology [140].
Solar power plants based on the concentrating parabolic systems, ordinarily use water as a
working fluid and are thus based on the Rankine Cycle [130].
18
1.7 Literature Review

The literature survey covered a wide range of areas, this section reviews the potential of solar
energy as a renewable source for a sustainable and clean energy future, Solar thermal power
and its components, thermodynamic aspects of candidate solar plants, thermal storage
materials, energy inputs and outputs from various thermal storage materials, energy recovery
industrial process and energy efficiency analyses for plant performance and design
parameters for realized Solar thermal power plants. This design data from realized Solar
thermal power plants has been used as a starting point for component and overall simulation,
as well as optimization formulations for carrying out sensitivity analyses leading to an
optimal pant design. Modeling and Simulation techniques for component and integrated plant
design are discussed in section 3.1.1 while review of optimization techniques is presented in
section 4.1.
Concentrating solar power is a method of increasing solar power density. CSP has been
theorized and contemplated by inventors for thousands of years. The first documented use of
concentrated power comes from the great Greek scientist Archimedes (287-212 B.C.) in 212
B.C. [175]. The modern solar concentration is believed to begin by the experiments of
Athanasius Kircher (1601-1680) in seventeenth century [175]. Solar concentrators then
began being used as furnaces in chemical and metallurgical experiments [161]. In eighteenth
and nineteenth centuries CSP applications were restricted to low pressure steam generation
and solar pumps etc.
CSP systems can provide energy storage fully integrated within the electricity-generating
plant [2][4][5]. Solar thermal radiation can be concentrated using parabolic mirrors in the
19
form of dishes, power towers, troughs and linear Fresnel etc. in commercial CSP systems.
The efficiency of these mechanisms can be evaluated on the basis of geometric concentration
ratio. The geometric concentration ratio for parabolic troughs and linear Fresnel systems can
be up to 100 and in excess of 1000 for power towers and dishes. This thermal energy can be
used to produce steam for immediate electricity generation, or alternatively it can be stored
prior to electricity generation using sensible heat storage in solids [27][49][66], molten salts
[88], phase change materials [9][39][145][153], or thermochemical storage cycles [15].
Thermochemical energy storage for CSP is less mature than molten salt and other thermal
storage methods, but it has the potential to achieve higher storage densities and hence smaller
storage size. Reactions involving ammonia, hydroxides, carbonates, hydrides, and sulfates
are the important candidates for thermochemical energy storage [15][67]. At first,
thermochemical storage loops based on methane reforming received considerable attention
[58][115][138][141]. Methane reforming is still under research for solar enhancement of
natural gas [30] and hydrogen production [31]. A lot of research is being conducted on solar
fuel production by making use of thermochemical processes [17][38].
The concept of ammonia-based energy storage for concentrating solar power systems was
first proposed by Carden in 1974 at the Australian National University [174][177] followed
by the researchers at Colorado State University in early 1980s [163].
Researchers at ANU [132][167] and Colorado State University [163] have concluded after
theoretical analysis and experimental results [109] that dish concentrators are the most
suitable solar receiver designs for ammonia dissociation because they provide a
circumferentially homogenous solar flux profile [136] which can facilitate thermochemical
20
reactor design inferring that only simple control systems are necessary, thus the mobile
receiver can be maintained at a light weight, and solar transients are easy to handle
[132][137]. Feasilbility of parabolic trough systems have also been investigated for use with
CSP employing ammonia based energy storage systems [97].
Prototype solar ammonia receiver/reactors, Mark I and Mark II were tested in 1994 and 1998
respectively both employing a 200-mm long cavity type reactor mounted on a 20-m2 faceted
paraboloidal dish. Haldor-Topse DNK-2R iron-cobalt catalyst was used in the annular
catalyst beds [108]. These reactors were rated for 1.0 2.2-kWchem conversion. Recent work
is being conducted on paraboloibal dishes of area 400-m2, 489-m2 and newly constructed
500-m2 for a base load plant size of upto 10 MWe [11].
For solar collector/receiver design improvements, investigations into convection losses from
cavity receivers have been undertaken [12][81] as these improvements can amount to solarto-chemical efficiency gains of up to 7% absolute [106].
The kinetic mechanisms for the synthesis and decomposition of ammonia have been
described by various authors for ironbased catalysts [120][186][189][195] and for rutheniumbased catalysts [111][121][126].
Comprehensive studies for solar energy heat [104],[106]] recovery have been carried out on
an experimental 1-kWchem. synthesis reactor by Kreetz and Lovegrove [106] in a laboratoryscale high-pressure closed-loop system with a feed-gas mass flow rate of
0.3 g s-1 at
pressures ranging from 9.3 to 19 MPa. With external pre-heating of the feed gas, average
external wall temperature varying between 250-480C and peak internal reactor temperatures
varying between 253-534C, the maximum reaction was reported by Kreetz and Lovegrove
21
[106] to have been achieved at approximately 450C. In their optimal system, a net heat
recovery rate of 391 W was reported. The study by Kreetz and Lovegrove [106] was extended
to a 10 kW system with an ammonia synthesis tubular reactor at a pressure of 20 MPa and a
flow rate of 0.9 g s-1 [79]. The larger system, with a controlled linear temperature profile in
the reactor wall, and the gas inlet temperature kept to 50 C lower than the wall temperature
at the inlet, resulted in a maximum thermal output achieved at an average wall temperature of
475C produced with an inlet temperature of 500 C and a slope of -50 C m-1. Such studies
have attempted to achieve optimal heat recovery by varying the inlet temperature arbitrarily
instead of attaining the optimal temperature suggested by theoretical models, such as
variational methods.
1.8 Thesis Motivation

Thermal Storage plants using ammonia as storage medium can take advantage of the wellunderstood and extensively deployed ammonia dissociation and synthesis technologies. Their
efficiency, however, will depend on the optimization of the process parameters typical of the
system pressure and temperatures in the dissociation and synthesis reactors taken together
with those at the solar receiver.
A lot of research has been carried out on solar collector design and dissociation efficiencies
of more than 90% have been practically achieved using cavity type dissociation reactors in
conjunction with paraboloidal dish type solar receivers[105][106]. The motivation of plant
optimization is to maximize the efficiency of the plant by maximizing the heat recovery from
the most critical process in the plant: the synthesis reactor. This research is of great value to
industry as well because the same optimization techniques can be used for improving
22
ammonia production rates at pressures lower than the industry standard pressures, hence
cutting the costs.
1.9 Objectives
The use of liquid ammonia, as a thermo-chemical energy storage medium, for endothermic
dissociation by solar energy during insolence and subsequent energy recovery by exothermic
synthesis is considered to be a strong candidate for the design of a base-load solar thermal
power plant.
The technology of ammonia production is well established as is the modeling and simulation
of ammonia synthesis. However, optimization of the process is an on-going challenge as
technological innovations enable better designs resulting in improved efficiency. As part of
this optimization challenge, this thesis considers the possible improvement in the recovery of
exothermic thermal energy by optimization of the ammonia synthesis process. While
ammonia production has remained almost the same for decades, the energy consumption has
reduced as technology improvements have been incorporated especially for the fertilizer
industry where over 90% of the energy utilization is for ammonia synthesis [76].
The objective of the study will be achieved by:
Parametric Sensitivity studies leading to an optimized design of a TSP
i.
Numerical Simulation of Conservation Equations,
ii.
Optimize physical dimensions of Synthesis Reactor,
iii.
Optimal distribution of Catalyst (Optimal Control analysis),
iv.
Overall Thermal Energy Recovery Analysis.
23
1.10 Summary of Following Chapters

The necessary background information is given in Chapter 1. Chapter 2 describes the thermal
storage plant features such as process design, operational parameters and process flow
diagram etc. Chapter 3 deals with the modeling and simulation of the components of thermal
storage plant while optimization of thermal storage plant has been done in chapter four both
by variational calculus and process engineering codes. The fifth chapter presents the optimal
TSP model, designed in the light of sensitivity and parmetric analyses in chapter four.
Conclusions and future recommendations are presented in Chapter 6.
24
2 DESCRIPTION OF THE THERMAL STORAGE

PLANT
2.1 Plant Features
A thermal storage plant may be used as a baseload plant, when it operates on a continuous
basis just like a coal-fired, nuclear or hydroelectric power plant, or as a traditional PV
intermittent solar plant. The baseload operation is only possible if the plant has an integrated
thermal storage feature.
The major components of a baseload plant are the receiver system, a storage system, an
energy recovery system, a power conversion unit, and associated plant systems such as
compressors, pumps and heat exchangers.
The objective of the Thermal Storage Plant (TSP) considered here is to maximize the overall
efficiency of the plant, which is essentially the optimization of the ammonia synthesis
process.
2.1.1 Process Design

This section considers some basic aspects of the overall plant design with the objective of
getting orders of magnitude. Table 2.1 shows such overall conditions for a conceptual MSExcel calculation for a baseload plant of 10 MWe. It is assumed that a solar insolation of 1
kW/m2 is available for 8 hours in a day. With 400 parabolic dishes, each of area 400 m2 of
the type available to the ANU group [101][105], the thermal power intercepted by the plant is
25
4.608 TJ in a day. These assumptions are optimistic even for the high solar insolence of
about 20 MJ/m2 for Pakistan [150].
TABLE 2.1: Overall Plant Design for a 10 MW(e) Baseload Plant
BASIC DATA
Dissociation Energy
Synthesis Energy
Power Density
Insolation Hours per Day
Dish Area
No. of Dishes
extent of dissociation reaction
Electrical Power Reqd (24hrs)
Synthesis Conversion
Rankine Cycle Effciency
kJ/mol
kJ/mol
Watts / m^2
Hr
m^2
MW(e)
66
46.6
1000
8
400
400
0.9
10
0.2
0.4
POWER INPUT
Thermal Power Available/day
Thermal Power Available/day
kW-hr/m^2 per
day
MJ/m^2 per day
8
28.8
ThPower/day on one dish

ThPower/day on all dishes
MJ per dish per

day
MJ per day
11520
4608000
Flow rate of NH3

Flow rate of NH3 per dish
mol per dish

during
insolation
kg NH3 per dish
during insolation
MTD NH3
during insolation
kg/s NH3
kg/s NH3
Electrical Energy Needed

Thermal Energy Needed
MJ(e) per day

MJ(th) per day
288000
720000
POWER OUTPUT
Recoverd Synthesis Energy
Converted Synthesis Energy
MJ per day
MJ per day
921600
368640
Overall Efficiency
Flow of NH3 per dish

Flow of NH3 per dish
Flow of NH3
26
193939.39
3296.97
1318.79
45.79
0.1145
Key design parameters are the thermal power intercepted by the plant during insolence (4.6
TJ), the thermal energy needed (2.1 TJ) for a baseload of 10 MW(e), the recovered synthesis
energy (0.922 TJ) and the final converted energy (0.368 TJ). In this scenario, three
efficiencies are assumed viz (i) the extent of dissociation (0.9) [47], (ii) the synthesis
conversion (0.2), and (iii) the Rankine efficiency (0.4) [[15],[79],[130].
The purpose of the present research is to estimate the best possible synthesis conversion, by
optimizing the catalyst distribution, to investigate the feasibility of such baseload operation.
2.1.2 Opertational Parameters

The operational parameters of TSP have to be chosen carefully as the use of a reversible
reaction to store energy is governed by the dependency of the thermodynamic equilibrium
composition on temperature and pressure. Conceptually, if a sample of ammonia were heated
slowly (quasi-statically), it would begin to decompose at temperatures of several hundred
degrees, around 700 K at 200 atmospheres (20MPa). Complete dissociation would only be
approached asymptotically at very high temperatures. The amount of energy absorbed at each
step would be proportional to the fraction of ammonia split. Reversing the process and
withdrawing heat would see ammonia resynthesize, with heat released progressively [196].
To implement this on an industrial scale, the limitations of reaction kinetics must also be
taken into account. Reaction rates are zero at equilibrium by definition; they increase by the
degree of departure from equilibrium (and in the direction needed to return the system to
equilibrium) and also increase rapidly with temperature in proportion to the well-known
27
Arrhenius factor. Thus, a real system absorbs heat at temperatures higher than the
equilibrium curves suggest and then releases it at lower temperatures.
The input temperature for the power cycle is an extremely important issue for all thermalbased energy storage systems, not just thermochemical ones. Electric power generation via a
thermal cycle is limited by the second law of thermodynamics lower temperature thermal
inputs reduce the efficiency of power generation. Thus, in designing and examining thermal
energy storage systems, it is necessary to consider both thermal efficiencies (energy
out/energy in) and second law efficiencies (potential for work out/potential for work in).
A TSP will have operational parameters, pressures, temperatures and flow rates, similar to
those in the ammonia units of urea fertilizer plants in the chemical process industry. These
require pressures in the range of 130-250 bar and temperatures in the range 250-600 oC for
flow rates typically of the order of 50 kg s-1 for a 1500 MTD ammonia plant. Such high
pressures require compression which is expensive in terms of equipment cost as well as
energy utilization
2.2 Overall Plant Layout and Description

The schematic diagram of TSP is shown in figure 2.1[2]. In this closed loop system, a fixed
inventory of ammonia passes alternately between energy-storing (solar dissociation) and
energy-releasing (synthesis) reactors, both of which contain a catalyst bed. Coupled with a
Rankine power cycle, the energy-releasing reaction could be used to produce baseload power
28
for the grid. At 20 MPa and 300 K, the enthalpy of reaction is 66.8 kJ/mol, equivalent to 1.09
kWh/kg of ammonia, or 2.43 MJ/L, with the corresponding density of 0.6195 kg/L [165].
Figure 2.1: Thermal Storage Plant Schematic
2.2.1 Ammonia Dissociation

Having the advantage of solar concentration of 3000 suns [105], a mirrored paraboloidal dish
focuses solar radiation onto a dissociation reactor (cavity type) through which anhydrous
ammonia is pumped. The reactor contains an annular catalyst bed which facilitates the
dissociation of ammonia at requisite temperature and pressure into gaseous nitrogen and
hydrogen termed syngas. The fact that the ammonia dissociation reaction has no possible
side reactions makes solar dissociation reactors easy to control and implement [2][160].
Typically, 400 such reactors mounted on paraboloidal dishes, of area 400 m2 each, are used
in an array patteren to feed the ammonia synthesis reactor.
29
Figure 2.2: Array of 400 m2 Paraboloidal Solar Collectors [3]
2.2.2 Ammonia Synthesis

A reactor is used for energy recovery from the exothermic synthesis reaction in which syngas
is synthesized to produce ammonia in the presence of an annular catalyst bed. Since
ammonia synthesis is a developed technology for more than 100 years, synthesis reactors
used for TSP are based on standard and proprietary industrial technologies from companies
that include Haldor-Topsoe, Kellogg Brown & Root (KBR), AkzoNobel (formerly Imperial
Chemical Industries (ICI)), and Cassal [16],[21],[23],[24].
For the reference TSP in this work, KBR Advanced Ammonia Process (KAAP) synthesis
convertor is chosen. In the KBR Advanced Ammonia Process (KAAP)[23], the synthesis
converter uses a combination of catalysts to maximize the conversion and heat recovery, such
as one stage of traditional magnetite catalyst, followed by three stages of a proprietary
KAAP catalyst consisting of ruthenium on a stable, high-surface-area graphite carbon base
(KBR). This KAAP catalyst has an intrinsic activity ten to twenty times higher than
30
conventional magnetite catalyst and is used to lower the synthesis operating pressure to 90
bar which is one-half to two-thirds the operating pressure of a conventional magnetite
ammonia synthesis loop and hence cutting plant costs.
2.2.3 Syn Gas and Ammonia Storage

The closed-loop TSP operates at a pressure (150 bar) above ambient temperature saturation
pressure of ammonia and the ammonia fraction in storage is present largely as a liquid which
causes automatic phase separation of ammonia. Thus, a common storage tank can be used to
store both syngas and liquid ammonia.
2.2.4 Heat Exchangers and Transport Piping

The heat exchangers shown in Fig. 2.1 serve to transfer heat from exiting reaction products to
the cold incoming reactants. In this way, the transport piping and energy storage volume are
all operated at close to ambient temperature, reducing thermal losses from the system, as well
as eliminating the need for costly specialized equipment.
2.2.5 Compressors and Pumps

Compressors are used for the pressure management of high pressure storage vessel and
synthesis loop. In the dissociation part of the system, a liquid ammonia feed pump is
incorporated with each paraboloidal dish. These pumps are used to control the actual process
conditions within the ammonia dissociation reactor. Mass flow control aims for 80% of the
ammonia feed being dissociated on average.
31
2.3 Thermal Storage Plant Process Flow Diagram

Figure 2.3 presents a simplified process flow diagram of thermal storage plant. The input
stream (DIS-IN) to the solar driven dissociation reactor (DISRCTR), consisting of liquid
ammonia, is pumped from the high pressure storage tank (S-TANK).
The stream DIS-IN is pre-heated by passing it through the counter flow heat exchanger (CFHX) in order to increase its temperature. The output syngas stream (DIS-OUT), consisting of
nitrogen, hydrogen and small amounts of other gases, looses heat in heat exchanger (CF-HX)
and is fed into storage tank (S-TANK). The feed-stream (FEED1) from storage tank is
compressed to the pressure required for synthesis, 150 bar. Due to the unfavourable reaction
equilibrium, only part of the Syngas is converted to ammonia on a single pass through the
Synthesis Reactor (SYNRCTR). Since the unconverted Syngas is valuable, the majority of it
is recycled back to the SYNRCTR. A Mixer is used to combine the Recycle Stream (FEED2)
and fresh stream FEED1.
Figure 2.3: TSP Process Flow Diagram

32
This mixed stream (MIX-OUT), heated in SRIN-HX to a temperature of 370 oC and is fed
into the catalyst-containing synthesis reactor (SYNRCTR) where the synthesis reaction, in
the forward direction, converts nitrogen and hydrogen into ammonia and hence producing
energy.
The effluent stream passes through the recovery heat exchanger (SROUT-HX) into the
Knock-Out drum FLASH, where the liquid ammonia is sent back to the storage tank through
stream PRODNH3 and stream VAPOR is carried to the purging system. The VAPOR stream
from Flash tank (FLASHT) contain traces of undesirable gasses such as Argon, Carbon
Monoxide and Carbon Dioxide. Argon has high partial pressure while Carbon Monoxide and
Carbon Dioxide are poisons for the Catalyst. Some of the cycle gas must be purged from the
Synthesis Loop. Otherwise, the argon that enters the loop in the Syngas has no way to leave
and will build up in concentration. This will reduce the rate of the ammonia synthesis
reaction to an unacceptable level. To prevent this from happening, a small amount of the
cycle gas must be purged, the amount being determined by the amount of argon in the feed
and its acceptable level in the Synthesis Converter feed (generally about 10 mol %). A
splitter is used to divide the VAPOR stream into PURGE and RECYCLE streams.
Another re-cycle compressor (RCOMP) is required at this stage to restore the pressure to the
required level till the stream (FEED2) is mixed with the feed stream (FEED1) and enters as
stream MIXER-OUT.
33
3 MODELLING & SIMULATION OF THERMAL

STORAGE PLANT
3.1 Mathematical Modelling

3.1.1 Review of Mathematical Models of TSP
The synthesis of ammonia can be modeled using the laws of conservation of mass,
momentum and energy for non-isothermal multi-component systems undergoing chemical
reactions and mass transfer [85]. In the case of unsteady flow the governing equations are:
Mass:
d
mtot = 1 2 + 0 = 2 v2 S 2 + 0
dt
3.1
Mass of Species i:
d
mi ,tot = i1 i 2 + i 0 + ri ,tot
dt
i = 1,2,3,......N
3.2
Momentum:
d
v 2
v 2
tot = ( 1 1 + p1S1 )1 ( 2 2 + p2 S2 )2 + mtot g + F0 F f s
dt
v1
v2
3.3
(Total) energy:
d
1 v13
1 v23
( K tot + tot + U tot ) = (
+ gh1 + H 1 )1 (
+ gh2 + H 2 )2 + w + Q0 Q
dt
2 v1
2 v 2
34
3.4
In terms of molar quantities, the continuity equation is expressed in terms of the molar
concentration c, and the mole fractions yi as
N
y
c i + (v* yi ) = ( J i* ) + Ri yi R
t
=1
i = 1,2,3,.....N
3.5
TABLE 3.1: Equations of change of Multi-component Mixtures in terms of the

Molecular Fluxes
Total mass:
D
= ( v)
Dt
Species mass:
D i
= ( ji ) + ri
(i=1,2,3,..N)
Dt
Momentum:
Dv
= [ ] + g
Dt
Energy:
D 1
(U + v 2 ) = ( q) ( pv) ( [ v]) ( v g )
Dt
2
The above have been expressed by Dashti [64] as
RNH 3
dz
=
dx 2 FNo2 / A
dT
vC p
+ ( H r )RNH 3 = 0
dx
2
2
dP = 2v = 150 (1 ) v 1.75 (1 ) v
dx
d p2
dp
3
3
3.6
A simpler analysis ignores the pressure drop in flow reducing to the conservation equations
for mass and energy with reaction kinetics, used by Yuguo [152] and Dashti [64]
dz RNH 3
=
dx 2 FNo / A
dT
vC p
+ ( H r )RNH 3 = 0
dx
3.7
3.8
35
For the reaction kinetics, the Temkin-Pyzhev [64],[152] form for the synthesis reaction rate
as a function of the pressure, temperature, and activities is used
R A RNH 3
2
a1H.52
a NH
= 2k K a a N 2
1.53
a NH 3
aH 2
3.9
where the activities are defined as ai = yii P . The individual activities are:
H 2 = exp e( 3.8402T + 0.541) P e( 0.1263T 15.98) P 2 + 300 e( 0.011901T 5.941) e P / 300
3
3
6 2
6 2
N 2 = 0.93431737 + 0.2028538 X 10 T + 0.295896 X 10 P 0.270727 X 10 T + 0.4775207 X 10 P
= 0.1438996 + 0.2028538 X 10 2 T + 0.4487672 X 10 3 P 0.1142945 X 10 5 T 2 + 0.2761216 X 10 6 P 2

NH 3
3.10
0.129
0.5
The Arrhenius rate form is given as:
E
k = ko exp
RT
3.11
and the specific heat capacities of hydrogen, nitrogen, methane and argon of the syngas (T in
Kelvin, Cp in J/mol-K) are expressed as:
C p H 2 = 4.184(6.952 0.04567 X 10 2 T + 0.09563 X 10 2 T 2 0.2079 X 10 3 T 3 )
2
5 2
9 3
C p N 2 = 4.184(6.903 0.03753 X 10 T + 0.01930 X 10 T 0.6861X 10 T )
C p CH 4 = 4.184(4.75 + 1.2 X 10 2 T + 0.303 X 10 5 T 2 2.63 X 10 9 T 3 )
C P Ar = 4.184 * 4.9675
3.12
For ammonia, the Shomate equations [28] are given as:

CP NH 3 = A + B * t + C * t 2 + D * t 3 +
E
t2
with T in the range 298-1400 K, and t =
3.13
T
.
1000
36
A = 19.99563; B = 49.77119; C = 15.37599; D = 1.921168; E = 0.18917
have been used for the temperature range of interest (500-800K) and compared with
simplified expressions [96]:
C P , H = 27.01 + 3.51X 10 3 T
2
3
C
P , N 2 = 27.27 + 4.93 X 10 T
3
C
P , NH 3 = 29.75 + 25.11X 10 T
3.14
In this model, the compressor power requirements [96], [130] for isentropic compression, are
obtained with the ideal gas assumption, as
P ( 1) /
ws =
RT 1 2
1 1 P1
3.15
The actual work will of course be larger than ws and the ratio ws / wactual will depend on the
compressor efficiency. In terms of the initial and final temperatures (T1 & T2 ) , the work can
also be found from:
ws = H = C p (T1 T2 )
3.16
More generally, for a multi-stage compressor with n units, with the compression ratios (Cr) in
all the stages equal, the total work can be estimated from
ws =
n
( 1) /
RT1 1 (C r )
1
3.17
where, for an ideal gas P1V1 = RT1 . The above expressions are based on the assumption that
specific heats remain constant in the pressure and temperature range.
37
Similar models are also used to determine the compression requirement for recycle in the
converter, refrigeration duty, vaporizer and purge systems. Additional objectives will be to
quantify process-variable trade-offs with an aim to progress towards an optimal design.
The above model can be used to carry out an energy balance of the Process Flow Diagram
(PFD). The energy input components are thus the compressors (FCOMP, RCOMP), while
the energy output system is the heat recovery system.
The equilibrium constant is obtained from
log K a = 2.691122 log T 5.51925 X 10 5 T + 1.848863 X 10 7 T 2 +
2001.6
+ 2.689
T
3.18
The overall synthesis rate (kmol of ammonia produced per hr per unit volume of catalyst) is
R A where is the catalyst effect factor [64]. It is defined as:
= bo + b1T + b2 Z + b3T 2 + b4 Z 2 + b5T 3 + b6 Z 3
3.19
and may have a significant effect on the overall efficiency. Equation 3.19 is in terms of T and
conversion percentage Z. The coefficients of this equation for three different pressures have
been depicted in table 3.2.
TABLE 3.2: Coefficients of the correction factor polynomial in terms of pressure
Pressure
(bar)
b0
b1
b2
b3
b4
b5
b6
150
-17.539096
0.07697849
6.900548
-1.08279e-4
-26.42469
4.927648e-8
38.937
225
-8.2125534
0.03774149
6.190112
-5.354571e-5
-20.86963
2.379142e-8
27.88
300
-4.6757259
0.02354872
4.687353
-3.463308e-5
-11.28031
1.540881e-8
10.46
38
The resulting equations are coupled non-linear partial differential equations, which are
converted to ordinary differential equations and solved by numerical integration [135].
The above model has been used by Siddiq et al [32], [33] to obtain the molar flow rates and
temperature of the syngas in a single-bed catalyst convertor, and the net power produced by
the TSP. For a plant of magnitude similar to that described in Dashti [64] the results for the
nitrogen conversion, syngas temperature and molar flow rates are shown in Figs. 3.1-3.4.
Conversion of N in the synthesis convertor
2
0.25
Conversion of N2 (Z)
0.2
0.15
0.1
0.05
0.5
1.5
2
2.5
Distance (m)
3.5
4.5
Figure 3.1 : Conversion of Nitrogen along a single-bed catalyst

