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Process Intensification and Integration for Sustainable Design
Process Intensification and Integration for
Sustainable Design
Edited by
Dominic C. Y. Foo
Mahmoud M. El-Halwagi
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Dominic C. Y. Foo would like to dedicate this book to his wife Cecilia and kids
Irene, Jessica, and Helena. Mahmoud M. El-Halwagi would like to dedicate this
book to his parents, his wife Amal, and sons Omar and Ali.
vii
Contents
Preface xv
1 Shale Gas as an Option for the Production of Chemicals and

Challenges for Process Intensification 1
Andrea P. Ortiz-Espinoza and Arturo Jiménez-Gutiérrez
1.1 Introduction 1
1.2 Where Is It Found? 1
1.3 Shale Gas Composition 3
1.4 Shale Gas Effect on Natural Gas Prices 3
1.5 Alternatives to Produce Chemicals from Shale Gas 4
1.6 Synthesis Gas 4
1.7 Methanol 5
1.8 Ethylene 6
1.9 Benzene 7
1.10 Propylene 7
1.11 Process Intensification Opportunities 8
1.12 Potential Benefits and Tradeoffs Associated with Process
Intensification 10
1.13 Conclusions 11
References 11
2 Design and Techno-Economic Analysis of Separation Units to

Handle Feedstock Variability in Shale Gas Treatment 15
Eric Bohac, Debalina Sengupta, and Mahmoud M. El-Halwagi
2.1 Introduction 15
2.2 Problem Statement 16
2.3 Methodology 17
2.4 Case Study 17
2.4.1 Data 18
2.4.2 Process Simulations and Economic Evaluation 19
2.4.2.1 Changes in Fixed and Variable Costs 20
2.4.2.2 Revenue 21
2.4.2.3 Economic Calculations 21
2.4.3 Safety Index Calculations 22
2.5 Discussion 23
viii Contents
2.5.1 Process Simulations 23

2.5.1.1 Dehydration Process 23
2.5.1.2 NGL Recovery Process 23
2.5.1.3 Fractionation Train 26
2.5.1.4 Acid Gas Removal 26
2.5.2 Profitability Assessment 26
2.5.3 High Acid Gas Case Economics 30
2.5.4 Safety Index Results 30
2.5.5 Sensitivity Analysis 32
2.5.5.1 Heating Value Cases 33
2.5.5.2 NGL Price Cases 34
2.6 Conclusions 35
Appendices 35
2.A Appendix A: Key Parameters for the Dehydration Process 36
2.B Appendix B: Key Parameters for the Turboexpander Process 36
2.C Appendix C: Key Parameters for the Fractionation Train 37
2.D Appendix D: Key Parameters for the Acid Gas Removal
System 37
References 39
3 Sustainable Design and Model-Based Optimization of Hybrid

RO–PRO Desalination Process 43
Zhibin Lu, Chang He, Bingjian Zhang, Qinglin Chen, and Ming Pan
3.1 Introduction 43
3.2 Unit Model Description and Hybrid Process Design 47
3.2.1 The Process Description 47
3.2.2 Unit Model and Performance Metrics 49
3.2.2.1 RO Unit Model 49
3.2.2.2 PRO Unit Model 52
3.2.3 The RO–PRO Hybrid Processes 54
3.2.3.1 Open-Loop Configuration 54
3.2.3.2 Closed-Loop Configuration 55
3.3 Unified Model-Based Analysis and Optimization 56
3.3.1 Dimensionless Mathematical Modeling 56
3.3.2 Mathematical Model and Objectives 58
3.3.3 Optimization Results and Comparative Analysis 59
3.4 Conclusion 62
Nomenclature 63
References 65
4 Techno-economic and Environmental Assessment of Ultrathin

Polysulfone Membranes for Oxygen-Enriched Combustion 69
Serene Sow Mun Lock, Kok Keong Lau, Azmi Mohd Shariff, Yin Fong Yeong, and
Norwahyu Jusoh
4.1 Introduction 69
4.2 Numerical Methodology for Membrane Gas Separation Design 70
4.3 Methodology 73
Contents ix
4.3.1 Simulation and Elucidation of Mixed Gas Transport Properties of