Temperature in synthesis convertor
675
Temperature (K)
670
665
660
655
650
0.5
1.5
2
2.5
Distance (m)
Figure 3.2 : Syngas temperature in converter
39
3.5
4.5
Molar flow rate of H2, N2 and NH3 in convertor

12000
Molar Flow Rate (kmols/hr)
10000
H2
N2
8000
NH3
6000
4000
2000
0.5
1.5
2
2.5
Distance (m)
3.5
4.5
Figure 3.3 : Molar flow rate in converter

8000
7000
Compressor Power (kW)
6000
5000
4000
3000
2000
1000
0
1.5
2.5
3
3.5
Compression Ratio
4.5
Figure 3.4 : Syngas compression requirement

It was found that the overall energy availability from the exothermic synthesis of ammonia is
of the order of 32.4 MW(th), of which about 50% is available in the top 30% of the
convertor. This energy availability was assessed in comparison with the syngas compression
requirement shown in Figure 3.4. As shown, the compressor power is dependent on the
syngas flow-rate, the compression ratio and the initial temperature. As a rough guide a
compression ratio of 3, typical of industrial multistage compressors, would require of the
order of 5 MW(e). The two dominating energy factors of a thermal storage plant based on the
40
endothermic dissociation and exothermic synthesis of ammonia are quantified. It is

determined that the syngas compression may greatly exceed the useful work realizable from
such a plant. Factors to investigate in greater detail include the hydrogen/nitrogen ratio, the
purge gas ratio, the ammonia content of the convertor feed-stream and the catalyst effect. The
computer program developed, using the model described above, can investigate all these
effects and quantify the sensitivity of each independent parameter on the overall system
efficiency, restricted, for the moment to only two important and dominating energy
components. Ammonia concentration in the convertor feed, for example, is an important
parameter as it determines the ammonia production, recirculation rate, and refrigeration
requirement. Yuguo and Changing [152] found that, when inerts and the H2/N2 ratio
remained constant, for ammonia content increase from 2 to 2.5%, power consumption
increased from 6 to 6.1 kW-hr/kmol and ammonia production increased 3% from 985 to
1015 MTD.
3.1.2 Mathematical Models for TSP

Synthesis reactor is considered a fixed bed catalytic reactor and Pseudo homogenous models
are the simplest to use in Catalytic fixed bed reactor modeling. This model assumes that all
the catalyst surface is totally exposed to the bulk conditions and having the same conditions
as the bulk fluid and can thus be fully described by bulk variables (temperature,
concentration, pressure). The Intrinsic reaction rates are used in the reaction model without
any modification.
41
The simplest Pseudo homogenous model is the one dimensional plug flow model, in which
the fluid is assumed to move as a plug through the reactor tube and the reaction rate which
depends on local species concentration, and temperature, is described as rate of specie
generation or consumption per unit reaction volume [148].
A flat velocity profile and uniform temperature and concentration at the radial cross-section
are assumed. The model ignores axial and radial dispersion and heterogeneous effects due to
solid-gas inter-phase gradients [82],[93],[113][134],[141]. This results in coupled non-linear
first-order ordinary differential equations of the initial value type which can be numerically
solved to obtain concentration and temperature profiles as a function of the axial position.
These equations are considerably simpler than a two-dimensional model which accounts for
axial and radial dispersion but results in coupled partial differential equations requiring
advanced numerical techniques and more computational effort.
For simulation of the synthesis process, mass and energy conservation equations are used,
henceforth referred to as the Two-Equation Model (TEM), for chemically reacting species
similar to the ones used by Dashti et. al. [64] and Yuguo and Changying [152]. A catalyst
spatial factor (x) is introduced which may be chosen to be a free parameter or specified
subject to a constraint of total available catalyst quantity. In the former case, a three-zone
single catalyst bed, for example could have discrete values [1 , 2 , 3 ] for (x) . The onedimensional steady-state mass and energy conservation equations in a pseudo-homogeneous
model [64], for the fractional conversion of nitrogen , z , along the synthesis reactor length x
and the temperature of the process gas, in a volume element of an adiabatic bed, are given as:
42
dz ( x) RA
=
dx 2 FNo / A
3.20
and
H r
dT
( x) RA
=
vC
dx
p
3.21
Where is the catalyst activity factor, it is defined to investigate the effects of temperature
and density of the catalyst interior and the difference between these parameters with those of
the catalyst surface, FNo / A is the initial molar flow rate of nitrogen, is the density, H r
is the heat of reaction and RA is the reaction rate.
In the above, the momentum conservation equation is ignored, which has been used, after
numerical solution of the above two equations, by Dashti et. al. [64] for estimating the
pressure drop along the catalyst beds. This introduces a small error as the pressure drop, in
the KBR reactor considered in this work, is less than 2% of the system pressure [64].
3.1.2.1 TEM Model using Activity based Temkin-Pyzhev Form (TP-A):
For the reaction kinetics, the Activity based Temkin-Pyzhev [64] form is used for the
synthesis reaction rate
2
a1H.52 aNH 3
R A = 2k K a a N 2
a NH 3 a1H.52
The equilibrium constant Ka is given by
3.22
log K a = 2.691122 log T 5.51925e 5T + 1.848863e 7T 2 + 2001.6 / T + 2.689
43
and the reaction constant is given by the Arrhenius rate form [93] as
E
k = 8.849 X 1014 exp
RT
where E=170.56 kJ/mol and respective activities ( a N , aH , a NH 3 ) and fugacity coefficients are
defined by equation 3.10.
The governing conservation, non-linear differential, equations are numerically solved using
the Runge-Kutta fourth order method in MATLAB.
The three-bed KBR reactor data used is [10],[23] : Pressure=15 MPa, Inlet Temperature =
643 K, mass flow rate = 183600 kg h-1, mole fractions: y H 2 = 0.6567006 , y N 2 = 0 .2363680 ,
y NH3 = 0.0269300 , y Ar = 0.0202874 , yCH4 = 0.0597140 . Figure 3.5 shows the homogeneous
reactor with the TP-A model. The temperature increases from 643 K to 780 K with a
maximum ammonia mole fraction of 0.1162, corresponding to a molar flow increasing from
486 kmol h-1 to 1930 kmol h-1. It can be seen that the reaction is almost complete at 1.5 m
from inlet.
44
Temperature (K)
800
750
700
650
600
0.5
1.5
2
2.5
Distance (m)
Mole Fraction
0.8
3.5
4.5
3.5
4.5
H2
0.6
0.4
N2
0.2
0
NH 3
0
0.5
1.5
2
2.5
Distance (m)
Figure 3.5 : 3-Bed Homogeneous Reactor with TP-A Kinetics
3.1.2.2 TEM Model using Partial Pressure based Temkin-Pyzhev Form (TP-B):
For the reaction kinetics, the Partial Pressure (Power Law) based Temkin-Pyzhev [142] (TPB) form is used for the synthesis reaction rate:
2
p H3 2
p NH
R A = k1 p N 2 2 k 2 3 3
p NH3
p H 2
3.23
for which the rate constants for synthesis and decomposition are
45
20800
47400
3
1.5
4
k1 = k1o exp
and k 2 = k 2 o exp
, k1o = 1.78954 10 kmol/m -atm
RT
RT
catalyst bed-hr, and k 2 o = 2.5714 1016 kmol-atm0.5/m3 catalyst bed-hr.

The parameter in the kinetic expressions depends on the catalyst characteristics as well as
the range of operating variables [141] and although Temkin and Pyzhev [195] assigned the
value 0.5 in the power-law model for iron catalysts, Dyson and Simon [183] showed that both
values 0.5 and 0.75 satisfied experimental data. Another point that has been observed for this
expression is that the decomposition rate coefficient k 2 , assumed constant, decreases with
pressure [194]. However different values of can be used for the same catalyst. A limitation
of this expression, clearly, is that it is not valid for very low ammonia composition due to the
divergence of the first term. The value =0.6 has been used in this work since Dashti et al
[64] have validated the results with industrial data, based on the Kellogg Brown and Root
horizontal ammonia synthesis reactor.
The governing conservation, non-linear differential, equations are again numerically solved
using the Runge-Kutta fourth order method in MATLAB. The three-bed KBR reactor data
is used to simulate the behavior of the reactor shown in figure 3.6.
46
Temperature (K)
800
750
700
650
600
0.5
1.5
2
2.5
Distance (m)
Mole Fraction
0.8
3.5
4.5
3.5
4.5
H2
0.6
0.4
N2
0.2
0
NH 3
0
0.5
1.5
2
2.5
Distance (m)
Figure 3.6 : 3-Bed Homogeneous Reactor with TP-B Kinetics
With the TP-B model, Figure 3.6 shows a temperature increases from 643 K at inlet to 788 K
with a maximum ammonia mole fraction of 0.1221, and a mole flow increase from 486 kmol
h-1 to 2018 kmol h-1. The error of the power-law model, relative to the activity-based model,
is thus ~6% in T and ~5% in the ammonia molar flow rate. A better model has been found
to be the activity based Temkin-Pyzhev model (TP-A) which does not have a singularity for
zero ammonia composition, which can be the case for a syngas inlet without recycle, and for
which k 2 is constant.
47
3.2 Modeling Unit Operations

The TSP model provides a useful description of the process. The simulations have been
developed using Aspen Plus and HYSYS modules of the AspenTech Process
Engineering Simulation Suit. These simulations make use of many of the capabilities of
AspenTech Process Engineering Simulation Suit including unit operation models, physical
property methods, models and data, and flowsheeting capabilities like convergence design
specs etc. The model provides rigorous mass and energy balance information for dissociation
process, ammonia production process, Flash tank and other components in storage plant [7].
This model can be used to support the conceptual process design. The TSP model is meant to
be used as a guide for process optimization for maximum energy recovery. It can also be
used as a starting point for more sophisticated models.
Both the Dissociation and Synthesis reactors are considered as fixed bed catalytic reactors.
In AspenTech Process Engineering Simulation Suit, the PFR is augmented by including
axial and radial dispersions, for both mass and heat transport [7] resulting in coupled partial
differential equations requiring advanced numerical techniques and more computational
effort.
3.2.1 Dissociation Reactor

The dissociation reactor, considered as a fixed bed catalytic reactor, is modeled using a Plug
Flow Reactor (PFR) with a specified uniform external heat flux profile in Aspen Plus as
48
shown in figure 3.7. If the length of Plug Flow Reactor is less than its diameter, the axial
dispersion of mass and heat are not significant [7],[148].
Figure 3.7 : PFR Dissociation Reactor in Aspen Plus

The dissociation is carried out in a temperature range of 520-580 oC and a pressure of 150
bar using Ni-Pt catalyst [128]. The data presented in table 3.3 is used as input to stream
DIS-IN.
TABLE 3.3: Input Data for Dissociation Reactor
Parameter
Process Pressure
Inlet Temperature
Mass Flow Rate
Reactor Length
Reactor Diameter
Value
P=15MPa (150 bar)
T=793 K (520 oC)
-1
m& =0.125 kgs
L=1m
D=1.5m
The Temkin-Pyzhev reaction rate is specified in Aspen Plus through the stoichiometric
coefficients for ammonia (-1), nitrogen (0.5), and hydrogen (1.5) and with basis specified to
be partial pressures, for a liquid-vapor reaction phase. The reaction is specified as a Powerlaw class for a kinetic expression of the form:
E
rNH 3 = ko exp
pNH 3
RT
49
where rNH 3 is the reaction rate for decomposition of ammonia, ko is the frequency factor and
its value is 1.33x108 kmol m-3 s-1 Pa-1 while activation energy E equals 190000 kJ kmol-1 [6].
Figure 3.8 : Dissociation Reactor Exit Composition
Figure 3.9 : Dissociation Reactor Temperature Profile
Simulation results of dissociation reactor are presented in figures 3.8 and 3.9. Ammonia
conversion completes at reactor length of 1m while the maximum possible temperature at
reactor exit is around 535 oC.
50
3.2.2 Synthesis Reactor-Aspen Plus Model

The Synthesis reactor is modeled using an Adiabatic Plug Flow Reactor (PFR) as shown in
figure 3.10. Since Synthesis reactor is adiabatic, radial dispersion in negligible because there
is no driving force for long range gradients to exist in the radial direction hence resulting in
two dimensional model [7],[148].
Figure 3.10 : PFR Synthesis Reactor in Aspen Plus

The three-bed KBR reactor data presented in table 3.4 is used as input to stream SYN-IN.
TABLE 3.4: Input Data for Synthesis Reactor
Parameter
Process Pressure
Inlet Temperature
Mass Flow Rate
Value
P=15MPa (150 bar)
T=643 K (370 oC)
m& total =183600 kgh-1
Hydrogen Mole Fraction

Nitrogen Mole Fraction
Ammonia Mole Fraction
Argon Mole Fraction
Methane Mole Fraction
Reactor Length
Reactor Diameter
y H = 0 . 6567006
y N = 0.2363680
y NH 3 = 0.0269300
y Ar = 0 .0202874
yCH 4 = 0.0597140
L=4.5m
D=5.046m
51
The Temkin-Pyzhev reaction rate is specified in Aspen Plus through the stoichiometric
coefficients for nitrogen (-1), hydrogen (-3) and ammonia (+2). The basis is specified to be
partial pressures, for a vapor reaction phase. The reaction is specified as a Power-law class
for a kinetic expression form of partial pressure based Temkin Pehzev (TP-B):
r = [ KineticFac tor ] [ DrivingFor ce]
The components are specified in Table 3.5.

TABLE 3.5: Reaction Input for Temkin-Pyzhev Power-Law Expression in Aspen Plus
Nitrogen
Hydrogen
Ammonia
A
B
C
D
Forward
1
1.8
-1.2
9.79227
-10467
-
Reverse
0
-1.2
0.8
37.785812
-23852.69
-
The parameter in the kinetic expression is taken to be equal to 0.6.
Figure 3.11 : Synthesis Reactor Exit Composition (Aspen Plus)

52
Figures 3.11 and 3.12 show a temperature increases from 370 oC at inlet to 513.82 oC with a
maximum ammonia mole fraction of 0.1231 at reactor length 1.5 m.
Figure 3.12 : Synthesis Reactor Temperature Profile (Aspen Plus)
3.2.3 Synthesis Reactor- HYSYS Model

Synthesis Reactor is modeled as Plug Flow Reactor PFR-100 shown in figure 3.13 The
Temkin Pyzhev kinetic rate expression, with = 0 .6 is used in HYSYS.
Figure 3.13 : Plug Flow Reactor in HYSYS

The Temkin-Pyzhev Model B is specified in HYSYS through the stoichiometric
coefficients for nitrogen (-1), hydrogen (-3) and ammonia (+2) and the forward order of the
rate information (nitrogen 1.00, hydrogen 1.80, and ammonia -1.20) and the backward order
(nitrogen 0, hydrogen -1.20, and ammonia 0.80). The base component is specified to be
53
nitrogen, the basis is specified to be pa

partial
rtial pressures, for a vapor reaction phase with
minimum temperature -273.1
273.1oC and maximum temperature 3000oC. HYSYS requires the
reaction rate to be specified in the form r = k * f ( Basis ) k ' f ' ( Basis ) where
k = A exp( E / RT ) T b
with
A = 17895
and
E = 87027 kJ / kmol , b = 0
'
16
'
5
'
k ' = A ' exp( E ' / RT ) T b with A = 2.5714 10 , E = 1.9832 10 kJ / kmol , b = 0 .
'
Figure 3.14 and Fig.3.15 show that for an inlet temperature of 370oC, the outlet is 513.7oC,
no pressure drop is assumed, and saturation is observed at 1.5m for an ammonia mole
fraction of 0.123.
Figure 3.14 : Synthesis Reactor Temperature Profile (HYSYS)
54
Figure 3.15 : Synthesis Reactor Exit Composition (HYSYS)
3.2.4 Flash Tank

The Flash Tank is modeled using a FLASH2 seperator (figure 3.16). It is used to separate
feed into two outlet streams, using rigor
rigorous vapor-liquid equilibrium.
Figure 3.16 : Flash Tank in Aspen Plus

55
TABLE 3.6: Flash Tank Output

Molar
Composition
Hydrogen
Nitrogen
Ammonia
Argon
0.5776749
0.21166301
0.12316376
0.02218853
Equilibrium
Liquid Mole
Fraction
0.00638187
0.03253954
0.93099292
0.00406039
Equilibrium
Vapor Mole
Fraction
0.61373434
0.2229691
0.07217439
0.02333276
3.2.5 Purge Gas & Recycle

A splitter is used to divide the VAPOR stream into PURGE and RECYCLE streams with a
purge split fraction of 0.095.
Figure 3.17 : Splitter in Aspen Plus
Stream data for VAPOR, PURGE and RECYCLE streams is presented in table 3.7.
TABLE 3.7: Molar Flow Rates of Components in and out of Splitter
Molar Flow
Rate
(kmol/hr)
Component
HYDROGEN
NITROGEN
AMMONIA
ARGON
VAPOR
9526.794
3461.075
1120.339
362.1868
56
PURGE
905.04543
328.802125
106.432205
34.407746
RECYCLE
8621.74857
3132.272875
1013.9068
327.779
A mixer (MIXER) is used to combine the Feed stream (FEED1) from storage tank and
Recycle stream (RECYCLE) as shown in figure 3.18
Figure 3.18 : Mixer in Aspen Plus
3.2.6 Heat Exchangers and Waste Heat Recovery

3.2.6.1 Counter Flow Heat Exchanger (CF-HX):
The stream DIS-IN is pre-heated by passing it through the counter flow heat exchanger (CFHX) in order to increase its temperature from 30 oC to 370 oC.
Heat duty of CF-HX= + 6.898 kWth
Figure 3.19 : Counter Flow Heat Exchanger (CF-HX)
57
3.2.6.2 Thermal Heat Exchanger (SRIN-HX):

The temperature of the output from mixer (MIX-OUT) is 30 oC so it is heated in SRIN-HX to
a temperature of 370 oC prior to enterance in SYNRCTR.
Figure 3.20 : Thermal Heat Exchanger (SRIN-HX)
Heat Duty of SRIN-HX = +51828.236 kWth
3.2.6.3 Thermal Heat Exchanger (SROUT-HX):

Heat generated in SYNRCTR is extracted in thermal heat exchanger SROUT-HX prior to
entry in FLASHT.
Figure 3.21 : Thermal Heat Exchanger (SROUT-HX)
Heat Duty of SROUT-HX: -76532.016 kWth
58
3.3 Modeling the Integrated Plant
Figure 3.22 : Integrated Plant
Net Heat Recovery = + 6.898 kWth + 51828.236 kWth -76532.016 kWth = -24696.882 kWth
Net Heat Recovery = - 24.7 MWth
3.4 Two Equation Model (TEM) Validation:

The one-dimensional pseudo-homogeneous model has been validated with industrial data to
quantify its accuracy for modeling and simulation of the ammonia conversion process.
Elnashaie and Elshishini [142] have compared results of the outlet temperatures from a
three-bed industrial ammonia reactor with inter-stage cooling and found a maximum
deviation of less than 2%. Industrial data from the Kellogg type ammonia synthesis reactor,
used in this work, is also considered for model validation [54][64][152] and optimization
with one- and two-dimensional models. Yuguo and Changying [152], using a onedimensional model for an ammonia plant incorporating unit operations for compression,
59
ammonia synthesis, vapor-liquid separation, and refrigeration, calculate 11.58% ammonia in

converter effluent compared with industrial data of 12%, i.e., a relative error of -3.5%.
Sadeghi and Kavianiboroujeni [54], validating the models for comparison of the bed outlet
temperatures with data from a four-bed Kellogg ammonia reactor, compute the first-bed
outlet temperature as 505.58C from a one-dimensional steady-state heterogeneous model,
and 502.85C from a two-dimensional rigorous cylindrical model, compared with the
industrial data temperature of 501.5C giving a relative error of 0.81% and 0.27%
respectively. The relative errors reported in the outlet temperatures for all beds are in the
range 0.8% to 1.5% for the one-dimensional model compared with 0.2% to 0.4% with the
two-dimensional model.
800
780
1D (TP-B)
RK-4
HYSYS
HYSYS
Aspen
Plus
AspenPlus
Temperature (K)
760
740
720
700
680
660
640
0.5
1.5
2
2.5
Distance (m)
3.5
4.5
Figure 3.23 : Comparison of 1-D (TP-B) model, HYSYS, and Aspen Plus results
60
Figure 3.23 illustrates the comparison between the 1-D model (TP-B), HYSYS and Aspen
Plus results. Though the 1-D model varies significantly from the HYSYS and Aspen
Plus results, there is little difference in the saturation values. Thus all models give
saturation, and hence the physical dimensions of the first bed of the reactor as between 1.5m
and 1.75m.
Percentage errors in 1-D, TEM-TPA and TEM-TPB models compared with 2-D HYSYS
and Aspen Plus models are presented in table 3.8.
TABLE 3.8: Percentage errors in 1-D Models compared with HYSYS and Aspen Plus
T 0
Model
1-D RK-4 TP-A
1-D RK-4 TP-B
HYSYS
Aspen Plus
137
145
134.7
134.7
% error
1.7
7.6
0
-
0
y NH
3
0.1162
0.1221
0.1230
0.1230
% error
-5.5
-0.7
0
-
It can be concluded that a one-dimensional model is adequate, and justified, to simulate the
ammonia conversion process and to carry out an optimization analysis, and uses considerably
less computational effort than a two-dimensional rigorous model.
61
4 PLANT OPTIMIZATION
4.1 Review of Optimization Techniques
Optimization is a widely used engineering tool for enhancing the energy efficiency, and
hence the economic competitiveness, in chemical industry. It is aimed at finding some
optimal set of design and operating parameters which enables industry to function in a best
possible way.
Design parameters, such as physical dimensions and materials of plant components, are the
basis of fabrication and subsequent plant erection. Operating parameters, on the other hand,
involve process variables, such as flow rates, pressures and temperatures, which are
integrated into the overall plant units. As an example, a urea fertilizer chemical process plant
has four large integrated units: reforming, ammonia, urea, and utilities, all of which involve
inter-dependent process variables. The overall system is thus not only large in magnitude, but
its interdependence in the form of re-cycle streams, for example, renders the determination of
optimality as a complex non-linear problem. The process of optimization is thus both
theoretical and practical as it is based on mathematical models which are non-linear and
utilize material properties at actual plant conditions. These can be obtained from on-line
chemical analysis during plant operation. Once formulated, the system of equations needs to
be solved by analytical or numerical methods often requiring powerful computer hardware
and sophisticated simulation software. Optimization analysis for a solar thermal plant
requires a mathematical framework to model the underlying processes, the physical and
62
chemical data of the plant and its materials, and numerical techniques to carry out a
simulation to achieve the objective of determining optimality.
Figure 4.1 : Optimization Process

The objective of optimization studies is to determine optimality which will result in
maximum efficiency of the plant, by which it will be taken to mean optimality of the
synthesis reactor in the integrated plant. Several other objectives, as diverse as plant and
equipment sizing, minimizing inventory charges, and allocating resources among several
processes, may be defined [65][100]. Other terms that are analogously used for objective
function, process model, and constraints are economic cost (or profitability) function and
feasible solution. An optimization problem, formulated as an objective function f ( x1 , x 2 )
with two independent variables x1 , x 2 , subject to an equality constraint g ( x1 , x 2 ) = 0 and
possibly N inequality constraints of the form hi ( x1 , x2 ) 0, i = 0,1,2L N will then have a
feasible region illustrated by Figure 4.1 [100]. An optimal solution will then be determined as
falling in the feasible region defined as satisfying all the constraints and having an extremum.
For such a problem, the dashed lines in the figure would show the infeasible regions for the
63
inequality constraints while the solid line would show the equality constraint. Of all the
values of the variables x1 , x 2 lying in the feasible region, one would need to determine the
particular one set, or a number of sets, which would correspond to the extremum.
Possible obstacles in the optimization process are non-linearities, discontinuities,
insensitivity of the objective function to independent variables, and local extrema confused
with a global extremum.
Figure 4.2 : Mathematical Methodology to solve governing equations
The mathematical methodology is then identified to solve the governing equations and carry
out a simulation to obtain the optimal set of parameters. These methodologies may be
64
broadly classified as deterministic or stochastic. The former are illustrated in Figure 4.2 [100].
Thus, numerical techniques such as the Runge-Kutta method for solving a non-linear set of
coupled first-order ordinary differential equations may be used, while the latter is based on
either an analogous stochastic simulation of the phenomena or on stochastic methods to solve
a deterministic set of governing equations. A typical example of a full stochastic simulation
is analog, or biased, Monte Carlo simulation, while a typical example of a stochastic
technique for a deterministic set of governing equations are random search methods such as
Genetic Algorithms (GA).
One way of classifying modeling problems [100] is from the degrees of freedom
N f = N v N e , in terms of the number of variables Nv , and the number of independent
equations Ne . When
N f = 0 the problem is exactly determined and for a linear set of
independent equations, there is a unique solution, while for non-linear equations there may
be multiple solutions or no real solution. Such problems do not constitute an optimization
problem. When N f > 0 , the problem is underdetermined and at least one process variable
can be optimized. Conversely N f < 0 , constitutes an over-determined problem and the set
of equations has no solutions and methods, such as the least squares method, can be used to
determine the unknowns.
Widely used optimization methods include the following areas [100]: one-dimensional search,
unconstrained multivariable optimization, linear programming, nonlinear programming,
optimization involving discrete variables, and global optimization (operations research,
65
including Monte Carlo, heuristic methods, GA and evolutionary methods). Some widely used
techniques for obtaining optimality are (i) the deterministic variational functional optimality
based on Pontryagins Maximum Principle, and (ii) the Genetic Algorithm optimization
search [80][100]. The GA search method has been used [65],[100] for the optimization of an
ammonia synthesis reactor [65] shown in Figure 4.3.
Figure 4.3 : Counter-Flow Ammonia Synthesis Reactor
First, the governing equations are numerically solved to obtain the temperature and
concentration profiles shown in Figure 4.4.
Figure 4.4 : Temperature & Concentration Profiles along Converter Length

66
Figure 4.4 uses the same scale for Temperature and Concentration, it is not clear in reference
65 , whether these values of temperature and concentration have been normalized to show
them on the same scale or not.
The numerical solution is followed by an optimization exercise in which an objective

function f ( x, N N 2 , T f , Tg ) is defined along with the three governing equations, taken as
constraints. Thus, the problem has one variable (x; the reactor length) one degree of freedom
( N f = 1) and, being underdetermined, can be solved for optimality. The GA search is carried
out as shown in Figure 4.5.
Figure 4.5 : GA Search Algorithm

The optimal solution found for the exit conditions shown in Table 4.1.
TABLE 4.1: Optimal solution for the exit conditions
67
The optimization thus concludes that a reactor with initial guesses of Nitrogen concentration,
Mole fraction, feed gas and reacting gas temperatures, reactor length and cost result in an
optimal solution with values given in table 4.1.
Figure 4.6 : Four-Bed Synthesis Reactor
Sadeghi and Kavianiboroujeni [54] have used the Genetic Algorithm for a 1-D and 2-D
optimization of a Kellog-type ammonia plant, located at Khorasan (Iran). The axial reactor
(Figure 4.6) has four promoted-Fe catalytic fixed beds with a heat exchanger at the top.
Syngas flows vertically upwards in the spaces between the two walls of the reactor, where it
is pre-heated, then turns down through the beds and from the bottom fourth bed again turns
upwards, exiting from the top of the reactor. The independent parameters investigated are the
quench flow and quench temperature. Between the beds, the hot syngas is mixed with quench
streams (shown in three streams between the beds) to control the temperature.
68
Figure 4.7 : Effect of Quench gas on conversion efficiency

The purpose of injecting the quench streams is, clearly, to increase the ammonia production
from the reactor; and since the forward synthesis chemical reaction is favoured by high
pressure and low temperature, the challenge is to reduce the temperature at every bed exit.
The ammonia and nitrogen conversion obtained by Sadeghi and Kavianiboroujeni [54] by a
numerical solution of the mass and energy balance equations is shown in the Figure 4.7. It
can be seen that most of the ammonia conversion takes place in the first bed even though it is
the shortest. The effect of the quench gas is to reduce the ammonia conversion after every
bed exit but this picks up as flow proceeds.
The paper uses GA for obtaining optimal temperature distribution, in this nonlinear
optimization problem, resulting from a given quench flow, and subsequently optimal quench
flow given quench temperature. In the optimization problem, the objective function is the
69
ammonia outlet flow-rate, while the constraints are (i) T < 800 K , in the reactor for avoiding
hotspots, (ii) an ascending nitrogen conversion during optimal flow: Z | x < Z | x +x , and (iii)
for the syngas: Tin < Tout .
Figure 4.8 : GA Algorithm for obtaining optimal temperature distribution
The flow-chart, Figure 4.8, for this optimization is reproduced from the paper [54] and their
results, in Figure 4.9, give maximum ammonia conversion at a quench temperature of 650 K
and a maximum conversion flow-rate of 47%
70
Figure 4.9 : Optimal and Normal Ammonia Production Rates

The important changes between normal and optimal operations for nitrogen conversion and
reaction rate are shown in Figure 4.10.
Figure 4.10 : Optimal and Normal Nitrogen Conversion and Reaction rates
GA used for obtaining optimal temperature distribution has increased the ammonia
production of the Khorasan plant by 3.3% (8,470 tons per year).
When the reactor is isothermal, different catalysts can be loaded to enhance productivity and
when it is non-isothermal i.e. it has temperature gradients, then the catalyst may be non71
uniformly loaded or different catalysts may be used for different temperature regions, to
enhance productivity. Finding the optimal (spatial) distribution of catalyst is crucial to
optimizing the performance. Numerical search can be carried out by dividing the reactor in
zones and assuming uniform values of catalyst material in each zone; this will mostly result
in a sub-optimal solution.
4.2 Optimal Analysis using Variational Calculus

Variational methods have also been used to find optimal configurations for process variables
in a synthesis convertor. These methods originate from the works of Leibniz (1646-1716) and
Newton (1643-1727) credited for inventing and formalizing Calculus; followed by
Variational Calculus attributed to Leonhard Euler (1707-1783) through his published work
of 1733. Among the several contributors to variational calculus were Lagrange (1736-1813),
Legendre (1752-1833), Gauss (1777-1855), Cauchy (1789-1857), and Poisson (1781-1840).
The field of Optimal Control [180] is an area of optimization in which the best possible
strategy is chosen using the calculus of variations. While calculus can be used for
optimization of a function of variables, calculus of variations is used to obtain the extremum,
or stationary condition, of a functional (function of a function) by finding the function which
extremizes the functional. The first variational calculus optimal problem was the
Brachistochrone (shortest time) Problem solved by Bernoulli in 1696 [185]. The formulations
used are by Lev Semenovich Pontryagin (1908-1988), who developed the Maximum
Principle, and the terminology of Bang-Bang control to steer a system with maximum or
minimum control parameters, and of Bellman (1920-1984) who extended works of Hamilton
72
(1805-1865) and Jacobi (1804-1851) to the now well-known Hamilton-Jacobi-Bellman

(HJB) equations in Dynamic Programming.
Variational calculus [181],[182],[185] is used in areas that include optimal control, particle
transport, mechanics, optics and chemical plant design [158]. There is a vast range of
problems that determine complexity, such as whether the functional involves one or several
functions, derivatives of functions, and one or more than one independent variable. Another
class of variational calculus problems involves constrained problems with algebraic, integral
or differential equation constraints.
The optimality conditions for Pontryagins Maximum Priciple (PMP) can be derived from
the first principle of conservation of matter. Consider the reversible Ammonia synthesis
process
N 2 + 3H 2 2 NH 3
The mass balance equation for this reaction can be written in dimensionless form as:
dy N
= f [ y N , y H , y NH 3 , K a ]
dx
4.1
Where yH , y NH 3 and y N represent the mole fractions of hydrogen, ammonia and nitrogen
respectively while x is the normalized distance along catalyst bed (m).
Mole fractions of hydrogen ( yH ) and ammonia ( y NH 3 ) are related to nitrogen mole fraction
( y N ) as:
o
y NH3 = y NH
+ 2( yNo y N )
3
4.2
73
y H = y Ho 3( y No y N )
4.3
o
Where y NH
, y No and y Ho are initial mole fractions of ammonia, nitrogen and hydrogen
3
respectively.
In equation 4.2 and 4.3, the term ( y No y N ) = z N represents the converted moles of nitrogen
and fractional conversion of nitrogen can be presented as:
y No y N
zN =
y No
4.4
So equations 4.2 and 4.3 in terms of fractional conversion of nitrogen are

o
yNH 3 = yNH
+ 2 y No z N
3
4.5
y H = y Ho 3 y No z N
4.6
Therefore mole fractions of hydrogen and ammonia can be removed from the reactor model
equation and making it only a function of y N
dy N
= f ( y N , K a ( )) f ( y N ( x), ( x))
dx
4.7
Where f ( y N , ) is the rate of reaction equation in terms of nitrogen mole fraction y N and
temperature at any point along the length of reactor such that
at t = 0,
y N = y No ;
x (0,1)
74
( x) is the control variable for which the optimal variation along the length of the reactor is
sought, that maximizes the exit conversion.
Equation 4.4 can be written as:
y N = z N y No y No
y N = y No (1 z N )
4.8
Differentiating Equation 4.8 w.r.t x yields

dy N
dz
= y No N
dx
dx
dz N
1 dy
= o N = G ( y N , )
dx
y N dx
The objective is to maximize the nitrogen conversion
M =
1
y No
4.9
dz N
, so we can write
dx
dy
0 dxN dx = 0 G ( y N , )dx
4.10
Now if we consider that the optimal temperature profile that gives the maximum conversion
( M ) is ( x) and consider an infinitesimal variation in ( x) to make it + then y N ( x)
will change to y N + y N and M to M + M . Thus,
1
M + M = [G ( y N , ) +
0
G
G
y N +
]dx
y N
4.11
and since, M = G ( y N , )dx

0
thus,
G
G
y N +
]dx
y N
0
1
M =
4.12
Comparing equation 4.7 and 4.9 yields
75
dy N
dz
= y No N = f ( y N ( x), ( x))
dx
dx
4.13
Consider the change in f
f =
f
f
y N +
y N
4.14
dz
f
dy f
yNo N = N =
yN +
dx
dx yN
f
y f
d N =
y N +
dx y N
4.15
Multiplying equation 4.15 by the Lagrange Multiplier (sensitivity coefficient/ adjoint

variable), ( x) integrating from x = 0 to x = 1 and adding the result to equation 4.12 gives:
1
dy N
f
f
G
G
M =
+
y N +
y N
dx
d
x
N
N
4.16
Rearranging equation 4.16 yields

1
M =
y N +
y N
dx +
y N dx
y
y
d
x
N
N
0
0
4.17
The last term on the right hand side of equation 4.17 is integrated by parts to give:
1
d
d
(y N )dx =y N (1). (1) y N (0). (0) y N
dx
dx
dx
0
1
4.18
If we consider the feed concentration to have a fixed value, then, y N (0) = 0 and we impose
76
the boundary condition on the Lagrange multiplier as (1) = 0 and define the Hamiltonian (
H ) of the system as,
H = . f G
4.19
Then equation 4.16 can be written as,

1
H d
H
M =
dx
y N dx +
y
d
x
0
0
1
4.20
For ( x) to be the optimal temperature profile, we must have, M = 0 .Thus the optimality
conditions are:
H
H d
=0
= 0 and
y N dx
for all values of x
4.21
The adjoint equation is therefore:

d H
=
dx y N
and
(1) = 0
4.22
and the optimality condition according to Pontryagins maximum principle is:

H
=0
4.23
Which gives the global maxima for the objective function [155],[180]
From the optimality condition (4.23), it can be shown that the problem reduces simply to that
of finding the temperature profile ( x) that maximizes the net rate of reaction at each point
along the length of the reactor. Since G =
f ( , y N )
terms of f ( , y N ) as follows:
77
yN
, the Hamiltonian can be written in
H = . f G = . f
1
1 dy N
dz
f = . f o
= . f + N
o
yN
y N dx
dx
Or
H=
dz N
+ . f
dx
4.24
4.3 Parametric Sensitivity Analysis

This section considers the optimal design of TSP by calculating the process variable
sensitivities for different components.
Sensitivity analysis is an optimization tool for determining how a process reacts to varying
key operating and design variables. It can be used to vary one or more flowsheet variables
and study the effect of that variation on other flowsheet variables. It is a valuable tool for
performing what if studies. Sensitivity analysis can be used to verify if the solution to a
design specification lies within the range of the manipulated variable [55].
4.3.1 Effect of Temperature on Dissociation

Objective: Minimize the molar composition of Ammonia in stream DIS-OUT
Manipulated Variable: Process Temperature
The results of Temperature Sensitivity of dissociation reaction at a pressure of 150 bar are
shown in figure 4.11. The favorable range of values for process temperature are from 450850 oC after which catalyst burns out and there is no conversion of ammonia.
78
Figure 4.11 : Effect of Temperature on Dissociation
4.3.2 Effect of Flow Rate on Dissociation

Objective: Minimize the molar composition of Ammonia in stream DIS-OUT
Manipulated Variable: Mass flow rate of ammonia in stream DIS-IN
Figure 4.12 : Effect of Flow Rate on Dissociation
The results of Flow rate Sensitivity of dissociation reaction at a pressure of 150 bar and
temperature of 520 oC are shown in figure 4.12. If the mass flow rate of ammonia in stream
79
DIS-IN increases 550 kg/hr, conversion process is not complete and mole fraction of
ammonia in stream DIS-OUT increases.
4.3.3 Effect of Pressure on Synthesis

Objective: Maximize the molar composition of Ammonia in stream SYN-OUT
Manipulated Variable: Process Pressure
Figure 4.13 : Effect of Pressure on Synthesis

The results of Pressure Sensitivity of Synthesis reaction at a temperature of 370 oC are
shown in figure 4.13. There exist nearly a direct proportionality in between increase in
pressure and mole fraction of ammonia at reactor exit from 100 bar to 500 bar. The limiting
case are the pressures below 100 bar, where ammonia production decreases.
4.3.4 Effect of Temperature on Synthesis

Objective: Maximize the molar composition of Ammonia in stream SYN-OUT.
Manipulated Variable: Process Temperature
80
Figure 4.14 : Effect of Temperature on Synthesis

The results of Temperature Sensitivity of Synthesis reaction at a pressure of 150 bar are
shown in figure 4.14. As temperature increases, there is a decrease in ammonia production in
the reactor. It is clear from figure 4.14 that a temperature range of 280-400 oC is suitable for
a process pressure of 150 bar.
Figure 4.15 presents the results of parametric sensitivity for synthesis reactor. For higher
pressures, Ammonia production is possible at even lower process temperatures.
Figure 4.15 :Temperature & Pressure Parametric Sensitivity for Synthesis

81
4.3.5 Effect of Flash Temperature on Liquid Ammonia Separation

For choosing flash temperature, there are two constraints, maximum liquification of
ammonia is desirable and the mole fraction of ammonia should be maximum in the stream
NH3PROD.
To achieve the desired results, two sensitivities are designed that yield exactly opposite
results to each other. Figure 4.16 depicts a decrease in molar flow of ammonia in stream
PRODNH3 with increase in temperature while an increase in flash temperature favors
increase in mole fraction of ammonia in product stream (figure 4.17).
Figure 4.16 :Effect of Flash Temperature on Ammonia Flow Rate
Figure 4.16 depicts a decrease in molar flow of ammonia in stream PRODNH3 with increase
in temperature while an increase in flash temperature favors increase in mole fraction of
ammonia in product stream (figure 4.17).
82
Figure 4.17 :Effect of Flash Temperature on Ammonia Mole Fraction
4.3.6 Effect of Purge Fraction on Ammonia Liquification

The effect of purge fraction in Splitter on Ammonia liquification in stream PRODNH3 is
presented in figure 4.18 which predicts a direct proportionality between the two factors but
the maximum purge fraction is limited by the fact that Syngas is precious and higher purge
fractions will result in decrease in mass flow rate of the closed loop system.
Figure 4.18 :Effect of Purge Fraction on Ammonia Liquification

83
4.3.7 Effect of Recycle Stream on Synthesis

By using Recycle Stream, ammonia mole fraction in SYN-OUT stream increases from
0.1231 to 0.1355.
84
5 AN OPTIMAL STORAGE PLANT

5.1 Process Modifications
This section is aimed at finding the optimal process parameters specially optimal temperature
profile for synthesis reactor using the principles of variational calculus described in section
4.2.
5.1.1 Optimal Analysis Problem Formulation- Process Modifications

The optimization problem for the activity based Two Equation Model (TEM-TPA) can be
L
formulated as: maximize = z ( L) z (0) =

0
dz
dx
dx
subject to the constraints given by the
governing equations 3.20 and 3.21. The Hamiltonian is written as

=
dz
+ 1 f1 + 2 f 2
dx
5.1
Where 1 and 2 are Lagrange multipliers and f1 and f 2 are constraint equations referring to
mass and energy conservation equations.
Equation 5.1 yields the Lagrange multipliers (Co-state equations) as:
d1
=
dx
z
5.2
and
d2
=
dx
T
5.3
85
with the boundary conditions 1 ( L ) = 2 ( L ) = 0 . For a stationary Hamiltonian / u = 0 ,

where u is the control variable that represents the optimal temperature.
5.1.2 OEM using Activity based Temkin-Pehzev form (OEM-TPA)

Considering the case f 2 0 , i.e. only the mass conservation equation, henceforth referred
to as the One-Equation Model (OEM-TPA), as considered by Mansson and Andresen [157],
an optimal condition can be found for the temperature T as the control variable. This reduces
to the case of a single Lagrange multiplier 1 . The Hamiltonian is thus = (1 + ) f 1 ,
and the optimality condition is

RA
=0=
u T
T 2 FN0 / A
5.4
The optimal temperature distribution can be obtained by solving the equation
RA
R
+ A = 0
T 0
T 0
5.5
Figure 5.1 shows the process gas temperature, the optimal temperature obtained from
equation 5.5, and the equilibrium temperature [1]. The gas temperature T increases rapidly in
the reactor saturating to 780 K while the predicted optimal temperature Topt starts at a high
value, decreases rapidly and saturates to 738 K. The equilibrium temperature Teqm , following
the same trend as Topt saturates to the higher value of 786 K. Best ammonia conversion is
thus achieved by realizing this optimal profile.
86
1000
950
Teqm
Temperature (K)
900
850
800
Topt
750
T
700
650
600
0.5
1.5
2
2.5
Distance (m)
3.5
4.5
Figure 5.1 : Homogeneous reactor with 1-D Model (TEM-TPA) showing gas
temperature T , equilibrium temperature Teqm , and optimal temeprature Topt
The equilibrium temperature, Teqm , is defined as the temperature at which the optimal
concentration would be at equilibrium. Thus, for the synthesis reaction N 2 + 3H 2 2 NH 3 ,
the optimal molar fractions X oi and system pressure P are used to obtain the equilibrium
constant at zero pressure K a 0 from which Teqm is found.
K a0
( X o , NH 3 ) 2
1
.
= 2
P ( X o,H 2 ) 3 ( X o,N 2 )
87
For the equilibrium composition [96], we determine the extent of the reaction, with the
optimal composition taken as the initial composition, from a numerical solution of the
equilibrium relationship
o
(n NH
+ 2 ) 2 (nTo 2 ) 2
3
(n Ho 3 ) 3 (n No )
= K ao (Topt ) P 2 .
The optimal and equilibrium temperatures show a trend, especially at reactor inlet, which
represent a theoretical goal to achieve optimality. It can be seen from Figure 5.1 that there
is a substantial difference between the inlet temperatures, actual and optimal, but this
decreases as the reaction proceeds. Ideally, the inlet gas should be heated to the optimal
temperature and a heat exchanger should gradually remove the heat of the (exothermic)
reaction so that the resulting temperature decreases, rather than increasing, as gas flows in the
reactor. The optimal profile of figure 5.1 is thus in line with the requirement of a high
temperature to favor a high reaction rate at inlet, but as the exothermic ammonia synthesis
reaction proceeds, heat is generated and, according to Le Chateliers principle, the reaction is
driven in the backward direction to favor reactants. Thus optimality requires a gradual
decrease in temperature, to increase the equilibrium constant given by the Vant Hoff
equation, and subsequently increase product formation [93],[96]. The actual temperature, as
shown in figure 5.1 is in sharp contrast to the optimal temperature since the inlet temperature
is limited by process parameters and the limits of the catalyst supplied by the manufacturer.
This work evaluates the approach-to-optimal by the use of inter-bed heat exchangers which
succesively reduce inlet temperatures and permit saturation to the optimal profile, achieving
88
higher conversion, in line with the S-300 Haldor Topse [21] which is a feature of all new
ammonia plants.
5.1.3 OEM using Partial Pressure based Temkin-Pehzev form (OEM-TPB)

A simpler formulation [141] is here considered for the determination of the optimal heat
removal strategy with the objective of maximizing ammonia conversion. In this case, the
energy equation (3.21) can be written, with a control variable u~ , as
vC p
dT
= (H r ) ( x) RA u~ f 2 [ z ( x), T ( x)] u~
dx
5.6
We thus seek heat removal 0 u~ u max which can be found by expressing the Hamiltonian as
=
dz
+ 1 f1 + 2 ( f 2 u )
dx
5.7
where u u~ /( vC p ) . The Costate equations are then

d1
f
f
=
= [(1 + 1 ) 1 + 2 2 ]
dx
z
z
z
5.8
and
d2
f
f
=
= [(1 + 1 ) 1 + 2 2 ]
dx
T
T
T
5.9
With boundary conditions 1 ( L) = 0 = 2 ( L) .

The Stationarity condition is defined as:
H
f
f
= 0 = (1 + 1 ) 1 + 2 2 2 = 0
u
u
u
5.10
89
H
= 0 = 2
u
5.11
Substituting value 2 of in equation 5.9 yields

d2
f
f
= [(1 + 1 ) 1 + 2 2 ] = 0
T
T
dx
5.12
This formulation yields the optimal temperature from a solution of

R A
T
PH3
E
= 1 2 k1 PN 2 2 2
PNH
RT
3
P2
E2 k 2 NH 3
RT 2 PH32
=0
5.13
Solving Eqn. 5.13 is thus analogous to maximizing the ammonia conversion in the reactor.
For equation 5.13, the optimal temperature is found in a compact form:
Topt =
E2 E1
R ln
where
5.14
2
k 20 E 2 PNH 3
.
k10 E1 PH32 PN 2
The effect of heat removal at the exit of the first bed is shown in figure 5.2. The drop in interbed temperature, taken here as 106 K, is arbitrary and can be adjusted according to the power
requirement, but this will have an effect on the entrance temperature for the second bed, and
hence on the saturation length.
90
1000
Temperature (K)
950
900
850
800
Topt
Teqm
750
700
650
0.5
1.5
2
2.5
Distance (m)
3.5
4.5
Figure 5.2 : Temperature in homogeneous reactor compared with one-equation optimal

temperature Topt and equilibrium temperature Teqm .
The mole fractions of hydrogen, nitrogen and ammonia at bed exits are: 0.5894, 0.2153,
0.1089; 0.5534, 0.2041, 0.1526; and 0.5419, 0.2005, 0.1667 (2648 kmol h-1) respectively.
Figure 5.3 shows the results of the homogeneous one-equation optimal model (OEM-TPB).
The optimal nitrogen mole fraction maintains an almost-constant gap with the equilibrium
mole fraction, which is the driving force of the reaction. A similar difference is observed
between the optimal and equilibrium temperatures. When the optimal temperature profile is
used for the reacting gas, the nitrogen conversion is 0.3003 compared with 0.2543 and the
subsequent ammonia composition at the reactor exit is 1246-MTD i.e. a 15% increase over
91
the Reference Design. Clearly, such a temperature profile is difficult to achieve but can serve
Ammonia Mole Fr
as a reference ideal goal.
0.2
0.15
0.1
0.05
0
0.5
1.5
2.5
3.5
4.5
Distance (m)
(a)
0.8
Mole Fraction
Temperature (K)
800
750
700
650
600
N2
0.4
NH3
0.2
0
H2
0.6
Distance (m)
Distance (m)
(b)
(c)
Figure 5.3 : Homogeneous reactor: (a) ammonia mole fraction, (b) temperature profile,
and (c) hydrogen/nitrogen/ammonia mole fractions.
With two inter-bed heat exchangers the resulting temperature profile, shown in figure 5.4,
yields an enhanced ammonia mole fraction at exit of 0.1817 (2850 kmol h-1) and an energy
availability of 109.02 kJ h-1 (30.28 MWth). The process flow diagram of the energy recovery
plant with propsed process modifications is presented in figure 5.5.
92
1000
950
Teqm
Temperature (K)
900
850
800
Topt
750
T
700
650
600
0.5
1.5
2
2.5
Distance (m)
3.5
4.5
Figure 5.4 : Homogeneous reactor with OEM-TPA, showing gas temperature T ,

equilibrium temperature Teqm , and optimal temperature Topt .
Figure 5.5 : The Proposed Energy Recovery Plant with Process Modifications
93
5.1.4 Process Modifications Validation:

This section uses HYSYS and AspenPlusTM to estimate the sensitivity of bed temperatures
on the overall thermal energy recovery. It assumes a homogenous catalyst concentration in
each of the three beds. The objective is to arrive at a set of optimal exit temperatures specific
to the heat exchangers rather than the reactor.
The effect of heat exchangers between reactors is simulated with the configuration shown in
Fig. 5.6. The Plug Flow Reactors PFR-100 and PFR-102 represent the first reactor for which
saturation is achieved at the length of the first bed and the second reactor with a lower inlet
temperature.
Figure 5.6 : PFR reactor beds with cooling between beds 1 and 2
The sensitivity of the temperature drop, in the inter-bed heat exchanger E-100, to the
ammonia mole fraction at reactor exit is shown in Fig. 5.8. The value of T1 , arbitrarily set
to 106 K in the previous sections, is seen in Fig. 5.8 to have an optimal value of 205K, for
which the optimal exit mole fraction is 0.223, and the thermal energy availability is 31.5
MWth.
Figure 5.7 shows the Aspen Plus three-bed (reactor) configuration with two inter-bed
(reactor) heat exchangers.
94
Figure 5.7 : PFR reactor beds with cooling between beds

The optimality now must differentiate between the bed configurations and the reactor
configurations. For the bed configuration, we consider the first bed of length 1.5m and beds 2
0.13 0.14 0.15 0.16 0.17 0.18 0.19 0.2 0.21 0.22 0.23 0.24
NH_3 Molar Fraction
and 3 of 4.5 m each to simulate the full effect of reactors.
-260.0 -240.0 -220.0 -200.0 -180.0 -160.0 -140.0 -120.0 -100.0 -80.0 -60.0
Delta T1
-40.0 -20.0
Figure 5.8 : Effect of temperature drop in the inter-bed heat exchanger, after the first
bed, on the ammonia mole fraction at reactor outlet.
95
With Aspen Plus the results indicate, with inter-bed temperature drops of 106 oC and 86 oC
respectively, an exit ammonia mole fraction of 0.2137. If the first temperature drop is
constant, an optimal is found for the second temperature drop at a value 90 oC, for which the
subsequent exit ammonia mole fraction increases to 0.2143. We now consider a theoretical
maximum by allowing infinite reactor length. For the same temperature drops, we obtain an
exit ammonia mole fraction of 0.2165, which is markedly better than the finite case
0.26
0.25
0.24
0.23
NH_3 Mole Fraction
0.27
0.28
previously considered.
-260.0 -240.0 -220.0 -200.0 -180.0 -160.0 -140.0 -120.0 -100.0 -80.0 -60.0
Delta T2 (C)
-40.0 -20.0
Figure 5.9 : Effect of temperature drop in the inter-bed heat exchangers, after the first
and second beds, on the ammonia mole fraction at reactor outlet.
96
In order to obtain the maximum achievable ammonia conversion, and hence a maximum
available thermal energy availability, we consider a sensitivity analysis of two parameters viz
the inter-reactor temperature drops. These are shown in Fig. 5.8 and Fig. 5.9. Figure 5.8
shows an optimal temperature drop of 205oC, as mentioned above, for which the exit
ammonia mole fraction is 0.2230. Similarly, Fig.5.9 shows an optimal at a temperature drop
of 95oC, for which the final exit ammonia mole fraction is 0.2762, and a thermal energy
availability of 45.6 MWth.
5.2 Design Modifications

Best ammonia conversion is achieved by realizing the optimal temperature profile as
described in section 5.1. For a solar thermal power plant, this inlet temperature will be
constrained by the maximum temperature achievable at the dissociation side of the plant.
Thus, it is practically difficult to have an inlet gas temperature high enough as 870 K as
predicted by theory. We thus seek the industrially viable option so that the resulting
temperature difference, between actual and optimal, is minimized.
Two technology options that can make this possible include pre-heating the inlet gas and
progressively removing the heat of reaction from the reactor acordingly, and with the given
inlet tempeature and increasing profile, removing process gas heat from the first catalyst bed
at first saturation and achieving optimal temperature in the second bed, and repeating the
procedure in the third bed. The first option has been extensively investigated [65][77][100]
using a counter-flow arrangement in which heat at reactor exit is used for pre-heating the
97
feed gas. Another technological option [1] consisting of varying the catalyst concentration
taking advantage of the importance of the beds, has been shown to enable optimal
configuration.
Figure 5.10 shows a steep 65% conversion in the first bed, a slower but increasing 35%
conversion in the second bed, followed by a slight 10% improvement in the third bed. All
beds are taken to be of height 1.5 m. A significant feature of figure 5.10 is the saturation of
the conversion z to a value 0.2534 at the reactor exit. Figure 5.3a shows the increase of
ammonia in the three beds at approximately linear rates with decreasing gradients in
successive beds. The homogeneous catalyst loading indicates that the third bed has a very
small contribution.
0.3
0.25
0.2
0.15
0.1
0.05
0.5
1.5
2
2.5
3
Distance (m)
3.5
4.5
Figure 5.10 : Homogeneous reactor: Nitrogen conversion in catalyst bed.