Ultrathin PSF Membranes (Molecular Scale) 73
4.3.2 Simulation of Mathematical Model Interfaced in Aspen HYSYS for
Mass and Heat Balance (Mesoscale) 75
4.3.3 Design of Oxygen-Enriched Combustion Using Ultrathin PSF
Membranes 75
4.4 Results and Discussion 77
4.4.1 Simulation and Elucidation of Mixed Gas Transport Properties of
Ultrathin PSF Membranes (Molecular) 77
4.4.2 Simulation of Mathematical Model Interfaced in Aspen HYSYS for
Mass and Heat Balance (Mesoscale) 79
4.4.3 Design of Oxygen-Enriched Combustion Using Ultrathin PSF
Membranes 82
4.4.3.1 Membrane Area Requirement 82
4.4.3.2 Compressor Power Requirement 83
4.4.3.3 Turbine Power Requirement 85
4.4.3.4 Economic Parameter 88
4.5 Conclusion 90
Acknowledgment 91
References 91
5 Process Intensification of Membrane-Based Systems for Water,

Energy, and Environment Applications 97
Nik A. H. M. Nordin, Zulfan A. Putra, Muhammad R. Bilad, Mohd D. H. Wirzal,
Lila Balasubramaniam, Anis S. Ishak, and Sawin Kaur Ranjit Singh
5.1 Introduction 97
5.2 Membrane Electrocoagulation Flocculation for Dye Removal 99
5.3 Carbonation Bioreactor for Microalgae Cultivation 102
5.4 Forward Osmosis and Electrolysis for Energy Storage and Treatment of
Emerging Pollutant 107
5.5 Conclusions and Future Perspective 111
References 113
6 Design of Internally Heat-Integrated Distillation Column

(HIDiC) 117
Vasu Harvindran and Dominic C. Y. Foo
6.1 Introduction 117
6.2 Example and Conceptual Design of Conventional Column 119
6.3 Basic Design of HIDiC 120
6.4 Complete Design of HIDiC 122
6.4.1 Top-Integrated Column 122
6.4.2 Bottom-Integrated Column 123
6.4.3 Geometrical Analysis for Heat Panels 124
6.5 Energy Savings and Economic Evaluation 126
6.6 Concluding Thoughts 128
References 128
x Contents
7 Graphical Analysis and Integration of Heat Exchanger

Networks with Heat Pumps 131
Minbo Yang and Xiao Feng
7.2 Influences of Heat Pumps on HENs 132
7.2.1 Case 1 133
7.2.2 Case 2 134
7.2.3 Case 3 134
7.2.4 Case 4 135
7.2.5 Case 5 136
7.2.6 Case 6 136
7.2.7 Case 7 136
7.3 Integration of Heat Pump Assisted Distillation in the Overall
Process 138
7.3.1 Increase of Pinch Temperature 138
7.3.2 Decrease of Pinch Temperature 140
7.3.3 No Change in Pinch Temperature 141
7.3.4 Heat Pump Placement 142
7.4 Case Study 145
7.5 Conclusion 148
References 148
8 Insightful Analysis and Integration of Reactor and Heat

Exchanger Network 151
Di Zhang, Guilian Liu, and Xiao Feng
8.2 Influence of Temperature Variation on HEN 152
8.2.1 Location of Cold and Hot Streams 152
8.2.2 Effect of Temperature Variation 153
8.3 Relation Among Reactor Parameters 156
8.3.1 Relation Among Temperatures, Selectivity, and Conversion of
Reactor 157
8.3.1.1 CSTR 159
8.3.1.2 PFR 159
8.3.2 Reactor Characteristic Diagram 160
8.4 Coupling Optimization of HEN and Reactor 161
8.5 Case Study 163
8.6 Conclusions 165
References 166
9 Fouling Mitigation in Heat Exchanger Network Through

Process Optimization 167
Yufei Wang and Xiao Feng
9.2 Operation Parameter Optimization for Fouling Mitigation in
HENs 169
9.2.1 Description on Velocity Optimization 169
Contents xi
9.2.2 Fouling Threshold Model 171

9.2.3 Heat Transfer Related Models 172
9.2.4 Pressure Drop Related Models 174
9.3 Optimization of Cleaning Schedule 175
9.4 Application of Backup Heat Exchangers 175
9.5 Optimization Constraints and Objective Function 176
9.5.1 Optimization Constraints 176
9.5.2 Objective Function 177
9.5.3 Optimization Algorithm 178
9.6 Case Studies 178
9.6.1 Case Study 1: Consideration of Velocity Optimization Alone 178
9.6.1.1 Optimization Results 180
9.6.2 Case Study 2: Simultaneous Consideration of Velocity and Cleaning
Schedule Optimization 186
9.6.2.1 Constraints for Case Study 188
9.6.2.2 Results and Discussion 189
9.6.2.3 Considering Backup Heat Exchanger 194
9.7 Conclusion 194
Acknowledgments 196
References 198
10 Decomposition and Implementation of Large-Scale Interplant