98
5.2.1 The Proposed Design

Figure 5.11 shows the comparison of the reference (homogeneous) design with the proposed
process modifications. The three cases shown, between the reference (1,1,1) and the optimal,
are a 10% and a 20% increase in catalyst concentration in the first bed only, followed by a
simultaneous 50% increase in the first bed and a 25% increase in the second bed
(1.50,1.25,1.00). The first two cases are shown to marginally improve the conversion since
the design change is small, while the last case achieves the optimal conversion before the exit
from the first bed. It is seen that there is further scope for improvement in subsequent catalyst
beds.
0.2
Proposed
Design
0.18
Mole Fraction NH3
0.16
0.14
0.12
0.1
optimal
1.00 1.00 1.00
1.10 1.00 1.00
1.20 1.00 1.00
1.50 1.25 1.00
0.08
0.06
Reference
Design
0.04
0.02
0.5
1.5
2
2.5
Distance (m)
3.5
4.5
Figure 5.11 : Effect of varying spatial composition in reactor beds on the mole fraction
of ammonia in the reactor compared with the reference (homogeneous) design with
spatial concentration [1.00, 1.00, 1.00]
99
In Figure 5.12, detailed results are illustrated for a 50% and 25% concentration increase in
the first and second beds respectively. The nitrogen conversion increases from 0.2534 to
0.2832 while the temperature profile moves closer to the OEM equilibrium for the first and
second beds.
0.3
0.2
0.1
0.5
1.5
2.5
3.5
4.5
Distance (m)
(a)
0.8
900
Topt
800
Mole Fraction
Temperature (K)
1000
Teqm
700
600
Distance (m)
(b)
H2
0.6
N2
NH3
0.4
0.2
0
Distance (m)
(c)
Figure 5.12 : Effect of varying spatial composition in reactor beds (1.50, 1.25, 1.00); a)
nitrogen conversion, b) actual, optimal and equilibrium temperatures, c) hydrogen,
nitrogen and ammonia mole fractions.
Saturation in the first bed appears in the last 0.30 m of the first bed. The engineering
implications are that, with fixed bed physical dimensions, this space could be utilized for
some other scheme such as pre-heating for the second bed inlet to bring inlet temperature
closer to the optimal. The highest temperature in the first bed increases to 780 K (from 775 K
100
in the homogeneous case) which brings it closer to the maximum permissible catalyst
temperature, and hence a reduction in the reactor safety margin. The ammonia mole fraction
at reactor exit has now increased to 0.1856; equivalent to 1186-MTD. Apart from an increase
in the ammonia production, the heat recovery potential from the first inter-bed heat
exchanger increases to 18.395 MW(th) and 14.277 MW(th) from the second inter-bed heat
exchanger. When the spatial concentration is also increased in the third bed so that the
concentrations are [1.50,1.25,1.25], the nitrogen conversion increases to 0.2901, and the
ammonia production increases to 0.1902 (1210-MTD); the heat recovery is 18.395 MW(th)
and 13.880 MW(th) (total: 32.275 MW(th)).
5.2.2 Design Modifications Validation:

This section uses AspenPlusTM to estimate the effect of heterogeneous catalyst distribution
on the temperature profile in bed 1 and bed 2 of the KBR Synthesis reactor .
Figure 5.13 : Bed1: Temperature Profile with different Catalyst Distribution
101
Figure 5.13 presents the temperature profiles in the reactor bed1 with catalyst spatial factors
of 1 and 1.5. It is clear that in case of catalyst spatial facor of 1.5, the temperature value
saturates at reactor length of 0.7m, thereby approaching the optimal temperature profile faster
than in the uniform case; the equilibrium temperature can be achieved before the exit of the
first bed and hence a wider span is available for heat/energy extraction to be used by Solar
Thermal power plant.
Figure 5.14 : Bed2: Temperature Profile with different Catalyst Distribution

The same results can be observed in figure 5.14 for temperature profile of bed2, where a
catalyst spatial factor of 1.25 is used.
102
6 CONCLUSIONS AND FUTURE WORK

This work is aimed at maximizing the heat recovery and hence improving the overall
efficiency of a thermal storage plant, by estimating optimal geometric and process variables
for system components including ammonia dissociation reactor, heat exchangers, Flash tank,
purge gas removal, recycle streams and most importantly ammonia synthesis reactor.
Kellogg KBR industrial ammonia synthesis reactor has been used
for computing the
ammonia production using mass and energy conservation equations with homogeneous as
well as non-uniform catalyst distributions. The momentum conservation equation has been
ignored since the pressure drop in this reactor has been shown [64] to be not more than 2% of
the system pressure. The optimal and equilibrium temperature profiles are then computed in
the reactor and compared with the temperature profile in the homogeneous reactor.
The optimal and equilibrium temperature profiles have been used as the desired profiles by
incorporating process, rather than design, changes in the heat recovery system. This led to a
study of a heterogeneous, or non-uniform, catalyst distribution in the beds.
The results indicated that optimal ammonia conversion requires a high inlet temperature to
favor a high reaction rate as opposed to the comparatively lower inlet temperatures which are
found in industrial reactors. The optimal design, based on the optimal temperature profile,
gives a 15% increase in ammonia yield, from 1082 MTD in the homogeneous configuration
103
to 1246 MTD in the optimal configuration. A non-uniform catalyst distribution can be used
to take advantage of the importance of the first bed, followed by successive beds, thereby
approaching the optimal temperature profile faster than in the uniform case; as a result of the
previous argument, the equilibrium temperature can be achieved before the exit of the first
bed; heterogeneous catalyst distribution, is a strategy which increases the concentration by 50%
in the first bed and 25% in the second bed, brings the temperature profile close to equilibrium
results with a 10% increase in ammonia conversion. A larger number of beds could be used,
in principle, to search for a catalyst distribution which would yield the optimal temperature
profile leading to a 15% increase in ammonia yield.
Finally it is concluded that a one-dimensional model, with mass and energy conservation
equations using the Temkin-Pyzhev activity and pressure-based kinetics rate expressions,
predicted an optimal ammonia conversion of 0.2137 with a thermal energy availability of 20
MWth. A comprehensive process simulation using Aspen Plus predicts an optimal
ammonia conversion of 0.2762 mole fraction at exit, with two inter-bed heat exchangers
having optimal temperature drops of 205K and 95K respectively, and yielding a thermal
availability of 45.6 MWth. The thermal energy availability of a base-load solar thermal plant
can be increased by 15% in the ammonia conversion and over 25% in thermal energy
availability for energy recovery.
104
Construction of experimental setup is recommended for validation of results presented in this

thesis and further research in this area. It is being considered at University of Engineering &
Technology Taxila through undergraduate students and development of initial funding
proposal is in progress.
Further work is suggested to quantify the performance increase in the considered system by
conducting an exergy analysis of the system components for better quantification of the
efficiency improvements as the major determinant of achievable performance for such a
system is the degree of thermodynamic irreversibility associated with the heat recovery
process.
The major irreversibilities occur within the exothermic reactor and the counterflow heat
exchanger between ingoing and outgoing reactants. In the suggested study, optimum reactor
control will yield exergetic efficiencies, which should translate to overall solar to electric
conversion efficiencies.
105
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120
APPENDIX A.
AMMONIA 3D PHASE DIAGRAMS
Figure A.1 Ammonia 3D Phase Diagram
Critical Point*
Substance
Nitrogen
Hydrogen
Ammonia
Tc
Pc
MPa
126.192
33.145
405.4
3.3958
1.2964
11.333
kg / m 3
31.3
31.263
225.0
121
Boiling Point
K
77.355
20.369
239.823
APPENDIX B MATLAB PROGRAMS FOR AMMONIA

SIMULATION
S.
No.
Name
SSATS
Functions Called
Description
ACTVT(P(IS),T(IS),x(1),x(2),x(4))
EQNCN(T(IS))
ETA(P,T,Z)
RTCNT(T(IS),R_un)
RRATE(kArh,Ka,aH2,aN2,aNH3)
SPCHT(T(IS),P(IS))
Solves 2
equations in
one zone; RK4
method
SSEqmProg
None
RunSSoptim
SSoptim
SSATS_NonUnif
MansonOneEqn
ACTVT(P(IS),T(IS),x(1),x(2),x(4))
EQNCN(T(IS))
ETA(P,T,Z)
RTCNT(T(IS),R_un)
RRATE(kArh,Ka,aH2,aN2,aNH3)
SPCHT(T(IS),P(IS))
OptimalT
122
Computes eqm
mol fractions,
extent and K
Solves 3
equations from
Babu; counter
flow
feed/reacting
Gas and
temperature
Same as
SSATSexcept it has 3
zones allowing
user variable
catalyst
activity
Solves one
equation with
optimal
temperature
found from
numerical
solution of
Hamiltonian
Remarks
APPENDIX B1: MATLAB PROGRAM FOR OUTPUT OF STEADY

STATE SYNTHESIS REACTOR
This section lists the Program SSATS and its functions: ACTVT, COMPR, DeltaH, EQNCN, ETA,
RCTHT, RRATE, RTCNT, SPCHT.
Program SSATS computes output for a synthesis reactor

Data: inlet conditions
Output: outlet conditions
% Program Name:
SSATS
% Steady State Ammonia Thermal Storage

% C:\MATLAB7\work\Ammonia\SSATS
% Author: Engr. Sadaf Siddiq (sdfabd2001@gmail.com)
%
First Written: JULY
Last
Update:
2010
APRIL 2011
% open output file

resl=fopen('out1.txt','w'); %
INPUT and STREAM OUTPUT
tic
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
% INPUT
% System Pressure (atm)
% Temp (K)
% Total Mass Flow Rate (kg/hr) =
% Mole fractions (H,N,Ar,Amm,Met) [x] =
% Area = 20.0 ; % cross-section area of catalyst m^2
% Length of converter Lmax (m)
% OUTPUT
% graph of mol fractions of H, N, Amm vs length
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
% program parameters
NS = 10; % number of streams
NC = 5;
% number of components, H2,N2,NH3,Ar,CH4
fprintf (resl,'\n No. of Streams
= %3.0f \n',NS);
fprintf (resl,'\n No. of Components = %3.0f \n',NC);
123
%%%%%%%%%%%%%%%%%%%%%%%%% DATA **********************

R_un = 8.314472; % universal gas const J/(mol-K)
%R_un = 1545.349 ; % lbf.ft/lbmol.R
%R_un = 1545.349;
fprintf (resl,'\n Universal Gas Const = %12.6f
kJ/(mol-K)\n',R_un);
% chemical data from http://wwwjmg.ch.cam.ac.uk/tools/magnus/PeriodicTable.html

% component ID:
1 : H2
2: N2
3: Ar
4: Ammonia
5:Methane
MW1=2.0*1.0079759; MW2=2.0*14.0067231; MW3= 39.9476613;

MW4=(14.0067231+3.0*1.0079759); MW5 = (12.0110369+4.0*1.0079759);
MW = [ MW1;MW2;MW3;MW4;MW5 ];
fprintf (resl,'\n ID
Name
Mol Wt (kg/kmol)\n');
fprintf (resl,'\n 1
Hydrogen
%8.4f ',MW(1));
fprintf (resl,'\n 2
Nitrogen
%8.4f ',MW(2));
fprintf (resl,'\n 3
Argon
%8.4f ',MW(3));
fprintf (resl,'\n 4
Ammonia
%8.4f ',MW(4));
fprintf (resl,'\n 5
Methane
%8.4f ',MW(5));
fprintf (resl,'\n ----------------------------\n');

% STREAM 1: SYN GAS ENTERING C-1
******************************************
IS=1;
fprintf (resl,'\n Stream No: %3.0f \n',IS);
% STREAM INPUT
P(1) = 100.0; % atm
P_SIunits(1) = P(1)*1.0e5; %Pascals
T(1) = 300.0; % Kelvin
TotMassFlRate(IS) = 183600; % kg/hr
%TotMassFlRate(IS) =1000; % kg/hr
% component ID:
1 : H2
Dashti p.20
Dashti p.20
2: N2
3: Ar
4: Ammonia
5:Methane
x= [ 0.6567006; 0.2363680; 0.0202874; 0.026930; 0.059714]; % mole

fractions
Area = 20.0 ; % cross-section area of catalyst m^2
% Radius = 1.0; % try a radius of 1 m
% Area = 3.142 * Radius^2 ;
fprintf (resl,'\n Area = %6.2f m^2',Area);
HghtReactor = 5.6; % meters
124
VolCatalyst = Area * HghtReactor;

fprintf (resl,'\n Vol of catalyst = %6.3f m^3 \n',VolCatalyst);
%x= [ 0.7426; 0.2475; 0.0099; 0.0; 0.0]; % mole fractions
%mfm = [ 750.0 ; 250.0 ;
10.0; 0.0; 0.0]; % kg-mols/hr
%
% stream computation.......................................
MWt(IS) = 0.0; % average molecular weight of stream
xT = 0.0; % total mol fr. this is should add up to 1.0
for i = 1:NC
MWt(IS)=MWt(IS)+x(i)*MW(i);
xT
= xT
+x(i);
end
RR(IS) = R_un/MWt(IS); % gas constant for this stream (gas)
%------------------------------% mfrT = 0.0; % total mass flow rate/hr
%
for j=1:NC
mfr(j)=mfm(j)*MW(j); % kg/hr
mfrT = mfrT + mfr(j);
% end
% MolarFlRateMix(IS) = mfrT/MWt(IS); % moles per hr
%-------------------------------MolarFlRateMix(IS) = TotMassFlRate(IS)/MWt(IS); % in kmols/hr
mfrT=0.0;
for jk=1:NC
mfr(jk) = x(jk)*MolarFlRateMix(IS);
mfrT = mfrT + mfr(jk);
mfm(jk) = mfr(jk)/MW(jk);
end
% end of stream computation...............................
%
125
% STREAM OUTPUT
fprintf (resl,'\n ----------------------------------------------------\n');
fprintf (resl,'\n STREAM No: %3.0f \n',IS);
fprintf (resl,'\n NC
Mole Fr
Molar flow rate
fprintf (resl,'\n
Mass flow rate');
kg-mols/hr
kg/hr\n');
for i=1:NC
fprintf (resl,'\n %2.0f
',i,x(i),mfm(i),mfr(i))
%8.4f
%8.4f
%8.4f
end
fprintf (resl,'\n \n Total
%6.4f
%12.4f\n',xT,mfrT);
fprintf (resl,'\n Mol Wt of mixture

\n',IS,MWt(IS));
MWt( %2.0f ) = %8.4f
fprintf (resl,'\n Gas Const of mixture RR ( %2.0f ) = %8.4f

\n',IS,RR(IS));
kg/kmol
kJ/(kmol-K)
fprintf (resl,'\n Molar Flow Rate of Stream %3.0f is %8.2f kmoles / hr

\n',IS,MolarFlRateMix(IS));
fprintf (resl,'\n ----------------------------------------------------\n');
% COMPRESSOR WORK FOR STREAM 1
% make the mixture Cp, Cv and gamma
CpMix = 0.0;
RMix
= 0.0;
% find the Cp values at this temp T1 and press P(1)

[CpH2,CpN2,CpNH3,CpCH4,CpAr] = SPCHT(T(1),P(1));
Cp(1) = CpH2; Cp(2) = CpN2; Cp(3) = CpAr; Cp(4)=CpNH3; Cp(5)=CpCH4;
jj=1;
for j= NC+1:2*NC
Cp(j) = Cp(jj)/MW(jj);
jj=jj+1;
end
fprintf (resl,'\n -----------------------------------------\n');
fprintf (resl,'\n Cp values from function SPCHT at T = %8.2f K and P
= %6.2f atm\n',T(1),P(1));
fprintf (resl,'\n Component
Cp
kJ/(kmol-K) kJ/(kg-K)\n');
fprintf (resl,'\n 1
Hydrogen
%12.4e %12.4e ',Cp(1),Cp(6));
fprintf (resl,'\n 1
Nitrogen
%12.4e %12.4e ',Cp(2),Cp(7));
fprintf (resl,'\n 1
Argon
%12.4e %12.4e ',Cp(3),Cp(8));
fprintf (resl,'\n 1
Ammonia
%12.4e %12.4e ',Cp(4),Cp(9));
126
fprintf (resl,'\n 1
Methane
%12.4e %12.4e ',Cp(5),Cp(10));
fprintf (resl,'\n ------------------------------------------\n');

for i = 1:NC
% individual gas constants
Rg(i) = R_un/MW(i);
RMix
= RMix
+ Rg(i)*mfr(i)/mfrT;
CpMix = CpMix + Cp(i)*mfr(i)/mfrT;

end
CvMix = CpMix - RMix;
GammaMix = CpMix/CvMix;
fprintf (resl,'\n Mixture properties (based on mass ratios)\n');
fprintf (resl,'\n
GammaMix\n');
CpMix
CvMix
fprintf (resl,'\n %12.4e

%12.4e
\n',CpMix,CvMix,RMix,GammaMix);
%12.4e
RMix
%8.2f
% compressor work
n=1;
P(2) = 1.5 * P(1); % discharge pressure
PressRatio = P(2)/P(1);
[Ws]=COMPR(n,T(1),RMix,P(1),P(2),GammaMix); % gives Work in kJ/kmol of
gas
PowerComp = Ws * MolarFlRateMix(1); % kJ/hr
PowerComp = (1./(60.*60.))*PowerComp; % kW
fprintf (resl,'\n Compressor Power \n');
fprintf (resl,'\n Reciprocating Compressor\n')
fprintf (resl,'\n No of stages = %2.0f ',n);
fprintf (resl,'\n Suction
Pressure = %12.4e atm \n',P(1));
fprintf (resl,'\n Discharge Pressure = %12.4e atm \n',P(2));

fprintf (resl,'\n Pressure Ratio
= %6.2f
\n\n',PressRatio);
fprintf (resl,'\n Compressor Work
= %12.4e kJ/kmol
fprintf (resl,'\n Compressor Work
= %12.4e kW
\n',Ws);
\n',PowerComp);
% example from K.V.Narayanan p.134

% the R used in this is the universal Gas Const; this prog uses RgasMix
% (check again)
127
%[Ws]=COMPR(1,300,8.314,1,10,1.3);
%PowerComp = Ws * 1.114e-3;
%fprintf (resl,'\n Compressor Work
= %12.4e kW
\n',PowerComp);
%------------------------------ SYNTHESIS -------------------------% STREAM 3

% give input data for stream
%
molar flow rate; mole fractions, pressure and temperature
% output will be mole fractions, temperature and pressure

% solve the equations using RK-4 method
% STREAM 3: SYN GAS ENTERING R-1
******************************************
IS=3;
% STREAM INPUT
P(IS) = 150 ; % bar
assume 1 bar = 1 atm
P_SIunits(IS) = P(IS)*1.0e5; %Pascals

T(IS) = 371+273; % Kelvin
TotMassFlRate(IS) = 183600; % kg/hr
% component ID:
1 : H2
2: N2
Dashti p.20
3: Ar
4: Ammonia
5:Methane
x= [ 0.6567006; 0.2363680; 0.0202874; 0.026930; 0.059714]; % mole

fractions
% mfm = [ 750.0 ; 250.0 ;
10.0; 0.0; 0.0]; % kg-mols/hr
%
MWt(IS) = 0.0; % average molecular weight of stream
for i = 1:NC
MWt(IS)=MWt(IS)+x(i)*MW(i);
xT
= xT
+x(i);
end
128
RR(IS) = R_un/MWt(IS); % gas constant for this stream (gas)

TotMolarFlRate(IS) = TotMassFlRate(IS)/MWt(IS); % kmoles per hr
sumMol = 0.0;
sumMas = 0.0;
for j=1:NC
MolFlRate(j) = x(j) * TotMolarFlRate(IS);
sumMol = sumMol + MolFlRate(j);
MassFlRate(j)= x(j) * TotMassFlRate(IS);
sumMas = sumMas + MassFlRate(j);
end
%
% STREAM OUTPUT
fprintf (resl,'\n ----------------------------------------------------\n');
fprintf (resl,'\n STREAM No: %3.0f \n\n',IS);
fprintf (resl,'\n\n Pressure = %8.2f atm
\n\n',P(IS),T(IS));
rate');
Mole Fr
Temperature = %8.2f
Molar flow rate
fprintf (resl,'\n
Mass flow
kmoles/hr
kg/hr\n');
for i=1:NC
%8.4f
',i,x(i),MolFlRate(i),MassFlRate(i))
%8.2f
%8.2f
end
fprintf (resl,'\n \n
Total %6.4f
%12.4f
%12.4f\n',xT,sumMol,sumMas);

\n',IS,MWt(IS));
MWt(%2.0f) = %8.2f
fprintf (resl,'\n Gas Const of mixture RR (%2.0f) = %8.2f

\n',IS,RR(IS));
kg/kmol
kJ/(kmol-K)

\n',IS,TotMolarFlRate(IS));
fprintf (resl,'\n Mass Flow Rate of Stream %3.0f is %8.2f kg /hr
\n',IS,TotMassFlRate(IS));
fprintf (resl,'\n ----------------------------------------------------\n');
129
% SECTION BEGINS
=====================================================
% do this section if you want to check manually the orders of magnitude

% otherwise remove this section
% activities: a_i = y_i * phi_i * P
% y_i is the mole fraction which is available above, as x(i)
% obtain phi_i from the function
% function[phiH2,phiN2,phiNH3,aH2,aN2,aNH3]=ACTVT(P,T,yH2,yN2,yNH3)
[phiH2,phiN2,phiNH3,aH2,aN2,aNH3]=ACTVT(P(IS),T(IS),x(1),x(2),x(4));
% now compute the equilibrium constant K
% function[Ka] = EQNCN(T)
[Ka] = EQNCN(T(IS));
% now find Arrhenius Rate Constant
[kArh]= RTCNT(T(IS),R_un);
% now find reaction rate
[RNH3]=RRATE(kArh,Ka,aH2,aN2,aNH3);
[CpH2,CpN2,CpNH3,CpCH4,CpAr] = SPCHT(T(IS),P(IS));
fprintf (resl,'\n check this part carefully; returned from SPCHT\n');
fprintf (resl,'\n temp = %6.2f
pressure = %6.2f \n',T(IS),P(IS));
fprintf (resl,'\n CpH2 = %8.2f kJ/kmol-K',CpH2);

fprintf (resl,'\n CpN2 = %8.2f kJ/kmol-K',CpN2);
fprintf (resl,'\n CpAr = %8.2f kJ/kmol-K',CpAr);
fprintf (resl,'\n CpNH3= %8.2f kJ/kmol-K',CpNH3);
fprintf (resl,'\n CpCH4= %8.2f kJ/kmol-K',CpCH4);
fprintf (resl,'\n now convert to kJ/kg-K');
jj=1;
for j= NC+1:2*NC
Cp(j) = Cp(jj)/MW(jj); % kJ/(kg-K)
fprintf (resl,'\n Cp( %2.0f )= %6.2f kJ/kg-K ',j,Cp(j));
jj=jj+1;
end
CpMix = 0.0;
for ii = 1:NC
CpMix = CpMix + Cp(ii+5)*MassFlRate(ii)/TotMassFlRate(IS);
130
end
fprintf (resl,'\n\n Mixture Cp kJ/kg-K');
fprintf (resl,'\n CpMix = %6.2f KJ/kg-K',CpMix);
[HtReact]= DeltaH(P(IS),T(IS));
% X is the height from the top of the catalyst (m) and StepX is the
% increment in X
fprintf (resl,'\n Test Section output begins ...\n');
fprintf (resl,'\n Pressure = %6.2f
atm
Temp = %6.2f',P(IS),T(IS));
X = 0.0; StepX=0.5;
fprintf (resl,'\n X = %6.2f m
StepX = %6.2f',X,StepX);
Zold = 0; % no N2 has been converted as yet

fprintf (resl,'\n Zold = %6.2f',Zold);
Told = T(IS); % this is temp at the inlet of this volume
N20 = MolFlRate(2); % kmols/hr of N2 entering this volume element
fprintf (resl,'\n N20 = %6.2f kmol/hr ',N20);
fprintf (resl,'\n Mdot = %12.4e kg/hr',TotMassFlRate(IS));
fprintf (resl,'\n Cp
= %12.4e kJ/(kg-K) ',CpMix);
fprintf (resl,'\n x(1) = %8.4f

',x(1),x(2),x(4));
x(2)=%8.4f
x(4)=%8.4f
fprintf (resl,'\n RNH3 = %12.4e kmol/(hr-m^3) ',RNH3);

fprintf (resl,'\n HtReact = %12.4e kJ/kmol ',HtReact);
dZdX = Area*RNH3 /(2.0*N20);
dTdX = abs(HtReact)*RNH3*Area/(TotMassFlRate(IS)*CpMix);
fprintf (resl,'\n\n
fprintf (resl,'\n
dZ/dx
dT/dx
=
=
%12.4e
%12.4e
conversion per meter',dZdX);

K per
meter
\n',dTdX);
% now use the above gradients to find new values for moles of H, N,
Ammonia
131
% the volume of this box is now
Area * StepX
DeltaVolume = Area * StepX;

Znew = Zold + dZdX * StepX;
Tnew = Told + dTdX * StepX;
fprintf (resl,'\n New values
Z = %6.2f
T = %6.2f K \n',Znew,Tnew);
% now compute new moles and mole fractions

% converted moles of N2
delta = Znew * MolFlRate(2);
% new mole rates (kmols/hr) and mass flow rates (kg/hr)
for ik =1:NC
MolFlRateOld(ik) = MolFlRate(ik);
MassFlRateOld(ik) = MassFlRate(ik);
MolFlRateNew(ik) = 0.0; % need to compute this now
MassFlRateNew(ik)= 0.0; % need to compute this now
xold(ik)
= x(ik); % old mole fractions
xnew(ik)
= 0.0;
% new mole fractions
end
% new totals
TotMolarFlRateOld(IS)=TotMolarFlRate(IS);
TotMolarFlRateNew(IS)=0.0;
TotMoleFrOld=0.0;
TotMoleFrNew=0.0;
TotMassFlRateOld(IS)=TotMassFlRate(IS);
TotMassFlRateNew(IS)=0.0;
MolFlRateNew(1) = MolFlRateOld(1) - 3.0* delta; % H2
MolFlRateNew(2) = MolFlRateOld(2) - 1.0* delta; % N2
MolFlRateNew(3) = MolFlRateOld(3);
% Argon
MolFlRateNew(4) = MolFlRateOld(4) + 2.0* delta; % NH3

%
132
% CH4
for ik1 = 1:NC

MassFlRateNew(ik1) = MW(ik1) * MolFlRateNew(ik1);
end
for ik2 = 1:NC
TotMolarFlRateNew(IS) = TotMolarFlRateNew(IS) + MolFlRateNew(ik2);
TotMassFlRateNew(IS)
= TotMassFlRateNew(IS)
+ MassFlRateNew(ik2);
end
for ik11 = 1:NC
xnew(ik11)
= MolFlRateNew(ik11)/TotMolarFlRateNew(IS);
end
for ik12 = 1:NC
TotMoleFrOld = TotMoleFrOld + xold(ik12);
TotMoleFrNew = TotMoleFrNew + xnew(ik12);
end
% now write a summary of the change

fprintf (resl,'\n\n SUMMARY AFTER CONVERSION
Area*StepX \n');
fprintf (resl,'\n
AFTER CONVERSION\n');
BEFORE
fprintf (resl,'\n
i
MolFlRate
MolFlRate
mol fr
MassFlRate');
fprintf (resl,'\n
kmol/hr
in this volume box
CONVERSION
mol fr
kmol/hr
kg/hr');
MassFlRate
kg/hr
for ik3=1:NC
fprintf (resl,'\n %3.0f %15.4e %8.4f %12.4e %20.4e %8.4f %12.4e
',ik3,MolFlRateOld(ik3),xold(ik3),MassFlRateOld(ik3),MolFlRateNew(ik3),x
new(ik3),MassFlRateNew(ik3));
end
fprintf
(resl,'\n %21.4e %8.4f %12.4e %21.4e %9.4f %13.4e',TotMolarFlRateOld(IS)
,TotMoleFrOld,TotMassFlRateOld(IS),TotMolarFlRateNew(IS),TotMoleFrNew,To
tMassFlRateNew(IS));
% how much energy is given off in this volume?
% mass flow rate is the same before or after so can use either
Power = TotMassFlRateOld(IS)*CpMix*(Tnew-Told); % (kg/hr)*(kJ/kg-K)*(K)
= kJ/hr
133
Power = Power/(60*60); % kW
fprintf (resl,'\n Power given off in synthesis of ammonia in this vol
element = %12.4e kW\n',Power);
fprintf (resl,'\n Test Section ends.............\n\n\n');
%SECTION ENDS
=======================================
Z=0.0; % N2 conversion percentage

at t=0
start with ) since no N2 is converted
[Eta1]=ETA(P(IS),T(IS),Z);%
\n',P(IS),T(IS));
%fprintf (resl,'\n
aN2
aNH3
Temp
Ka
phiH2
kArh
Temperature = %8.2f
phiN2
phiNH3
RNH3\n');
aH2
%fprintf
(resl,'\n %6.1f %10.2e %10.2e %10.2e %10.2e %10.2e %10.2e %10.2e %10.2e
%10.2e\n',T(IS),phiH2,phiN2,phiNH3,aH2,aN2,aNH3,Ka,kArh,RNH3);
%---------------------------------------------------------% begin RK 4th order for 2 1st-order coupled ODEs
fprintf (resl,'\n\n R-K method \n\n');
%Area is defined above
FoverA = MolFlRate(2)/Area; % molar flow rate for Nitrogen at inlet
fprintf (resl,'\n FoverA = %8.3f kmols per hr per m^2\n',FoverA);
Z = 0.0;
T = T(IS);
P = P(IS);
%LL = [0 ; 0.50; 1.00; 1.50; 2.00; 2.50; 3.00; 3.50; 4.00; 4.50; 5.00];
ZZ(1)=0.0; % initial value of conversion percentage
TT(1)=T;
% initial value of temperature (K)
Lmin =0.0;
Lmax= HghtReactor; % height of the convtr in meters
NPTS = 20;
h = (Lmax-Lmin)/NPTS;
LL(1)=Lmin;
134
for i = 2: NPTS
LL(i) = LL(i-1)+h;
end
LL
L = LL(1);
i = 1 ;
% component ID:
1 : H2
Hmoles(i) =
MolFlRate(1);
Nmoles(i) =
MolFlRate(2);
Rmoles(i) =
MolFlRate(3);
Amoles(i) =
MolFlRate(4);
Mmoles(i) =
MolFlRate(5);
2: N2
3: Ar
4: Ammonia
5:Methane
TotalMoles(i) = Hmoles(i) + Nmoles(i) + Rmoles(i) + Amoles(i) +

Mmoles(i);
AmolesPC(i) = Amoles(i)/TotalMoles(i);
HmoleFr(i)=x(1);
NmoleFr(i)=x(2);
AmoleFr(i)=x(4);
%
fprintf (resl,'\n
x(1)
x(2)
x(4)
Total Mole Fl Rate');
%
Toptimal(i) = 800.0;
NPTS1=NPTS-1;
while (i <= NPTS1) %---------------------------------- RK4 LOOP BEGINS
i
fprintf
(resl,'\n %3.0f %8.4f %8.4f %8.4f %15.4e',i,x(1),x(2),x(4),TotalMoles(i)
);
135
%%%%%%%%%%%%%%%%%%%%%%%%%%%
k1_z
k1_T
%%%%%%%%%%%%%%%%%%%%
% first function
% evaluate RHS of mass conservation equation FUNC1
[Eta1]=ETA(P,T,Z);
[phiH2,phiN2,phiNH3,aH2,aN2,aNH3]=ACTVT(P,T,x(1),x(2),x(4));
[Ka] = EQNCN(T);
[kArh]= RTCNT(T,R_un);
FUNC1 = Eta1*RNH3/(2.0*FoverA);
k1_z
= FUNC1;
% second function
% evaluate RHS of energy conservation equation FUNC2
[CpH2,CpN2,CpNH3,CpCH4,CpAr] = SPCHT(T,P);
jj=1;
for j= NC+1:2*NC
jj=jj+1;
end
CpMix = 0.0;
for ii = 1:NC
end
[HtReact]= DeltaH(P,T);
FUNC2 = ( HtReact * Eta1 * RNH3 ) / ((TotMassFlRate(IS)/Area) * CpMix );
k1_T
= -FUNC2;
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
%
k2_z
= ZZ(i) + k1_z * h/2.0;
= TT(i) + k1_T * h/2.0;
k2_P
LL(i) + h/2. ;
% first function
[Eta1]=ETA(P,T,Z);
136
[Ka] = EQNCN(T);
k2_z
= FUNC1;
% second function
jj=1;
for j= NC+1:2*NC
jj=jj+1;
end
CpMix = 0.0;
for ii = 1:NC
end
k2_T
= -FUNC2;
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
%
k3_z
k3_P
= ZZ(i) + k2_z * h/2.0;
= TT(i) + k2_T * h/2.0;
% first function
[Eta1]=ETA(P,T,Z);
[Ka] = EQNCN(T);
137
k3_z
= FUNC1;
% second function
jj=1;
for j= NC+1:2*NC
jj=jj+1;
end
CpMix = 0.0;
for ii = 1:NC
end
k3_T
= -FUNC2;
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
%
k4_z
= LL(i) + h;
= ZZ(i) + k3_z * h;
= TT(i) + k3_T * h;
k4_P
% first function
[Eta1]=ETA(P,T,Z);
[Ka] = EQNCN(T);
138
k4_z
= FUNC1;
% second function
jj=1;
for j= NC+1:2*NC
jj=jj+1;
end
CpMix = 0.0;
for ii = 1:NC
end
k4_T
= -FUNC2;
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
%
get new values for Z, T
i = i + 1;
ZZ(i) = ZZ(i-1) + (h/6.)*(k1_z + 2.0*k2_z + 2.0*k3_z + k4_z);
TT(i) = TT(i-1) + (h/6.)*(k1_T + 2.0*k2_T + 2.0*k3_T + k4_T);
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
% update mole fractions
% component ID:
1 : H2
2: N2
3: Ar
4: Ammonia
ConvertedMolesOfN = ZZ(i)*MolFlRate(2);
Hmoles(i) =
MolFlRate(1) - 3.0*( ConvertedMolesOfN ) ;
Nmoles(i) = (1.0-ZZ(i)) *MolFlRate(2);
139
5:Methane
Rmoles(i) =
MolFlRate(3);
Amoles(i) =
MolFlRate(4) + 2.0*( ConvertedMolesOfN ) ;
Mmoles(i) =
MolFlRate(5);
%
TotalMoles(i) = Hmoles(i) + Nmoles(i) + Rmoles(i) + Amoles(i) +
Mmoles(i);
% mole fractions
HmoleFr(i) = Hmoles(i)/TotalMoles(i);
NmoleFr(i) = Nmoles(i)/TotalMoles(i);
AmoleFr(i) = Amoles(i)/TotalMoles(i);
Power(i-1) = TotMassFlRate(IS)*CpMix*(TT(i)-TT(i-1)); %
(kg/hr)*(kJ/kg.K)*K=kJ/hr
Power(i-1) = Power(i-1)/(60*60); % kW
% now to go back to the beginning of the loop, set new local parameters
% P,T,Z. and also need P, T, x(1), x(2), x(4) for next iteration step
x(1) = Hmoles(i)/TotalMoles(i);
x(2) = Nmoles(i)/TotalMoles(i);
x(4) = Amoles(i)/TotalMoles(i);
MolFlowRate(2) = Nmoles(i); % this is the N2 inlet for the next volume
element
% Pressure remains same
P=P;
T=TT(i);
Z=ZZ(i);
% now go to find optimal temp at this point --------------------- 10 may
2011
% scan between 500 and 800
Tchk=495;
fprintf (resl,'\n Temp (K)
diff=fLHS-fRHS');
140
for iTchk = 1:60

Tchk = Tchk+5;
[phiH2,phiN2,phiNH3,aH2,aN2,aNH3]=ACTVT(P,Tchk,x(1),x(2),x(4));
[Ka] = EQNCN(Tchk);
FatT = Ka^2*aN2*aH2^1.5/aNH3 - aNH3/aH2^1.5;
fRHS
= -( (20.523e3)/Tchk^2 ) * FatT;
% now find deriv at this point

T1=Tchk-1; T2=Tchk+1;
[phiH2,phiN2,phiNH3,aH2,aN2,aNH3]=ACTVT(P,T1,x(1),x(2),x(4));
[Ka] = EQNCN(T1);
FatT1 = Ka^2*aN2*aH2^1.5/aNH3 - aNH3/aH2^1.5;
[Ka] = EQNCN(T2);
fLHS = 0.5*(FatT2-FatT1);
diff=fLHS-fRHS;
rootT(iTchk) = Tchk;
rootY(iTchk) = diff;
fprintf(resl,'\n %3.0f %6.2f %12.4e',iTchk,rootT(iTchk),rootY(iTchk));
end
Topt=0;
for jTchk = 1:59
jT1=jTchk+1;
if ((rootY(jTchk)>0)&(rootY(jT1)<0))
Topt = rootT(jTchk+1);
end
end
for jTchk = 1:59
jT1=jTchk+1;
if ((rootY(jTchk)<0)&(rootY(jT1)>0))
end
end
Toptimal(i) = Topt;
% what if Topt is not found? set it to max
141
if (Topt==0)
Toptimal(i)=800.0;
end
%----------------------------------------------------------------
% now go back
end %
-------------------------------------
RK4
LOOP ENDS
fprintf
(resl,'\n %3.0f %8.4f %8.4f %8.4f %15.4e',i,x(1),x(2),x(4),TotalMoles(i)
);
fprintf (resl,'\n\n\n Summary of RK numerical solution \n \n \n');

fprintf (resl,'\n
Conversion % of N \n');
fprintf (resl,'\n
CH4
Total
Moles
H2
N2
Ar
Toptimal\n');
NH3
for i = 1: NPTS
fprintf
(resl,'\n %3.0f %6.4f %8.2f %8.2f
%8.2f %8.2f %8.2f
%10.2f %8.4
f %8.2f %8.2f',i,LL(i),Hmoles(i),Nmoles(i),Rmoles(i),Amoles(i),Mmoles(i
),TotalMoles(i),ZZ(i),TT(i),Toptimal(i));
end
% Power available from exothermic reactions
fprintf (resl,'\n\n\n\n
Power (kW)\n');
sumPower =0.0;
for i = 1: NPTS1
fprintf (resl,'\n
%3.0f
%12.4e
',i,Power(i));
sumPower=sumPower+Power(i);
end
fprintf (resl,'\n total exothermic energy avaiable is %12.4e kW
',sumPower);
ThisPlot=4;
142
if (ThisPlot==1)
plot (LL,ZZ,'-k')
xlabel ('Distance (m)')
ylabel ('Conversion of N_2
(Z)')
title 'Conversion of N_2 in the synthesis convertor'

end
if (ThisPlot==2)
plot (LL,TT,'-k')
ylabel ('Temperature (K)')
title 'Temperature in synthesis convertor'
end
if (ThisPlot==3)
plot (LL,Hmoles,'-k')
hold on
plot (LL,Nmoles,'-.k')
hold on
plot (LL,Amoles,'--k')
ylabel ('Molar Flow Rate (kmols/hr)')
h = legend('H_2','N_2','NH_3',2);
title 'Molar flow rate of H_2, N_2 and NH_3 in convertor'
end
if (ThisPlot==4)
subplot(2,2,1)
plot (LL,AmolesPC,'-k')
143
ylabel ('Ammonia Mole Fr')

grid on
%
title 'Mole % NH_3'

subplot(2,2,2)
plot (LL,ZZ,'-k')
ylabel ('Conversion of N_2
%
(Z)')
title 'Conversion of N_2'

grid on
subplot(2,2,3)
plot (LL,TT,'-k')
hold on
% now plot the optimal temp on this
plot (LL,Toptimal,'--k');
h = legend('Temp','Topt',2);
grid on
%
title 'Temperature'
subplot(2,2,4)
%plot (LL,Hmoles,'-k')
plot (LL,HmoleFr,'-k')
hold on
%plot (LL,Nmoles,'-.k')
plot (LL,NmoleFr,'-.k')
hold on
%plot (LL,Amoles,'--k')
plot (LL,AmoleFr,'--k')
%ylabel ('Molar Flow Rate (kmols/hr)')
ylabel ('Mole Fractions')
grid on
h = legend('H_2','N_2','NH_3',2);
144
% title 'Mol fl rate of H_2, N_2 and NH_3'

end
toc
fclose(resl);
function[phiH2,phiN2,phiNH3,aH2,aN2,aNH3]=ACTVT(P,T,yH2,yN2,yNH3)
%% Program Name:
%
ACTVT
ACTIVITY CALCULATION OF H2, N2 & NH3
%
% C:\MATLAB7\work\Ammonia\ACTVT.m
% Written: JULY
2010
% Pressure in atm
% Temp
in K
A=(-3.8402*T^0.125)+0.541;
B=(-0.1263*T^0.5)-15.98;
C=(-0.011901*T)-5.941;
% Fugacity Coefficients
tt1 = exp(A)*P; tt2 = exp(B)*P^2; tt3 = exp(C)*exp(-P/300); % check
last term sign again
phiH2=exp(tt1-tt2 +300*tt3);
phiN2=0.93431737+((0.2028538E-3)*T)+((0.295896E-3)*P)-((0.270727E6)*T^2)+(0.4775207E-6*P^2);
phiNH3=0.1438996+((0.2028538E-2)*T)-((0.4487672E-3)*P)-((0.1142945E5)*T^2)+((0.2761216E-6)*P^2);
% Activities
aH2=phiH2*yH2*P;
aN2=phiN2*yN2*P;
aNH3=phiNH3*yNH3*P;
function[Ws]=COMPR(n,T,RMix,P1,P2,gamma)
145
% Ws
= Work Done On Compressor
% r
= Pressure ratio for each stage in compression
% n
= Number of compressor stages
% T
= inlet temperature (K)
% RMix
= Gas constant for this gas mixture
% P1
= inlet pressure (Pa)
% P2
= discharge pressure (Pa)
tt1 = gamma/(gamma-1.0);
tt2 = 1./tt1;
ratio = (P2/P1)^(1./n);
tt3 = tt1 * RMix * T;
tt4 = (1.0 - ratio^tt2);
Ws=
n* tt3 * tt4 ;
function[HtReact]= DeltaH(P,T)
% heat of reaction in kJ/kmol
% DASHTI
tt1 = 0.54526 + 846.609/T + 459.734e6/T^3;
tt2 = -0.2525e-3*T^2 + 1.69197e-6*T^3-9157.09;
HtReact = 4.184*( -tt1*P - 5.34685*T + tt2 );
function[Ka] = EQNCN(T)
% equilibrium constant
% T in K
Ka=10^(-(2.691122*log10(T))-(5.519265E-5*T)+(1.848863E7*(T^2))+(2001.6/T)+2.689);
function[Eta1]= ETA(P,T,Z)
% eta is the catalyst activity factor
% P units of atm
if (P <= 150)
b0 = -17.539096; b1=0.07697849; b2=6.900548; b3= -1.08279e-4;
b4 = -26.42469;
b5=4.927648e-8; b6=38.937;
end
if ((P > 150)&(P<=250))
b0 = -8.2125534; b1=0.03774149; b2=6.190112; b3= -5.354571e-5;
b4 = -20.86963;
b5=2.379142e-8; b6=27.88;
146
end
if (P > 250)
b0 = -4.6757259; b1=0.2354872; b2=4.687353; b3= -3.463308e-5;
b4 = -11.28031;
b5=1.540881e-8; b6=10.46;
end
Eta1 = b0 + b1*T + b2*Z + b3*T^2 + b4*Z^2
+ b5*T^3 + b6*Z^3;
function[delHr]=RCTHT(T,P)
delHr=(-(0.54526+(846.609/T)+(459.734E6/T^3))*P-5.34685*T-(0.2525E3*T^2)+(1.069197E-6*T^3)-9157.09);
function[RNH3]=RRATE(kArh,Ka,aH2,aN2,aNH3)
% reaction rate; units:
kmol of NH3/(hr-m^3 of catalyst)
tt1 = aH2^1.5;
RNH3 = 2.0 * kArh *
( Ka^2*
aN2 * tt1/aNH3 - aNH3/tt1 );
function[kArh]= RTCNT(T,R)
% rate constant
k0 = 8.849e14;
% 1 J = 2.389x10-4 kcal
% E = 40765 kcal/kmol
E
= 40765 / 2.389e-4; %
= 1.0e-3*E ;
J/kmol
% kJ/kmol
kArh = k0*exp(-E/(R*T));
function[CpH2,CpN2,CpNH3,CpCH4,CpAr] = SPCHT(T,P)
% specific heat capacities
% cp in kJ/(kmol-K);
% T in K
% P in atm
CpH2=6.952-(0.04567E-2*T)+(0.09563E-5*T^2)-(0.2079E-9*T^3);
CpH2=4.184*CpH2;
CpN2=6.903-(0.03753E-2*T)+(0.1930E-5*T^2)-(0.6861E-9*T^3);
CpN2=4.184*CpN2;
% this expression from Dashti does not give results matching with nist
% a simple model from VKN
%CpNH3a=6.5846-(0.61251E-2*T)+(0.23663E-5*T^2)-(1.5981E-9*T^3);
147
%CpNH3b=(96.1678-0.067571*P+(0.2225+1.6847E-4*P)*T+(1.289E-4-1.0095E7*P)*T^2);
%CpNH3 = 4.184*(CpNH3a+CpNH3b);
% use Shomate equations from NIST 298-1400 K
A=19.99563; B=49.77119; C=-15.37599; D=1.921168; E=0.189174;
t = T/1000;
CpNH3=A + B*t + C*t^2 + D*t^3 + E/t^2;
CpCH4=4.75+(1.2E-2*T)+(0.303E-5*T^2)-(2.63E-9*T^3);
CpCH4=4.184*CpCH4;
CpAr=4.9675;
CpAr=4.184*CpAr;
148
APPENDIX B2: MATLAB PROGRAM FOR FINDING EQUILIBRIUM

CONCENTRATIONS
This section lists the Program SSEqmProg
Program SSEqmProg computes equilibrium mole fraction, extent & Equilibrium
Constant K
% Program Name: SSEqmProg
%
To find the eqm concn
%
% C:\MATLAB7\work\Ammonia\SSEqmProg.m
%
% Jan 2011
%
% open output file
resl=fopen('out1.txt','w'); % INPUT and STREAM OUTPUT
tic
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
% step 1 specify an initial conc N2 mole = 1 H2=3 NH3 = 0
% step 2 specify T, P
% step 3 evaluate K(T)
% step 4 calc eps (extent of reaction)
% step 5 plot eps vs T for fixed P
% STATIC DATA
fprintf (resl,'\n physical data');
fprintf (resl,'\n universal data');
fprintf (resl,'\n Universal Gas Const = %12.6f kJ/(mol-K)\n',R_un);
%
chemical
data
from
http://wwwjmg.ch.cam.ac.uk/tools/magnus/PeriodicTable.html
% component ID:
1 : H2
2: N2
3: Ar
4: Ammonia
5:Methane
MW1=2.0*1.0079759; MW2=2.0*14.0067231; MW4= 39.9476613;
MW3=(14.0067231+3.0*1.0079759); MW5 = (12.0110369+4.0*1.0079759);
%----------------% STEP 1 initial composition
n(2) = 1.0;
% moles of nitrogen
n(1) = 3*n(2); % moles of hydrogen
n(3) = 0.0; % ammonia mole fraction
nI = 0.0; % inerts mole fraction
kappa= 0; % ratio of Ar/Methane
n(4) = (kappa/(1+kappa))*nI;
n(5) = nI - n(4);
fprintf
fprintf
fprintf
fprintf
fprintf
fprintf
(resl,'\n
(resl,'\n
(resl,'\n
(resl,'\n
(resl,'\n
(resl,'\n
ID
1
2
3
4
5
Name
Hydrogen
Nitrogen
Ammonia
Argon
Methane
Mol Wt (kg/kmol)
Moles\n');
%8.4f %21.4f',MW(1),n(1));
%8.4f %21.4f',MW(2),n(2));
%8.4f %21.4f',MW(4),n(3));
%8.4f %21.4f',MW(3),n(4));
%8.4f %21.4f',MW(5),n(5));
149
fprintf (resl,'\n ----------------------------\n');

%-----------------NP = 6; NT = 20;
% STEP 2 specify T, P
Pressure = 0.0; % atm
for j = 1:NP
Pressure = Pressure+50 ; % atm
ppp(j) = Pressure; % pressure of reaction
fprintf (resl,'\n\n
System pressure is %8.2f atm',Pressure);
temp = -50.0;
% deg C
for i = 1:NT
temp = temp + 50.0;
Temp = temp +273.15 % K
%temp = 675-273.15; Temp=temp+273.15;
% STEP 3 evaluate K(T,P)
%[Ka] = EQNCN(Temp); % Dashti expression
% Ka from Narayanan p.417 Eq. 9.58
lnKa = 79201/(R_un*Temp) - (48.8/R_un)*log(Temp) + (17.38e-3/R_un)*Temp +
14.169;
Ka = (exp(1))^lnKa;
% STEP 4 calc eps
alpha = sqrt( 27.0 * Ka * Pressure^2 );
beta = alpha + 4.0;
tt1 = 1.0 - alpha/beta;
eps = 1.0e23;
if (tt1>=0)
tt2 = sqrt(tt1);
eps1 = 1.0 + tt2;
eps2 = 1.0 - tt2;
end
%fprintf (resl,'\n eps1 = %12.4f
eps2 = %12.4e \n',eps1,eps2);
% now select the value less than 1

if (eps1 <= 1 ) eps = eps1;
end
if (eps2 <= 1 ) eps = eps2;
end
% what if both epsilons are +ve ?
ttt(j,i)
TTT(j,i)
eee(j,i)
kkk(j,i)
aaa(j,i)
=
=
=
=
=
temp; % deg C
Temp; % Kelvin
eps; % extent of reaction
log10(Ka); % log10 of eqm const
2*eps/(4 - 2*eps);
end % end of temperature loop
150
% write the results

fprintf (resl,'\n
No. temp (C)
Temp (K)
Ka
eps');
for iP = 1: NT
fprintf
(resl,'\n %4.0f %9.2f %9.2f %12.4e %12.4f',iP,ttt(j,iP),TTT(j,iP),kkk(j,iP)
,eee(j,iP));
end
end
% end of pressure loop
% STEP 5
plot the results
PlotExtent = 0;
PlotNH3eqm = 1;
PlotEqmConst = 0;
if (PlotExtent == 1)
for plotP = 1:NP
for k = 1:NT
X(k) = ttt(plotP,k); % temp deg C
Y(k) = eee(plotP,k); % extent of reaction
% Y(k) = kkk(plotP,k); % eqm const
end
plot(X,Y,'-k')
hold on
end
xlabel (' Temp (^oC)','Fontsize',16)
ylabel ('Extent (\epsilon ) ','Fontsize',16)
grid off
text(400,0.15,'50 ','Fontsize',12)
text(560,0.35,'300','Fontsize',12)
text(530,0.90,'\bf Pressure','Fontsize',12)
text(450,0.85,'50,100,150,200,250,300 atm','Fontsize',12)
end % end of plot of extent reaction
if (PlotNH3eqm == 1)
for plotP = 1:NP
for k = 1:NT
Y(k) = aaa(plotP,k); % mol fraction of ammonia in eqm mixture
% Y(k) = kkk(plotP,k); % eqm const
end
plot(X,Y,'-k')
hold on
end
ylabel ('NH_3 in Eqm. Mix. (mol. fr.) ','Fontsize',16)
grid on
text(320,0.15,'50 ','Fontsize',12)
text(480,0.35,'300','Fontsize',12)
text(530,0.90,'\bf Pressure','Fontsize',12)
text(450,0.85,'50,100,150,200,250,300 atm','Fontsize',12)
end % end of plot of ammonia in eqm mixture
if (PlotEqmConst == 1)
for plotP = 1:NP
for k = 1:NT
151
Y(k) = kkk(plotP,k); % eqm const

end
plot(X,Y,'-k')
hold on
end
ylabel ('Eqm. Const. (log_{10}K_a) ','Fontsize',16)
grid on
end % end of plot of Equilibrium Constant
toc
fclose(resl);
152
APPENDIX B3: MATLAB PROGRAM FOR FINDING OUTPUT OF

COUNTER-FLOW SYNTHESIS REACTOR
This section lists the Program RunSSoptim and its function SSoptim
Program SSoptim computes output for counter flow synthesis reactor by
solving three equations as described by B.V.Babu: counterflow feed/reacting
Gas and temperature
Data: inlet conditions
Output: outlet conditions
% Program Name: RunSSoptim
%
% C:\MATLAB7\work\Ammonia\RunSSoptim.m
% Last modified May 28 2011
%
%
% open output file
resl=fopen('out1.txt','w'); % INPUT and STREAM OUTPUT
tic
options = odeset('RelTol',1e-6,'AbsTol',[1e-8 1e-8 1e-8]);
[t,Y] = ode15s(@SSoptimKREETZ,[0 0.8],[663 663 0.0251],options);
% ammonia moles
AmmMolesInit = 0.0029;
NMolesInit = 0.0251;
Amm = AmmMolesInit + 2*( NMolesInit - Y(:,3));
PlotTemp = 1;
PlotComp = 0;
PlotBoth = 0;
% for plot showing temperatures only

if (PlotTemp ==1)
plot (t,Y(:,1),'-ok')
hold on
plot (t,Y(:,2),'-sk')
grid on
h = legend('Feed Gas','Reacting Gas',1);
% title 'Feed Gas Temperature and Reacting Gas Temperature'
end
153
% for plot showing molar compositions only

if (PlotComp ==1)
plot (t,Y(:,3),'-ok')
hold on
plot (t,Amm,'-sk')
grid on
h = legend('N_2','NH_3',1);
title 'Nitrogen and Ammonia Molar Flow Rates'
end
if (PlotBoth ==1)
subplot(2,1,1)
plot (t,Y(:,1),'-ok')
hold on
plot (t,Y(:,2),'-sk')
grid on
h = legend('Feed Gas','Reacting Gas',1);
% title 'Feed Gas Temperature and Reacting Gas Temperature'
subplot (2,1,2)
plot (t,Y(:,3),'-ok')
hold on
plot (t,Amm,'-sk')
grid on
h = legend('N_2','NH_3',1);
%title 'Nitrogen and Ammonia Molar Flow Rates'
end
toc
fclose(resl);
function dy = SSoptim(t,y)
dy = zeros(3,1);
% a column vector
%
% last modified 28 May 2011
%
% MATLAB commands to run this program
%
options = odeset('RelTol',1e-6,'AbsTol',[1e-8 1e-8 1e-8]);
%
[t,Y] = ode15s(@SSoptim,[0 8],[700 700 701.2],options);
%
plot(t,Y(:,1),'-',t,Y(:,2),'-.',t,Y(:,3),'.')
Cpf=3.0 ; % kJ/(kg-K) cold feed gas
Cpg=3.1 ; % kJ/(kg-K) hot reacting gas flowing downwards
U=140.0;
% heat transfer coefficient kW/(m^2-K)
154
s1=2.*3.14159*7.9/1000;
% surface area of cooling tubes per length of
reactor
W=1.08; % mass flow rate kg/s
f=1.0;
% catalyst effectiveness or concentration
H=-100000.0;% kJ/(kmol N_2)
R= 8.314472;
% universal gas constant kJ/(kmol-K)
Press=150; % system pressure atm
s2=3.14159*7.9*7.9*1.0e-6;
% cross-section area of catalyst zone
% Moles kmol/h-m^2 at Feed
% component ID:
1 : H2
2: N2
3: Ar
4: Ammonia
5:Methane
xFeed= [ 0.6567006; 0.2363680; 0.0202874; 0.026930; 0.059714]; % mole
fractions
TotalFeed = 0.1062; % kmols / hr
H2F
= xFeed(1) * TotalFeed;
% kmol/h
N2F
= xFeed(2) * TotalFeed ;
% kmol/h
NH3F
= xFeed(4) * TotalFeed;
% kmol/h
InertsF
= (xFeed(3) + xFeed(5)) * TotalFeed; % kmol/h
%fprintf (resl,'\n Total Feed = %12.4f moles/h-m^2 \n',TotalFeed);
%
dy(1)
is dTf
dy(2) is dTg
dy(3) is dN
% feed gas temp eqn

dy(1)=((-U*s1)/(W*Cpf))*(y(2)-y(1));
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
% hot gas temp
%Tf = TfLast;
T=y(2); %this is the temp of the gas flowing downwards
convertedN = N2F - y(3);
H2Now = H2F - 3*convertedN ;
N2Now = y(3);
NH3Now= NH3F + 2*convertedN;
InertsNow = InertsF;
TotalMolesNow = TotalFeed - 2.0*convertedN ;
xH = H2Now/TotalMolesNow;
xN = N2Now/TotalMolesNow;
xA = NH3Now/TotalMolesNow;
[phiH2,phiN2,phiNH3,aH2,aN2,aNH3]=ACTVT(Press,T,xH,xN,xA);
[Ka] = EQNCN(T);
[kArh]= RTCNT(T,R);
dndx = -f* RNH3/2.0 ;
dy(2) =(-U*s1)/(W*Cpg)*(y(2)-y(1))+ ( (-H*s2)/(W*Cpg) ) * ( -dndx );
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
% moles of N2
% parameter T represents moles of N2 (normalized)
%Tg=TgLast;
Tg = y(2);
[phiH2,phiN2,phiNH3,aH2,aN2,aNH3]=ACTVT(Press,T,xH,xN,xA);
155
[Ka] = EQNCN(T);
[kArh]= RTCNT(T,R);
dy(3) = -f* s2* RNH3/2.0 ;
156
APPENDIX B4: MATLAB PROGRAM FOR FINDING OUTPUT OF

STEADY STATE SYNTHESIS REACTOR WITH 3 CATALYST ZONES
% Program Name: SSATSNonUnif
%
Steady State Ammonia Thermal Storage
%
% C:\MATLAB7\work\Ammonia\SSATS_NonUnif_New
%
% First Written: JULY 2010
% Last Update: 24 May 2011
% open output file
resl=fopen('outSSATSnu.txt','w'); % INPUT and STREAM OUTPUT
tic
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
%
%
%
%
%
%
%
INPUT
System Pressure (atm)
Temp (K)
Total Mass Flow Rate (kg/hr) =
Mole fractions (H,N,Ar,Amm,Met) [x] =
Length of converter Lmax (m)
% OUTPUT
% graph of mol fractions of H, N, Amm vs length
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
NS = 10; % number of streams
NC = 5; % number of components, H2,N2,NH3,Ar,CH4
fprintf (resl,'\n No. of Streams
= %3.0f \n',NS);
%%%%%%%%%%%%%%%%%%%%%%%%% DATA **********************
%R_un = 1545.349 ; % lbf.ft/lbmol.R
%R_un = 1545.349;
% component ID:
1 : H2
2: N2
3: Ar
4: Ammonia
5:Methane
MW1=2.0*1.0079759; MW2=2.0*14.0067231; MW3= 39.9476613;
MW4=(14.0067231+3.0*1.0079759); MW5 = (12.0110369+4.0*1.0079759);
Name
fprintf (resl,'\n 1 Hydrogen %8.4f ',MW(1));
fprintf (resl,'\n 2 Nitrogen %8.4f ',MW(2));
fprintf (resl,'\n 3 Argon
%8.4f ',MW(3));
fprintf (resl,'\n 4 Ammonia
%8.4f ',MW(4));
fprintf (resl,'\n 5 Methane
%8.4f ',MW(5));
fprintf (resl,'\n ----------------------------\n');
% STREAM 1: SYN GAS ENTERING C-1 ******************************************
IS=1;
% STREAM INPUT
157
P(1) = 100.0; % atm

P_SIunits(1) = P(1)*1.0e5; %Pascals
T(1) = 300.0; % Kelvin
TotMassFlRate(IS) = 0.3*60*60/1000; % kg/hr
line 207
this for comp; for stream 3,
% component ID:
1 : H2
2: N2
3: Ar
4: Ammonia
5:Methane
x= [ 0.6567006; 0.2363680; 0.0202874; 0.026930; 0.059714]; % mole
fractions
% x= [ 0.78; 0.20 ; 0.0 ; 0.02; 0.0]
Area = 3.14159 * (1.58e-2)^2 ; % cross-section area of catalyst m^2
fprintf (resl,'\n Area = %12.4e m^2',Area);
fprintf (resl,'\n Vol of catalyst = %12.4e m^3 \n',VolCatalyst);
%x= [ 0.7426; 0.2475; 0.0099; 0.0; 0.0]; % mole fractions
%mfm = [ 750.0 ; 250.0 ;
10.0; 0.0; 0.0]; % kg-mols/hr
%
MWT(IS) = 0.0; % average molecular weight of stream
for i = 1:NC
MWT(IS)=MWT(IS)+x(i)*MW(i);
xT
= xT
+x(i);
end
RR(IS) = R_un/MWT(IS); % gas constant for this stream (gas)
%------------------------------% mfrT = 0.0; % total mass flow rate/hr
% for j=1:NC
%
mfr(j)=mfm(j)*MW(j); % kg/hr
%
mfrT = mfrT + mfr(j);
% end
% MolarFlRateMix(IS) = mfrT/MWT(IS); % moles per hr
%-------------------------------MolarFlRateMix(IS) = TotMassFlRate(IS)/MWT(IS); % in kmols/hr
mfrT=0.0;
mfmT=0.0;
for jk=1:NC
mfr(jk) = x(jk)*MolarFlRateMix(IS); % units kmol/hr
mfm(jk) = mfr(jk)*MW(jk);
mfmT = mfmT + mfm(jk);
% units should be kg/hr
end
158
%
% STREAM OUTPUT
fprintf (resl,'\n ----------------------------------------------------\n');
fprintf (resl,'\n STREAM No: %3.0f \n',IS);
Mole Fr
Molar flow rate
Mass flow rate');
fprintf (resl,'\n
kg-mols/hr
kg/hr\n');
for i=1:NC
%8.4f
%8.4f
%8.4f
',i,x(i),mfr(i),mfm(i))
end
fprintf (resl,'\n \n Total %6.4f
%8.4f
%8.4f\n',xT,mfrT,mfmT);
MWt( %2.0f ) = %8.4f kg/kmol
',IS,MWT(IS));
fprintf (resl,'\n Gas Const of mixture RR ( %2.0f ) = %8.4f kJ/(kmol-K)
',IS,RR(IS));
',IS,MolarFlRateMix(IS));
fprintf (resl,'\n ----------------------------------------------------\n');
% COMPRESSOR WORK FOR STREAM 1
CpMix = 0.0;
RMix = 0.0;
% find the Cp values at this temp T1 and press P(1)
[CpH2,CpN2,CpNH3,CpCH4,CpAr] = SPCHT(T(1),P(1)); % kJ/(kmol-K)
jj=1;
for j= NC+1:2*NC
Cp(j) = Cp(jj)/MW(jj);
jj=jj+1;
end
fprintf (resl,'\n -----------------------------------------\n');
fprintf (resl,'\n Cp values from function SPCHT at T = %8.2f K and P =
%6.2f atm\n',T(1),P(1));
Cp kJ/(kmol-K) kJ/(kg-K)\n');
fprintf (resl,'\n 1 Hydrogen %12.4e %12.4e ',Cp(1),Cp(6));
fprintf (resl,'\n 1 Nitrogen %12.4e %12.4e ',Cp(2),Cp(7));
%12.4e %12.4e ',Cp(3),Cp(8));
%12.4e %12.4e ',Cp(4),Cp(9));
%12.4e %12.4e ',Cp(5),Cp(10));
fprintf (resl,'\n ------------------------------------------\n');
for i = 1:NC
Rg(i) = R_un/MW(i); % kJ/(kmol-K) * kmol/kg = kJ/(kg-K)
%RMix = RMix + Rg(i)*mfm(i)/mfmT; % based on mass fl rates
RMix = RMix + R_un *mfr(i)/mfrT; % based on molar fl rates
CpMix = CpMix + Cp(i)*mfr(i)/mfrT; % based on molar flow rates
end
CvMix = CpMix - RMix; % molar basis
fprintf (resl,'\n Mixture properties (based on molar ratios)\n');
fprintf (resl,'\n
CpMix (kJ/(kmol-K) CvMix
RMix
GammaMix\n');
%12.4e
%12.4e
%8.2f
159
% compressor work
n=1;
P(2) = 1.5 * P(1); % discharge pressure
PressRatio = P(2)/P(1);
[Ws]=COMPR(n,T(1),RMix,P(1),P(2),GammaMix); % gives Work in kJ/kmol of gas
PowerComp = Ws * MolarFlRateMix(1); % kJ/hr
PowerComp = (1./(60.*60.))*PowerComp; % kW
fprintf
fprintf
fprintf
fprintf
fprintf
fprintf
fprintf
fprintf
(resl,'\n
(resl,'\n
(resl,'\n
(resl,'\n
(resl,'\n
(resl,'\n
(resl,'\n
(resl,'\n
Compressor Power \n');

Reciprocating Compressor\n')
No of stages = %2.0f ',n);
Suction
Pressure = %12.4e atm \n',P(1));
Discharge Pressure = %12.4e atm \n',P(2));
Pressure Ratio
= %6.2f
\n\n',PressRatio);
Compressor Work
= %12.4e kJ/kmol \n',Ws);
Compressor Work
= %12.4e kW \n',PowerComp);
% example from K.V.Narayanan p.134

% the R used in this is the universal Gas Const; this prog uses RgasMix
% (check again)
%[Ws]=COMPR(1,300,8.314,1,10,1.3);
%PowerComp = Ws * 1.114e-3;
%fprintf (resl,'\n Compressor Work
= %12.4e kW \n',PowerComp);
%------------------------------ SYNTHESIS -------------------------% STREAM 3
% give input data for stream
% molar flow rate; mole fractions, pressure and temperature
% output will be mole fractions, temperature and pressure
% solve the equations using RK-4 method
% STREAM 3: SYN GAS ENTERING R-1 ******************************************
IS=3;
% STREAM INPUT
P(IS) =150.0 ; % atm
P_SIunits(IS) = P(IS)*1.0e5; %Pascals
%T(IS) = 371+273; % Kelvin Dashti paper inlet T
%T(IS) = 291 + 273 - 10 ; % Kelvin with Manson Set 2
T(IS) = 390
+273; % Kreetz and Lovegrove 1999
InletTemp = T(IS);
TotMassFlRate(IS) = 0.3*60*60/1000; % kg/hr
Dashti p.20
% component ID:
1 : H2
2: N2
3: Ar
4: Ammonia
5:Methane
%x= [ 0.6567006; 0.2363680; 0.0202874; 0.026930; 0.059714]; % mole
fractions
%x= [ 0.6567006; 0.2363680; 0.0202874; 0.026930; 0.059714]; % mole
fractions
% mfm = [ 750.0 ; 250.0 ;
10.0; 0.0; 0.0]; % kg-mols/hr
%
MWT(IS) = 0.0; % average molecular weight of stream
160

for i = 1:NC
MWT(IS)=MWT(IS)+x(i)*MW(i);
xT
= xT
+x(i);
end
RR(IS) = R_un/MWT(IS); % gas constant for this stream (gas)
TotMolarFlRate(IS) = TotMassFlRate(IS)/MWT(IS); % kmoles per hr
sumMol = 0.0;
sumMas = 0.0;
for j=1:NC
MolFlRate(j) = x(j) * TotMolarFlRate(IS); % kmol/hr
MassFlRate(j)= MolFlRate(j) * MW(j); % kmol/hr * kg/kmol = kg/hr
end
%
% STREAM OUTPUT
fprintf (resl,'\n ----------------------------------------------------\n');
fprintf (resl,'\n STREAM No: %3.0f \n\n',IS);
Temperature = %8.2f
\n\n',P(IS),T(IS));
Mole Fr
Molar flow rate
Mass flow rate');
fprintf (resl,'\n
kmoles/hr
kg/hr\n');
for i=1:NC
%8.4f
%8.4f
%8.4f
end
%12.4f
MWt(%2.0f) = %8.2f kg/kmol
\n',IS,MWT(IS));
fprintf (resl,'\n Gas Const of mixture RR (%2.0f) = %8.2f kJ/(kmol-K)
',IS,RR(IS));
',IS,TotMolarFlRate(IS));
fprintf (resl,'\n Mass Flow Rate of Stream %3.0f is %8.4f kg /hr
',IS,TotMassFlRate(IS));
fprintf (resl,'\n ----------------------------------------------------\n');
% SECTION BEGINS =====================================================
% do this section if you want to check manually the orders of magnitude
% otherwise remove this section
% activities: a_i = y_i * phi_i * P
% y_i is the mole fraction which is available above, as x(i)
% obtain phi_i from the function
% function[phiH2,phiN2,phiNH3,aH2,aN2,aNH3]=ACTVT(P,T,yH2,yN2,yNH3)
[phiH2,phiN2,phiNH3,aH2,aN2,aNH3]=ACTVT(P(IS),T(IS),x(1),x(2),x(4));
% now compute the equilibrium constant K
% function[Ka] = EQNCN(T)
[Ka] = EQNCN(T(IS));
% now find Arrhenius Rate Constant
[kArh]= RTCNT(T(IS),R_un);
161
% now find reaction rate

[CpH2,CpN2,CpNH3,CpCH4,CpAr] = SPCHT(T(IS),P(IS));
jj=1;
for j= NC+1:2*NC
jj=jj+1;
end
CpMix = 0.0;
for ii = 1:NC
end
[HtReact]= DeltaH(P(IS),T(IS));
% X is the height from the top of the catalyst (m) and StepX is the
% increment in X
fprintf (resl,'\n Test Section output begins ...\n');
fprintf (resl,'\n Pressure = %6.2f atm
Temp = %6.2f',P(IS),T(IS));
X = 0.0; StepX=0.5;
fprintf (resl,'\n X = %6.2f m
StepX = %6.2f',X,StepX);
Zold = 0; % no N2 has been converted as yet
fprintf (resl,'\n Zold = %6.2f',Zold);
Told = T(IS); % this is temp at the inlet of this volume
N20 = MolFlRate(2); % kmols/hr of N2 entering this volume element
fprintf (resl,'\n N20 = %6.2f kmol/hr ',N20);
fprintf (resl,'\n Mdot = %12.4e kg/hr',TotMassFlRate(IS));
fprintf (resl,'\n Cp
= %12.4e kJ/(kg-K) ',CpMix);
fprintf (resl,'\n x(1) = %8.4f
x(2)=%8.4f
x(4)=%8.4f
',x(1),x(2),x(4));
fprintf (resl,'\n RNH3 = %12.4e kmol/(hr-m^3) ',RNH3);
fprintf (resl,'\n HtReact = %12.4e kJ/kmol ',HtReact);
dZdX = Area*RNH3 /(2.0*N20);
dTdX = abs(HtReact)*RNH3*Area/(TotMassFlRate(IS)*CpMix);
fprintf (resl,'\n\n dZ/dx = %12.4e conversion per meter',dZdX);
fprintf (resl,'\n dT/dx = %12.4e K per meter
\n',dTdX);
% now use the above gradients to find new values for moles of H, N, Ammonia
% the volume of this box is now
DeltaVolume = Area * StepX;
Area * StepX
Znew = Zold + dZdX * StepX;

Tnew = Told + dTdX * StepX;
fprintf (resl,'\n New values
Z = %6.2f
T = %6.2f K \n',Znew,Tnew);
% now compute new moles and mole fractions

% converted moles of N2
delta = Znew * MolFlRate(2);
% new mole rates (kmols/hr) and mass flow rates (kg/hr)
162
for ik =1:NC
MolFlRateOld(ik) = MolFlRate(ik);
MassFlRateOld(ik) = MassFlRate(ik);
MolFlRateNew(ik) = 0.0; % need to compute this now
MassFlRateNew(ik)= 0.0; % need to compute this now
xold(ik)
xnew(ik)
= x(ik); % old mole fractions

= 0.0;
end
% new totals
TotMolarFlRateOld(IS)=TotMolarFlRate(IS);
TotMolarFlRateNew(IS)=0.0;
TotMoleFrOld=0.0;
TotMoleFrNew=0.0;
TotMassFlRateOld(IS)=TotMassFlRate(IS);
TotMassFlRateNew(IS)=0.0;
MolFlRateNew(1) = MolFlRateOld(1) - 3.0* delta; % H2

MolFlRateNew(2) = MolFlRateOld(2) - 1.0* delta; % N2
% Argon
MolFlRateNew(4) = MolFlRateOld(4) + 2.0* delta; % NH3
% CH4
%
for ik1 = 1:NC
MassFlRateNew(ik1) = MW(ik1) * MolFlRateNew(ik1);
end
for ik2 = 1:NC
TotMolarFlRateNew(IS) = TotMolarFlRateNew(IS) + MolFlRateNew(ik2);
TotMassFlRateNew(IS) = TotMassFlRateNew(IS) + MassFlRateNew(ik2);
end
for ik11 = 1:NC
xnew(ik11)
end
= MolFlRateNew(ik11)/TotMolarFlRateNew(IS);
for ik12 = 1:NC

TotMoleFrOld = TotMoleFrOld + xold(ik12);
TotMoleFrNew = TotMoleFrNew + xnew(ik12);
end
% now write a summary of the change
fprintf (resl,'\n\n SUMMARY AFTER CONVERSION in this volume box Area*StepX
\n');
fprintf (resl,'\n
BEFORE CONVERSION
AFTER CONVERSION\n');
fprintf (resl,'\n
i
MolFlRate
mol fr MassFlRate
MolFlRate
mol fr
MassFlRate');
fprintf (resl,'\n
kmol/hr
kg/hr
kmol/hr
kg/hr');
for ik3=1:NC
163
fprintf (resl,'\n %3.0f %15.4e %8.4f %12.4e %20.4e %8.4f %12.4e

',ik3,MolFlRateOld(ik3),xold(ik3),MassFlRateOld(ik3),MolFlRateNew(ik3),xnew
(ik3),MassFlRateNew(ik3));
end
fprintf (resl,'\n %21.4e %8.4f %12.4e %21.4e %9.4f
%13.4e',TotMolarFlRateOld(IS),TotMoleFrOld,TotMassFlRateOld(IS),TotMolarFlR
ateNew(IS),TotMoleFrNew,TotMassFlRateNew(IS));
% how much energy is given off in this volume?
% mass flow rate is the same before or after so can use either
Power = TotMassFlRateOld(IS)*CpMix*(Tnew-Told); % (kg/hr)*(kJ/kg-K)*(K) =
kJ/hr
fprintf (resl,'\n Test Section ends.............\n\n\n');
%SECTION ENDS =======================================

t=0
[Eta1]=ETA(P(IS),T(IS),Z);%
start with ) since no N2 is converted at

Temperature = %8.2f
\n',P(IS),T(IS));
%fprintf (resl,'\n Temp
phiH2
phiN2
phiNH3
aH2
aN2
aNH3
Ka
kArh
RNH3\n');
%fprintf (resl,'\n %6.1f %10.2e %10.2e %10.2e %10.2e %10.2e %10.2e %10.2e
%10.2e %10.2e\n',T(IS),phiH2,phiN2,phiNH3,aH2,aN2,aNH3,Ka,kArh,RNH3);
%---------------------------------------------------------% begin RK 4th order for 2 1st-order coupled ODEs
%Area is defined above
Z = 0.0;
T = T(IS);
P = P(IS);
TT(1)=T;
% initial value of temperature (K)
Lmin =0.0;
NZONES = 3;
NPTZ=10; % 10 meshes in each zone
NPTS = NPTZ*NZONES; % 30 meshes total
164
LL(1)=Lmin;
for i = 2: NPTS+1
LL(i) = LL(i-1)+h;
end
LL
L = LL(1);
i = 1 ;
% component ID:
1 : H2
2: N2
3: Ar
4: Ammonia
5:Methane
Hmoles(i) = MolFlRate(1);
Nmoles(i) = MolFlRate(2);
Rmoles(i) = MolFlRate(3);
Amoles(i) = MolFlRate(4);
Mmoles(i) = MolFlRate(5);
TotalMoles(i) = Hmoles(i) + Nmoles(i) + Rmoles(i) + Amoles(i) + Mmoles(i);
HmolesFr(i) = Hmoles(i)/TotalMoles(i); % for plotting, instead of mole fl
rates
NmolesFr(i) = Nmoles(i)/TotalMoles(i);
AmolesFr(i) = Amoles(i)/TotalMoles(i);
%
%%%%%%%%%%%%%%% patch added 18 May 2011 %%%%%%% for printout only
Tsend = T;
TotMassSend = TotMassFlRate(IS);
[MWtMixture,CpMixKg,CpMixMo,TotMolarFlRateMix,Moles,masses]=CpSummary(Tsend
,P,x,MW,TotMassSend);
CpKg(i) = CpMixKg; % kJ/(kg-K)
CpMo(i) = CpMixMo; % kJ/(kmol-K)
MWmix(i)= MWtMixture; % kg/kmol
MdotCpKT(i) = ((TotMassFlRate(IS))/3600)*CpKg(i)*Tsend; % kg/s * kJ/(kg-K)
* K = kW
TMFMix(i)=TotMolarFlRateMix;
hhh(i)=Moles(1); nnn(i)=Moles(2); rrr(i)=Moles(3); amm(i)=Moles(4);
ch4(i)=Moles(5);
massh(i)=masses(1); massn(i)=masses(2); massr(i)=masses(3);
massa(i)=masses(4); massc(i)=masses(5);
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% end of patch 18 May 2011 %%%%%%%%
%%%%%%%%%%%%%% patch added 15 May 2011
% now find, at this point as an initial condition, the equilibrium position
Epsilon=0.0;
i=1;
[Epsilon] = EquilibriumC (P,T,Hmoles(i),Nmoles(i),Amoles(i),TotalMoles(i));
HmolesEq(i) = Hmoles(i) - 3.0*Epsilon ;
NmolesEq(i) = Nmoles(i) - Epsilon ;
RmolesEq(i) = Rmoles(i) ;
AmolesEq(i) = Amoles(i) + 2.0*Epsilon ;
MmolesEq(i) = Mmoles(i) ;
%
TotalMolesEq(i) = HmolesEq(i) + NmolesEq(i) + RmolesEq(i) + AmolesEq(i) +
MmolesEq(i);
165
AmolesPCEq(i) = AmolesEq(i)/TotalMolesEq(i);
TTeps(1) = Epsilon;
% now find equilibrium temp
[Teqm] = EquilibriumT (x,P,T);
TTeqm(i)=Teqm;
% what if Teqm is not found? set it to max
if (Teqm==0)
TTeqm(i)=800.0;
end
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
EachZoneHgt = Lmax/NZONES;
LBDRY(1) = 0.0;
for ibdry = 2:NZONES+1
LBDRY(ibdry)=LBDRY(ibdry-1)+EachZoneHgt;
end
LBDRY
%%%%%%%%%%%%%%%%%%%%%%%%% CATALYST LOADING %%%%%%%%%%%%%%%%%%
fprintf (resl,'\n No of catalyst zones = %2.0f \n',NZONES);
frac = [1.5;1.25;1.0];
fprintf (resl,'\n Zone
LBDRY Fraction of Catalyst');
for icat = 1:NZONES
fprintf (resl,'\n %2.0f %6.2f %6.2f ',icat,LBDRY(icat+1),frac(icat));
end
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
CatFrac = frac(1); % start with the fraction of zone 1
fprintf (resl,'\n
i
x(1)
x(2)
x(3)
x(4)
Mole Fl Rate');
fprintf (resl,'\n %3.0f %8.4f %8.4f %8.4f %8.4f %8.4f
%15.4e',i,x(1),x(2),x(3),x(4),x(5),TotalMoles(i));
x(5)
Toptimal(i) = 896.0;
NPTS1=NPTS-1;
PZ1 = 0; PZ2 =0; PZ3 = 0;
% limits of i in zones
% in zone 1
i goes from
1
to
%
2
i
NPTZ+1
to
%
3
i
2*NPTZ+1 to
iLIM1 = NPTZ+1; iLIM2 = 2*NPTZ+1; iLIM3
NPTZ+1
2*NPTZ+1
3*NPTZ+1
= 3*NPTZ+1;
while (i <= NPTS) %---------------------------------- RK4 LOOP BEGINS

i;
% zone is defined by height from top
L
if (i<=iLIM1)
thisZone = 1;
166
Total
LastZone = thisZone;
%
PZ1 = PZ1 +1; % this counter runs from 1 to last value of PZ1=NPTZ
fprintf (resl,'\n PZ1 = %3.0f ',PZ1);
TMB(1,PZ1)=TT(i);
LMB(1,PZ1)=LL(i);
end
if ((i>=iLIM1)&(i<=iLIM2))
thisZone = 2;
if (LastZone==1)
TT(i)=TT(3);
end
%
PZ2 = PZ2 +1; % this counter runs from 1 to last value of PZ2 (20)
TMB(2,PZ2)=TT(i);
LMB(2,PZ2)=LL(i);
end
if ((i>=iLIM2)&(i<=iLIM3))
thisZone = 3;
if (LastZone==2)
%
TT(i)=TT(2);
end
PZ3 = PZ3 +1; % this counter runs from 1 to last value of PZ3
TMB(3,PZ3)=TT(i);
LMB(3,PZ3)=LL(i);
end
CatFrac = frac(thisZone);
%%%%%%%%%%%%%%%%%%%%%%%%%%%
k1_z
k1_T %%%%%%%%%%%%%%%%%%%%
% first function
[Eta1]=ETA(P,T,Z);
[Ka] = EQNCN(T);
FUNC1 = Eta1*CatFrac*RNH3/(2.0*FoverA);
k1_z = FUNC1;
% second function
% evaluate RHS of energy conservation equation FUNC2
167

jj=1;
for j= NC+1:2*NC
jj=jj+1;
end
CpMix = 0.0;
for ii = 1:NC
end
FUNC2 = ( HtReact * Eta1 * CatFrac*RNH3 ) / ((TotMassFlRate(IS)/Area) *
CpMix );
k1_T = -FUNC2;
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
%
k2_z
k2_P
L
= LL(i) + h/2. ;
Z
= ZZ(i) + k1_z * h/2.0;
T
= TT(i) + k1_T * h/2.0;
% first function
[Eta1]=ETA(P,T,Z);
[Ka] = EQNCN(T);
k2_z = FUNC1;
% second function
jj=1;
for j= NC+1:2*NC
jj=jj+1;
end
CpMix = 0.0;
for ii = 1:NC
end
FUNC2 = ( HtReact * Eta1 * CatFrac* RNH3 ) / ((TotMassFlRate(IS)/Area) *
CpMix );
k2_T = -FUNC2;
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
%
k3_z
k3_P
Z
= ZZ(i) + k2_z * h/2.0;
T
= TT(i) + k2_T * h/2.0;
% first function
[Eta1]=ETA(P,T,Z);
168
[Ka] = EQNCN(T);
FUNC1 = Eta1*CatFrac* RNH3/(2.0*FoverA);
k3_z = FUNC1;
% second function
jj=1;
for j= NC+1:2*NC
jj=jj+1;
end
CpMix = 0.0;
for ii = 1:NC
end
FUNC2 = ( HtReact * Eta1 * CatFrac* RNH3 ) / ((TotMassFlRate(IS)/Area) *
CpMix );
k3_T = -FUNC2;
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
%
k4_z
k4_P
L
Z
T
= LL(i) + h;
= ZZ(i) + k3_z * h;
= TT(i) + k3_T * h;
% first function
[Eta1]=ETA(P,T,Z);
[Ka] = EQNCN(T);
k4_z = FUNC1;
% second function
jj=1;
for j= NC+1:2*NC
jj=jj+1;
end
CpMix = 0.0;
for ii = 1:NC
end
169

k4_T = -FUNC2;
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
%
get new values for Z, T
i = i + 1;
TT(i) = TT(i-1) + (h/6.)*(k1_T + 2.0*k2_T + 2.0*k3_T + k4_T);
% if this is the last point, it will not go back, so store the last point
if (i==(NPTS+1))
TMB(3,PZ3+1)=TT(i);
LMB(3,PZ3+1)=LL(i);
end
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
% component ID:
1 : H2
2: N2
3: Ar
4: Ammonia
5:Methane
Hmoles(i) = MolFlRate(1) - 3.0*( ConvertedMolesOfN ) ;

Amoles(i) = MolFlRate(4) + 2.0*( ConvertedMolesOfN ) ;
%
Power(i-1) = TotMassFlRate(IS)*CpMix*(TT(i)-TT(i-1)); %
(kg/hr)*(kJ/kg.K)*K=kJ/hr
Power(i-1) = Power(i-1)/(60*60); % kW
x(3) = Rmoles(i)/TotalMoles(i);
x(5) = Mmoles(i)/TotalMoles(i);
%%%%%%%%%%%%%%% patch added 18 May 2011 %%%%%%% for printout only
Tsend = TT(i);
TotMassSend = TotMassFlRate(IS);
[MWtMixture,CpMixKg,CpMixMo,TotMolarFlRateMix,Moles,Masses]=CpSummary(Tsend
,P,x,MW,TotMassSend);
CpKg(i) = CpMixKg; % kJ/(kg-K)
CpMo(i) = CpMixMo; % kJ/(kmol-K)
MWmix(i)= MWtMixture; % kg/kmol
MdotCpKT(i) = ((TotMassFlRate(IS))/3600)*CpKg(i)*Tsend; % kg/s * kJ/(kg-K)
* K = kW
TMFMix(i)=TotMolarFlRateMix;
hhh(i)=Moles(1); nnn(i)=Moles(2); rrr(i)=Moles(3); amm(i)=Moles(4);
ch4(i)=Moles(5);
massh(i)=masses(1); massn(i)=masses(2); massr(i)=masses(3);
massa(i)=masses(4); massc(i)=masses(5);
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% end of patch 18 May 2011 %%%%%%%%
170

element
%FoverA = MolFlRate(2)/Area; % molar flow rate for Nitrogen at inlet
% Pressure remains same
P=P;
T=TT(i);
Z=ZZ(i);
fprintf (resl,'\n %3.0f %8.4f %8.4f %8.4f %8.4f %8.4f
%15.4e',i,x(1),x(2),x(3),x(4),x(5),TotalMoles(i));
% now go to find optimal temp at this point --------------------- 10 may
2011
[Topt] = OptimalT (x,P);
Toptimal(i) = Topt;
if (Topt==0)
Toptimal(i)=850.0;
end
% now go back
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% patch added May 15 2011
TTeqm(i)=Teqm;
if (Teqm==0)
TTeqm(i)=800.0;
end
%HmolesInit=Hmoles(i)
%NmolesInit=Nmoles(i)
%AmmMolesInit=Amoles(i)
%TotMoles=TotalMoles(i)
Epsilon=0.0;
[Epsilon] = EquilibriumC (P,T,Hmoles(i),Nmoles(i),Amoles(i),TotalMoles(i));
TTeps(i) = Epsilon;
%
MmolesEq(i);
rates
171
%xEq(1) = HmolesEq(i)/TotalMolesEq(i);
%xEq(2) = NmolesEq(i)/TotalMolesEq(i);
%xEq(4) = AmolesEq(i)/TotalMolesEq(i);
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% end of patch added
on May 13, 2011
%%%%%%%%%%%%% patch entered on 17 may 2011
% compute new mass fractions since Cp changes
%%%%%%%%%%%%% end of patch 17 may 2011 %%%%%%%%%%%%%%%%%%
end %
-------------------------------------
RK4
fprintf (resl,'\n\n i
Toptimal
Tequilibrium
for i2 = 1:NPTS+1
fprintf (resl,'\n %3.0f %8.2f %8.2f
%12.4e',i2,Toptimal(i2),TTeqm(i2),TTeps(i2));
end
LOOP ENDS
Epsilon');
fprintf (resl,'\n\n\n Summary of RK numerical solution \n \n \n');

fprintf (resl,'\n
Moles
Conversion
% of N \n');
fprintf (resl,'\n
i
L
H2
N2
Ar
NH3
CH4
Total
Z
T
Topt\n');
for i = 1: NPTS+1
fprintf (resl,'\n %3.0f %6.4f %8.4f %8.4f
%8.4f %8.4f %8.4f
%10.4f %6.4f %6.2f
%6.2f',i,LL(i),Hmoles(i),Nmoles(i),Rmoles(i),Amoles(i),Mmoles(i),TotalMoles
(i),ZZ(i),TT(i),Toptimal(i));
end
fprintf (resl,'\n\n\n
Summary of Molar Quantities
computed from CpSummary ');
fprintf (resl,'\n
i
L
H2
N2
Ar
NH3
CH4
Total
Z
T
CpKg CpMo MWtMix Power kW\n');
for i = 1: NPTS+1
fprintf (resl,'\n %2.0f %4.3f %8.4f %8.4f %8.4f %8.4f %8.4f %10.4f
%6.4f %6.2f %6.2f %6.2f %6.2f
%6.2f',i,LL(i),hhh(i),nnn(i),rrr(i),amm(i),ch4(i),TMFMix(i),ZZ(i),TT(i),CpK
g(i),CpMo(i),MWmix(i),MdotCpKT(i));
end
% temps in each catalyst bed
% straight line between x = LMB(1,20), y =TMB(1,20)
%
and x = LMB(2,1) , y =TMB(2,1)
xSt12(1) = LMB(1,iLIM1); ySt12(1) = TMB(1,iLIM1);
xSt12(2) = LMB(2,1) ; ySt12(2) = TMB(2,1);
% straight line between x = LMB(2,20), y =TMB(2,20)
%
and x = LMB(3,1) , y =TMB(3,1)
xSt23(1) = LMB(2,NPTZ+1); ySt23(1) = TMB(2,NPTZ+1);
xSt23(2) = LMB(3,1) ; ySt23(2) = TMB(3,1);
172
LMB;
TMB;
for ibed = 1: 3
fprintf (resl,'\n Bed no: %2.0f ',ibed);
fprintf (resl,'\n j
Length
Temp ');
for ip1 = 1:NPTZ+1
fprintf (resl,'\n %3.0f %9.3f
%9.3f',ip1,LMB(ibed,ip1),TMB(ibed,ip1));
end
end
for ip1=1:NPTZ+1
LMB1(ip1) = LMB(1,ip1);
TMB1(ip1) = TMB(1,ip1);
end
% Power available from exothermic reactions
fprintf (resl,'\n\n\n\n
i
Power (kW)\n');
sumPower =0.0;
for i = 1: NPTS1
%12.4e ',i,Power(i));
sumPower=sumPower+Power(i);
end
fprintf (resl,'\n total exothermic energy available is %12.4e kW
',sumPower);
Power = TotMassFlRateOld(IS)*CpMix*(Tnew-Told); % (kg/hr)*(kJ/kg-K)*(K) =
kJ/hr
% Energy Available between 1st and 2nd bed
TempBed1 = TMB(1,NPTZ+1);
fprintf(resl,'\n Exit Temp from 1st Bed = %8.2f K\n',TempBed1);
fprintf(resl,'\n i
Cp kJ/(kg-K)
Mass Fl Rate(i) kg/hr');
CpMix1 = 0.0;
for ii = 1:NC
CpMix1 = CpMix1 + Cp(ii+5)*MassFlRate(ii)/TotMassFlRate(IS);
fprintf(resl,'\n %3.0f %8.2f
%8.2f',ii,Cp(ii+5),MassFlRate(ii));
end
fprintf(resl,'\n Total Mass Flow Rate = %12.2f kg/hr',TotMassFlRate(IS));
fprintf(resl,'\n Cp Mixture = %8.2f kJ/kg-K',CpMix1);
HeatValue1 = (1./3600)*TotMassFlRate(IS)*CpMix1*TempBed1 ;
fprintf (resl,'\n Power Value 1 = %12.4e kW',HeatValue1);
TempBed2 = TMB(2,1);
fprintf(resl,'\n\n Exit Temp from 2nd Bed = %8.2f K\n',TempBed2);
fprintf(resl,'\n i
Cp kJ/(kg-K)
Mass Fl Rate(i) kg/hr');
CpMix2 = 0.0;
for ii = 1:NC
CpMix2 = CpMix2 + Cp(ii+5)*MassFlRate(ii)/TotMassFlRate(IS);
173
fprintf(resl,'\n %3.0f %8.2f

%8.2f',ii,Cp(ii+5),MassFlRate(ii));
end
fprintf(resl,'\n Total Mass Flow Rate = %12.2f kg/hr',TotMassFlRate(IS));
fprintf(resl,'\n Cp Mixture = %8.2f kJ/kg-K',CpMix2);
HeatValue2 = (1./3600)*TotMassFlRate(IS)*CpMix2*TempBed2 ;
fprintf (resl,'\n Power Value 2 = %12.4e kW ',HeatValue2);
PowerExtracted = HeatValue1 - HeatValue2;
fprintf (resl,'\n\n Power Extracted = %12.4e kW',PowerExtracted);
InletTemp
LL
ZZ
ThisPlot=4;
if (ThisPlot==1)
plot (LL,ZZ,'-k')
grid on
ylabel ('Conversion of N_2 (Z)')
xlim([0 HghtReactor])
% title 'Conversion of N_2 in the synthesis convertor'
end
if (ThisPlot==2)
% plot (LL,TT,'-k')
plot (LMB1,TMB1,'-k')
hold on
plot(xSt12,ySt12,'-k')
hold on
hold on
hold on
hold on
%
plot (LL,Toptimal,'-k');
%
hold on
%
plot (LL,TTeqm,'--k')
grid on

end
if (ThisPlot==3)
plot (LL,HmolesFr,'-k')
hold on
174
plot (LL,NmolesFr,'-k')
hold on
plot (LL,AmolesFr,'-k')
% ylabel ('Molar Flow Rate (kmols/hr)')
ylabel ('Molar Fraction)')
h = legend('H_2','N_2','NH_3',2);
%title 'Molar flow rate of H_2, N_2 and NH_3 in convertor'
title 'Molar fractions in convertor'
end
if (ThisPlot==4)
subplot(2,2,1:2)
%
%
%
%
grid on
% title 'Mole % NH_3'
plot (LL,ZZ,'-k')
% ylim([0 0.301])
grid on
% title 'Conversion of N_2 in the synthesis convertor'
subplot(2,2,3)
% plot (LL,TT,'-k')
hold on
hold on
hold on
hold on
hold on
hold on
grid on
text (0.3,750,'T_{opt}');
text (0.5,850,'T_{eqm}');
%ylim([600 1000])
%
title 'Temperature'
subplot(2,2,4)
hold on
175
plot (LL,NmolesFr,'-.k')
hold on
plot (LL,AmolesFr,'--k')
grid on
ylabel ('Molar Fraction')
h = legend('H_2','N_2','NH_3',2);
%title 'Molar fractions in convertor'
end
if (ThisPlot==5)
subplot(2,1,1)
% plot (LL,TT,'-k')
hold on
hold on
hold on
hold on
hold on
hold on
grid on
text (0.15,810,'T_{opt}');
text (0.62,870,'T_{eqm}');
%ylim([600 1000])
%
title 'Temperature'
subplot(2,1,2)
hold on
hold on
grid on
ylabel ('Mole Fraction')
h = legend('H_2','N_2','NH_3',2);
176

%title 'Molar fractions in convertor'
end
toc
fclose(resl)
177
APPENDIX B5: MATLAB PROGRAM FOR FINDING OPTIMAL

TEMPERATURE
This section lists the Program MansonOneEqn and its function OptimalT
% Program Name: MansonOneEqn
%
Steady State Ammonia Thermal Storage
%
% C:\MATLAB7\work\Ammonia\MansonOneEqn.m
%
% First Written: JULY 2010
% Last Update: Oct 19 2011
% open output file
resl=fopen('outm.txt','w'); % INPUT and STREAM OUTPUT
tic
fprintf (resl,'\n MansonOneEqn.m \n');
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
NC = 5; % number of components, H2,N2,NH3,Ar,CH4
% component ID:
1 : H2
2: N2
3: Ar
4: Ammonia
5:Methane
MW1=2.0*1.0079759; MW2=2.0*14.0067231; MW3= 39.9476613;
MW4=(14.0067231+3.0*1.0079759); MW5 = (12.0110369+4.0*1.0079759);
Name
fprintf (resl,'\n 1 Hydrogen %8.4f ',MW(1));
fprintf (resl,'\n 2 Nitrogen %8.4f ',MW(2));
%8.4f ',MW(3));
%8.4f ',MW(4));
%8.4f ',MW(5));
fprintf (resl,'\n ----------------------------\n');
% STREAM INPUT
P = 150.0; % atm
P_SIunits = P*1.0e5; %Pascals
TotMassFlRate = 183600; % kg/hr
Dashti p.20
% component ID:
1 : H2
2: N2
3: Ar
4: Ammonia
5:Methane
x= [ 0.6567006; 0.2363680; 0.0202874; 0.026930; 0.059714]; % mole fractions
% x= [ 0.75; 0.235 ; 0.0 ; 0.015; 0.0]; % mole fractions
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
Toptimal(1) = Topt;
if ((Topt==0)|(Topt>800))
178
Toptimal(1)=780.0;
end
T=Toptimal(1);
TT(1)=T; % for plotting
Teqm=0;
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% patch added May 13 2011
TTeqm(1)=Teqm;
if (Teqm==0)
TTeqm(1)=780.0;
end
on May 13, 2011
fprintf (resl,'\n Area = %6.2f m^2',Area);
fprintf (resl,'\n Vol of catalyst = %6.3f m^3 \n',VolCatalyst);
MWt = 0.0; % average molecular weight of stream
for i = 1:NC
MWt=MWt+x(i)*MW(i);
xT
= xT
+x(i);
end
RR = R_un/MWt; % gas constant for this stream (gas)
MolarFlRateMix = TotMassFlRate/MWt; % in kmols/hr
TotMolarFlRate = TotMassFlRate/MWt; % kmoles per hr
mfrT=0.0;
mfmT=0.0;
for jk=1:NC
mfr(jk) = x(jk)*MolarFlRateMix;
mfm(jk) = mfr(jk)*MW(jk);
mfmT = mfmT + mfm(jk);
end
%
% STREAM OUTPUT
fprintf (resl,'\n ----------------------------------------------------\n');
Mole Fr
Molar flow rate
Mass flow rate');
fprintf (resl,'\n
kg-mols/hr
kg/hr\n');
for i=1:NC
%8.4f
%8.4f
%8.4f
',i,x(i),mfr(i),mfm(i))
end
%12.4f %12.4f\n',xT,mfrT,mfmT);
MWt = %8.4f kg/kmol
\n',MWt);
fprintf (resl,'\n Gas Const of mixture RR = %8.4f kJ/(kmol-K) \n',RR);
fprintf (resl,'\n Molar Flow Rate of Stream is %8.2f kmoles / hr
\n',MolarFlRateMix);
179
fprintf (resl,'\n ----------------------------------------------------\n');

CpMix = 0.0;
RMix = 0.0;
% find the Cp values at this temp T1 and press P
[CpH2,CpN2,CpNH3,CpCH4,CpAr] = SPCHT(T,P); % kJ/(kmol-K)
jj=1;
for j= NC+1:2*NC
jj=jj+1;
end
fprintf (resl,'\n -----------------------------------------\n');
fprintf (resl,'\n Cp values from function SPCHT at T = %8.2f K and P =
%6.2f atm\n',T,P);
Cp kJ/(kmol-K) kJ/(kg-K)\n');
fprintf (resl,'\n 1 Hydrogen %12.4e %12.4e ',Cp(1),Cp(6));
fprintf (resl,'\n 2 Nitrogen %12.4e %12.4e ',Cp(2),Cp(7));
%12.4e %12.4e ',Cp(3),Cp(8));
%12.4e %12.4e ',Cp(4),Cp(9));
%12.4e %12.4e ',Cp(5),Cp(10));
fprintf (resl,'\n ------------------------------------------\n');
for i = 1:NC
Rg(i) = R_un/MW(i);
%RMix = RMix + Rg(i)*mfr(i)/mfrT;
RMix = RMix + R_un*mfr(i)/mfrT; % kJ/(kmol-K)
CpMix = CpMix + Cp(i)*mfr(i)/mfrT; % kJ/(kmol-K)
end
CvMix = CpMix - RMix;
fprintf (resl,'\n Mixture properties (based on mass ratios)\n');
fprintf (resl,'\n
CpMix
CvMix
RMix
GammaMix\n');
%12.4e
%12.4e
%8.2f
sumMol = 0.0;
sumMas = 0.0;
for j=1:NC
MolFlRate(j) = x(j) * TotMolarFlRate; % kmol/hr
MassFlRate(j)= MolFlRate(j) * MW(j); % kmol/hr * kg/kmol = kg/hr
end
% STREAM OUTPUT
fprintf (resl,'\n ----------------------------------------------------\n');
Temperature = %8.2f \n\n',P,T);
Mole Fr
Molar flow rate
Mass flow rate');
fprintf (resl,'\n
kmoles/hr
kg/hr\n');
for i=1:NC
%8.4f
%8.2f
%8.2f
end
180

%12.4f
MWt = %8.2f kg/kmol
\n',MWt);
fprintf (resl,'\n Gas Const of mixture RR = %8.2f kJ/(kmol-K) ',RR);
fprintf (resl,'\n Molar Flow Rate of Stream is %8.2f kmoles / hr
',TotMolarFlRate);
fprintf (resl,'\n Mass Flow Rate of Stream is %8.2f kg /hr
',TotMassFlRate);
fprintf (resl,'\n ----------------------------------------------------\n');
t=0
[Eta1]=ETA(P,T,Z);%
start with ) since no N2 is converted at
Temperature = %8.2f \n',P,T);
%---------------------------------------------------------% begin RK 4th order for 1st-order coupled ODE

Z = 0.0;
Toptimal(1)=T;
TT(1)=T; % for plotting
Lmin =0.0;
NPTS = 20 ; % meshes total
LL(1)=Lmin;
for i = 2: NPTS+1
LL(i) = LL(i-1)+h;
end
LL
L = LL(1);
i = 1 ;
% component ID:
1 : H2
2: N2
3: Ar
4: Ammonia
5:Methane
Hmoles(i) = MolFlRate(1);
Nmoles(i) = MolFlRate(2);
Amoles(i) = MolFlRate(4);
rates
fprintf (resl,'\n
i
x(1)
x(2)
%15.4e',i,x(1),x(2),x(4),TotalMoles(i));
181
x(4)
Total Mole Fl Rate');
%%%%%%%%%%%%%% patch added 15 May 2011

Epsilon=0.0;
i=1;
[Epsilon] = EquilibriumC (P,T,Hmoles(i),Nmoles(i),Amoles(i),TotalMoles(i))
%
MmolesEq(i);
NmolesPCEq(i) = NmolesEq(i)/TotalMolesEq(i);
TTeps(1) = Epsilon;
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
CatFrac = 1.0;
NPTS1=NPTS-1;
while (i <= NPTS) %---------------------------------- RK4 LOOP BEGINS
i
%%%%%%%%%%%%%%%%%%%%%%%%%%%
k1_z
%%%%%%%%%%%%%%%%%%%%
% first function
[Eta1]=ETA(P,T,Z);
[Ka] = EQNCN(T);
k1_z = FUNC1;
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
%
k2_z
k2_P
L
= LL(i) + h/2. ;
Z
= ZZ(i) + k1_z * h/2.0;
% first function
[Eta1]=ETA(P,T,Z);
[Ka] = EQNCN(T);
k2_z = FUNC1;
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
%
k3_z
k3_P
Z
= ZZ(i) + k2_z * h/2.0;
% first function
[Eta1]=ETA(P,T,Z);
[Ka] = EQNCN(T);
182
FUNC1 = Eta1*CatFrac* RNH3/(2.0*FoverA);

k3_z = FUNC1;
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
%
k4_z
L
= LL(i) + h;
Z
= ZZ(i) + k3_z * h;
% first function
[Eta1]=ETA(P,T,Z);
[Ka] = EQNCN(T);
k4_z = FUNC1;
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
%
get new values for Z
i = i + 1;
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
% component ID:
1 : H2
2: N2
3: Ar
4: Ammonia
5:Methane
Hmoles(i) = MolFlRate(1) - 3.0*( ConvertedMolesOfN ) ;
Amoles(i) = MolFlRate(4) + 2.0*( ConvertedMolesOfN ) ;
%
rates
NmolesPC(i) = Nmoles(i)/TotalMoles(i);
element
Z=ZZ(i);
%15.4e',i,x(1),x(2),x(4),TotalMoles(i));
Toptimal(i) = Topt;
if (Topt==0)
Toptimal(i)=800.0;
end
183
% now go back
T=Toptimal(i);
TT(i)=T; % for plotting
T
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%% patch added May 13 2011
TTeqm(i)=Teqm;
if (Teqm==0)
TTeqm(i)=800.0;
end
%HmolesInit=Hmoles(i)
%NmolesInit=Nmoles(i)
%AmmMolesInit=Amoles(i)
%TotMoles=TotalMoles(i)
Epsilon=0.0;
[Epsilon] = EquilibriumC (P,T,Hmoles(i),Nmoles(i),Amoles(i),TotalMoles(i))
TTeps(i) = Epsilon;
%
MmolesEq(i);
NmolesPCEq(i) = NmolesEq(i)/TotalMolesEq(i);
%xEq(1) = HmolesEq(i)/TotalMolesEq(i);
%xEq(2) = NmolesEq(i)/TotalMolesEq(i);
%xEq(4) = AmolesEq(i)/TotalMolesEq(i);
on May 13, 2011
end %
-------------------------------------
RK4
fprintf (resl,'\n\n i
Toptimal
Tequilibrium
for i2 = 1:NPTS+1
%12.4e',i2,Toptimal(i2),TTeqm(i2),TTeps(i2));
end
LOOP ENDS
Epsilon');
Toptimal
TTeqm
fprintf (resl,'\n\n\n Summary of RK numerical solution');
fprintf (resl,'\n
Moles
% of N \n');
184
Conversion
fprintf (resl,'\n
i
L
H2
N2
Ar
NH3
CH4
Total
Z
T \n');
for i = 1: NPTS+1
%8.2f %8.2f %8.2f
%10.2f %8.4f
%8.2f',i,LL(i),Hmoles(i),Nmoles(i),Rmoles(i),Amoles(i),Mmoles(i),TotalMoles
(i),ZZ(i),TT(i));
end
%------------------- sept 4 2011 ---------------------LLHom =
[0;0.15;0.30;0.45;0.60;0.75;0.90;1.05;1.20;1.35;1.50;1.65;1.80;1.95;2.10;2.
25;2.40;2.55;2.70;2.85;3.00;3.15;3.30;3.45;3.60;3.75;3.90;4.05;4.20;4.35;4.
50];
NmolesHom =
[0.2364;0.2349;0.2332;0.2312;0.2289;0.2262;0.2233;0.2202;0.2174;0.2153;0.21
42;0.2132;0.2121;0.2109;0.2097;0.2085;0.2073;0.2062;0.2051;0.2041;0.2032;0.
2025;0.2020;0.2015;0.2012;0.2009;0.2008;0.2007;0.2006;0.2005;0.2005];
fprintf (resl,'\n Comparison of Optimal, Equilibrium from this program, and
Normal from SSATS_NonUnif');
fprintf (resl,'\n
i
L
Nopt
Neq ');
for izzz = 1:NPTS+1
%8.4f',izzz,LL(izzz),NmolesPC(izzz),NmolesPCEq(izzz));
end
fprintf (resl,'\n
i
L
Nhom');
for izzz = 1:31
',izzz,LLHom(izzz),NmolesHom(izzz));
end
%%%%%%%%%%---------------------------------------------ThisPlot=5;
if (ThisPlot==1)
plot (LL,ZZ,'-k')
title 'Conversion of N_2 in the synthesis convertor'
end
if (ThisPlot==2)
plot (LL,TT,'-k')
end
if (ThisPlot==3)
plot
hold
plot
hold
plot
(LL,Hmoles,'-k')
on
(LL,Nmoles,'-.k')
on
(LL,Amoles,'--k')
185

h = legend('H_2','N_2','NH_3',2);
title 'Molar flow rate of H_2, N_2 and NH_3 in convertor'
end
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
if (ThisPlot==4)
subplot(2,2,1:2)
% plot (LL,AmolesPC,'-k')
plot (LL,NmolesPC,'-k')
ylabel ('Mole Fraction N_2')
% title 'Optimal Conversion of N_2 in the synthesis convertor'
hold on
%plot (LL,AmolesPCEq,'--k')
plot (LL,NmolesPCEq,'-k')
% now get the results from SSATS_NonUnif (hom case) and paste the Nmoles
% from a simple run, to compare with the optimal and eqm Nmoles obtained
% in this prog
hold on
plot (LLHom,NmolesHom,'-k')
xlim([0.25 4.5])
text (3.1,0.24,'{N_2}_{,hom}');
text (2.1,0.21,'{N_2}_{,opt}');
text (1.1,0.19,'{N_2}_{,eqm}');
% h = legend('opt','eqm',2);
%
%

grid on
% title 'Mole % NH_3'
subplot(2,2,3)
% plot the optimal temp
plot (LL,TT,'-k')
hold on
% plot the eqm temp
plot (LL,TTeqm,'-k')
%h = legend('opt','eqm',2);
text (0.3,730,'T_{opt}');
text (1.5,800,'T_{eqm}');
grid on
xlim([0.2 4.5])
%
title 'Temperature'
subplot(2,2,4)
% plot (LL,Hmoles,'-k')
hold on
xlim([0.225 4.51])
186
hold on
%ylabel ('Molar Flow Rate (kmols/hr)')
ylabel ('Optimal Mole Fraction')
h = legend('H_2','N_2','NH_3',2);
grid on
%
end
title 'Mol fl rate of H_2, N_2 and NH_3'
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
if (ThisPlot==5)
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
%%%%%%%%%%%%%%%
% these are the results for runs below
%run C:\MATLAB7\work\Ammonia\SSATS_NonUnif_2Sept2011
% cat distribution 1 1 1
Length =
[0;0.1500;0.3000;0.4500;0.6000;0.7500;0.9000;1.0500;1.2000;1.3500;1.5000;1.
6500;1.8000;1.9500;2.1000;2.2500;2.4000;2.5500;2.7000;2.8500;3.0000;3.1500;
3.3000;3.4500;3.6000;3.7500;3.9000;4.0500;4.2000;4.3500;4.5000];
NmolesFr1 =
[0.2364;0.2349;0.2332;0.2312;0.2289;0.2262;0.2233;0.2202;0.2174;0.2153;0.21
42;0.2132;0.2121;0.2109;0.2097;0.2085;0.2073;0.2062;0.2051;0.2041;0.2032;0.
2026;0.2019;0.2013;0.2006;0.2000;0.1993;0.1986;0.1979;0.1973;0.1966];
AmolesFr1 =
[0.0269;0.0325;0.0392;0.0470;0.0560;0.0664;0.0780;0.0900;0.1009;0.1089;0.11
33;0.1172;0.1215;0.1261;0.1307;0.1354;0.1401;0.1446;0.1488;0.1526;0.1560;0.
1585;0.1610;0.1635;0.1661;0.1687;0.1714;0.1740;0.1766;0.1792;0.1817];
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
%%%%%%%%%%%%%%
% 1.10 1.00 1.00
NmolesFr2
=[0.2364;0.2348;0.2329;0.2306;0.2279;0.2249;0.2215;0.2183;0.2157;0.2143;0.2
137;0.2128;0.2116;0.2105;0.2093;0.2081;0.2069;0.2058;0.2047;0.2038;0.2030;0
.2023;0.2017;0.2010;0.2003;0.1997;0.1990;0.1983;0.1977;0.1970;0.1964];
AmolesFr2
=[0.0269;0.0331;0.0405;0.0494;0.0598;0.0717;0.0848;0.0974;0.1073;0.1129;0.1
152;0.1189;0.1233;0.1278;0.1325;0.1371;0.1417;0.1461;0.1503;0.1539;0.1571;0
.1596;0.1621;0.1647;0.1672;0.1698;0.1725;0.1751;0.1777;0.1802;0.1827];
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
%%%%%%%%%%%%%%
% 1.20 1.00 1.00
NmolesFr3
=[0.2364;0.2346;0.2325;0.2299;0.2269;0.2234;0.2198;0.2166;0.2146;0.2138;0.2
135;0.2126;0.2114;0.2102;0.2090;0.2078;0.2066;0.2055;0.2045;0.2036;0.2028;0
.2022;0.2015;0.2009;0.2002;0.1995;0.1989;0.1982;0.1975;0.1969;0.1963];
AmolesFr3
=[0.0269;0.0337;0.0420;0.0519;0.0638;0.0773;0.0916;0.1040;0.1118;0.1150;0.1
187
159;0.1196;0.1241;0.1287;0.1334;0.1381;0.1427;0.1471;0.1511;0.1546;0.1576;0
.1601;0.1626;0.1652;0.1678;0.1704;0.1730;0.1756;0.1782;0.1807;0.1832];
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
%%%%%%%%%%%%%%
% 1.50 1.25 1.00
NmolesFr4
=[0.2364;0.2341;0.2313;0.2277;0.2234;0.2188;0.2153;0.2138;0.2135;0.2134;0.2
134;0.2122;0.2107;0.2091;0.2076;0.2061;0.2049;0.2038;0.2030;0.2024;0.2021;0
.2015;0.2008;0.2002;0.1995;0.1988;0.1982;0.1975;0.1969;0.1962;0.1956];
AmolesFr4
=[0.0269;0.0356;0.0467;0.0606;0.0773;0.0952;0.1090;0.1148;0.1160;0.1162;0.1
162;0.1210;0.1271;0.1332;0.1392;0.1448;0.1497;0.1538;0.1569;0.1591;0.1606;0
.1628;0.1654;0.1679;0.1705;0.1732;0.1758;0.1783;0.1808;0.1833;0.1856];
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
%%%%%%%%%%%%%%
% optimal ammonia concentration
hold on
% equilibrium ammonia concentration
%plot (LL,AmolesPCEq,'-k')
%hold on
plot (Length,AmolesFr1,'--k')
hold on
plot (Length,AmolesFr2,':k')
hold on
plot (Length,AmolesFr3,'-.k')
hold on
plot (Length,AmolesFr4,'+k')
hold on
ylabel ('Mole Fraction NH_3')
% title 'Optimal NH_3 in the synthesis convertor'
% text (3.1,0.24,'{N_2}_{,hom}');
% text (2.1,0.21,'{N_2}_{,opt}');
% text (1.1,0.19,'{N_2}_{,eqm}');
h = legend('optimal','1.00 1.00 1.00','1.10 1.00 1.00','1.20 1.00
1.00','1.50 1.25 1.00',2);
%
%

grid on
% title 'Mole Fraction % NH_3'
end
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
if (ThisPlot==6)
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
%%%%%%%%%%%%%%%
% these are the results for runs below
%run C:\MATLAB7\work\Ammonia\SSATS_NonUnif_2Sept2011
% cat distribution 1 1 1
Length =
[0;0.1500;0.3000;0.4500;0.6000;0.7500;0.9000;1.0500;1.2000;1.3500;1.5000;1.
188
6500;1.8000;1.9500;2.1000;2.2500;2.4000;2.5500;2.7000;2.8500;3.0000;3.1500;
3.3000;3.4500;3.6000;3.7500;3.9000;4.0500;4.2000;4.3500;4.5000];
NmolesFr1 =
[0.2364;0.2349;0.2332;0.2312;0.2289;0.2262;0.2233;0.2202;0.2174;0.2153;0.21
42;0.2132;0.2121;0.2109;0.2097;0.2085;0.2073;0.2062;0.2051;0.2041;0.2032;0.
2026;0.2019;0.2013;0.2006;0.2000;0.1993;0.1986;0.1979;0.1973;0.1966];
AmolesFr1 =
[0.0269;0.0325;0.0392;0.0470;0.0560;0.0664;0.0780;0.0900;0.1009;0.1089;0.11
33;0.1172;0.1215;0.1261;0.1307;0.1354;0.1401;0.1446;0.1488;0.1526;0.1560;0.
1585;0.1610;0.1635;0.1661;0.1687;0.1714;0.1740;0.1766;0.1792;0.1817];
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
%%%%%%%%%%%%%%
% 1.10 1.00 1.00
NmolesFr2
=[0.2364;0.2348;0.2329;0.2306;0.2279;0.2249;0.2215;0.2183;0.2157;0.2143;0.2
137;0.2128;0.2116;0.2105;0.2093;0.2081;0.2069;0.2058;0.2047;0.2038;0.2030;0
.2023;0.2017;0.2010;0.2003;0.1997;0.1990;0.1983;0.1977;0.1970;0.1964];
AmolesFr2
=[0.0269;0.0331;0.0405;0.0494;0.0598;0.0717;0.0848;0.0974;0.1073;0.1129;0.1
152;0.1189;0.1233;0.1278;0.1325;0.1371;0.1417;0.1461;0.1503;0.1539;0.1571;0
.1596;0.1621;0.1647;0.1672;0.1698;0.1725;0.1751;0.1777;0.1802;0.1827];
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
%%%%%%%%%%%%%%
% 1.20 1.00 1.00
NmolesFr3
=[0.2364;0.2346;0.2325;0.2299;0.2269;0.2234;0.2198;0.2166;0.2146;0.2138;0.2
135;0.2126;0.2114;0.2102;0.2090;0.2078;0.2066;0.2055;0.2045;0.2036;0.2028;0
.2022;0.2015;0.2009;0.2002;0.1995;0.1989;0.1982;0.1975;0.1969;0.1963];
AmolesFr3
=[0.0269;0.0337;0.0420;0.0519;0.0638;0.0773;0.0916;0.1040;0.1118;0.1150;0.1
159;0.1196;0.1241;0.1287;0.1334;0.1381;0.1427;0.1471;0.1511;0.1546;0.1576;0
.1601;0.1626;0.1652;0.1678;0.1704;0.1730;0.1756;0.1782;0.1807;0.1832];
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
%%%%%%%%%%%%%%
% 1.50 1.25 1.00
NmolesFr4
=[0.2364;0.2341;0.2313;0.2277;0.2234;0.2188;0.2153;0.2138;0.2135;0.2134;0.2
134;0.2122;0.2107;0.2091;0.2076;0.2061;0.2049;0.2038;0.2030;0.2024;0.2021;0
.2015;0.2008;0.2002;0.1995;0.1988;0.1982;0.1975;0.1969;0.1962;0.1956];
AmolesFr4
=[0.0269;0.0356;0.0467;0.0606;0.0773;0.0952;0.1090;0.1148;0.1160;0.1162;0.1
162;0.1210;0.1271;0.1332;0.1392;0.1448;0.1497;0.1538;0.1569;0.1591;0.1606;0
.1628;0.1654;0.1679;0.1705;0.1732;0.1758;0.1783;0.1808;0.1833;0.1856];
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
%%%%%%%%%%%%%%
% optimal nitrogen concentration
plot (LL,NmolesPC,'-k')
hold on
% equilibrium nitrogen concentration
%plot (LL,NmolesPCEq,'-k')
%hold on
plot (Length,NmolesFr1,'--k')
hold on
plot (Length,NmolesFr2,':k')
189
hold on
plot (Length,NmolesFr3,'-.k')
hold on
plot (Length,NmolesFr4,'+k')
hold on
grid on
ylabel ('Mole Fraction N_2')
% title 'Optimal N_2 in the synthesis convertor'
% text (3.1,0.24,'{N_2}_{,hom}');
% text (2.1,0.21,'{N_2}_{,opt}');
% text (1.1,0.19,'{N_2}_{,eqm}');
h = legend('opt','1','2','3','4',2);
end
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
toc
fclose(resl);
function [Topt] = OptimalT (x,P)
% DATA
% P, x(1), x(2), x(4)
% gives Topt
% scan between 500 and 1000
scanTlow = 500; scanTup=1000.0;
scanDel = 2.0;
Tchk = scanTlow-scanDel;
scanT = (scanTup-scanTlow)/scanDel;
% fprintf (resl,'\n Temp (K)
diff=fLHS-fRHS');
for iTchk = 1:scanT
Tchk = Tchk+scanDel;
[phiH2,phiN2,phiNH3,aH2,aN2,aNH3]=ACTVT(P,Tchk,x(1),x(2),x(4));
[Ka] = EQNCN(Tchk);
FatT = Ka^2*aN2*aH2^1.5/aNH3 - aNH3/aH2^1.5;
fRHS = -( (20.523e3)/Tchk^2 ) * FatT;
% now find deriv at this point
T1=Tchk-1; T2=Tchk+1;
[Ka] = EQNCN(T1);
[Ka] = EQNCN(T2);
fLHS = 0.5*(FatT2-FatT1);
diff=fLHS-fRHS;
rootT(iTchk) = Tchk;
rootY(iTchk) = diff;
% fprintf(resl,'\n %3.0f %6.2f %12.4e',iTchk,rootT(iTchk),rootY(iTchk));
end
Topt=0;
for jTchk = 1:scanT-1
jT1=jTchk+1;
190
if ((rootY(jTchk)>0)&(rootY(jT1)<0))
end
end
for jTchk = 1:scanT-1
jT1=jTchk+1;
if ((rootY(jTchk)<0)&(rootY(jT1)>0))
end
end
191

Dr. Sadaf Siddiq 08F UET PHD ME 47

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Dr. Sadaf Siddiq 08F UET PHD ME 47

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PhD Thesis

OPTIMAL PERFORMANCE ANALYSIS OF A SOLAR

Department of Mechanical Engineering

OPTIMAL PERFORMANCE ANALYSIS OF A SOLAR

A proposal submitted for research leading to the degree of Doctor of Philosophy

Pakistan Institute of Engineering & Applied Sciences

Department of Mechanical Engineering,

Internal Examiner (Research Supervisor)

Department of Mechanical Engineering

Authors Name: ________________________

Cross-sectional area (m2)

Austrailian National University

Specific heat at constant pressure (kJ kmol-1 K-1)

Concentrating Solar Power

Activation energy (kJ kmol-1)

Force (external, fluid to solid)

Initial nitrogen molar flow rate (kmol h-1)

Giga-ton (109 ton)

Enthalpy per unit mass

Kellogg Brown and Root

Length of synthesis reactor (m)

Metric tonnes per day

Million ton of oil equivalent

One Equation Model

Pontryagins Maximum Principle

Universal gas constant 8.3144 kJ kmol-1 K-1

Reaction rate (kmol NH3 h-1 m-3 catalyst)

4th order Runge-Kutta

Surface Area (m2)

Two Equation Model

Thermal Storage Plant

Terawatt-hours (1012 Watt-hrs)

Internal Energy (kJ)

Internal Energy per unit mass

Activity for specie i

Total Molar Concentration

Molar Concentration of Specie i

Gravitational acceleration (9.81 ms-2)

Initial mole flow rate of specie i (kmol h-1)

Parts per million

Distance along catalyst bed (m)

Normalized Distance along catalyst bed (m)

Mole fraction for specie i

Initial Mole fraction for specie i

Heat of reaction (kJ kmol-1 NH3)

Fugacity coefficient for specie i

Mass Flow Rate (kghr-1)

Catalyst effectiveness factor

The void space of the bed

Catalyst spatial factor

Density (kg m-3)

Vector containing state variables

Species in a multi component system, i =1,2,3,4,....N

Total amount of entity in a macroscopic system

Evaluated at cross sections 1 and 2

Haldor Topsoe Ammonia Synthesis Process ........................................................................................... 15

THERMODYNAMIC CYCLES FOR SOLAR THERMAL POWER PLANTS ........................................................ 18

DESCRIPTION OF THE THERMAL STORAGE PLANT .............................................................. 25

MODELLING & SIMULATION OF THERMAL STORAGE PLANT .......................................... 34

TEM Model using Activity based Temkin-Pyzhev Form (TP-A): .......................................................... 43

3.2 MODELING UNIT OPERATIONS ................................................................................................................ 48

Counter Flow Heat Exchanger (CF-HX): ................................................................................................ 57

MODELING THE INTEGRATED PLANT ...................................................................................................... 59