Heat Integration 201
Runrun Song, Xiao Feng, Mahmoud M. El-Halwagi, and Yufei Wang
10.1.1 Reviews and Discussions for Stream Selection 202
10.1.2 Reviews and Discussions for Plant Selection 204
10.1.3 Reviews and Discussions for Plant Integration 204
10.2 Methodology 205
10.2.1 Strategy 1 – Overview 205
10.2.2 Identification of Heat Sources/Sinks for IPHI from Individual
Plants 206
10.2.3 Decomposition of a Large-Scale IPHI Problem into Small-Scale
Subsections 207
10.2.4 Strategy 2 for Indirect IPHI 209
10.3 Case Study 212
10.3.1 Example 1 212
10.3.2 Example 2 215
10.4 Conclusion 217
References 218
11 Multi-objective Optimisation of Integrated Heat, Mass and

Regeneration Networks with Renewables Considering
Economics and Environmental Impact 221
So-Mang Kim, Adeniyi J. Isafiade, and Michael Short
11.2 Literature Review 222
xii Contents
11.2.1 Regeneration in Process Synthesis 222

11.2.2 The Analogy of MEN and REN 222
11.2.3 Combined Heat and Mass Exchange Networks (CHAMENs) 224
11.3 Environmental Impact in Process Synthesis 225
11.3.1 Life Cycle Assessment 225
11.4 The Synthesis Method and Model Formulation 226
11.4.1 Synthesis Approach 227
11.4.2 Assumptions 229
11.4.3 MINLP Model Formulation 230
11.4.3.1 HENS Model Equations 230
11.4.3.2 MEN and REN Model Equations 233
11.4.3.3 The Combined Economic Objective Function 236
11.4.3.4 Initializations and Convergence 239
11.5 Case Study 240
11.5.1 H2 S Removal 240
11.5.1.1 Synthesis of MEN (The First Step) 242
11.5.1.2 Simultaneous Synthesis of MEN and REN (The Second Step) 243
11.5.1.3 Simultaneous Synthesis of MEN, REN, and HEN (The Third
Step) 244
11.5.1.4 Absorption and Regeneration Temperature Optimization 247
11.5.1.5 The Synthesis of Combined Model Using MOO 252
11.6 Conclusions and Future Works 254
References 256
12 Optimization of Integrated Water and Multi-regenerator

Membrane Systems Involving Multi-contaminants: A
Water-Energy Nexus Aspect 261
Musah Abass and Thokozani Majozi
12.2 Problem Statement 263
12.3 Model Formulation 263
12.3.1 Material Balances for Sources 264
12.3.2 Mass and Contaminants Balances for Regeneration Units 265
12.3.3 Mass and Contaminant Balances for Permeate and Reject
Streams 265
12.3.4 Mass and Contaminant Balances for Sinks 266
12.3.5 Modeling of the Regeneration Units 266
12.3.5.1 Performance of Regeneration Units 266
12.3.6 Logical Constraints 267
12.3.7 The Objective Function 267
12.4 Illustrative Example 268
12.5 Conclusion 272
Acknowledgments 272
12.A Appendix: Detailed Models for the ED and RO Modules 273
Nomenclature 280
References 282
Contents xiii
13 Optimization Strategies for Integrating and Intensifying

Housing Complexes 285
Jesús M. Núñez-López, and José M. Ponce-Ortega
13.2 Methods 288
13.2.1 Total Annual Cost for the Integrated System 289
13.2.2 Fresh Water Consumption 289
13.2.3 GHGE Emissions 290
13.2.4 Environmental Impact 290
13.2.5 Sustainability Return of Investment 293
13.2.6 Process Route Healthiness Index 293
13.2.7 Multistakeholder Approach 295
13.3 Case Study 295
13.4 Results 296
13.5 Conclusions 296
References 299
14 Sustainable Biomass Conversion Process Assessment 301

Eric C. D. Tan
14.2 Methodology and Assumptions 302
14.3 Results and Discussion 305
14.3.1 Environmental Indicators 305
14.3.2 Energy Indicators 310
14.3.3 Efficiency Indicators 312
14.3.4 Economic Indicators 313
14.4 Conclusions 314
Acknowledgments 316
References 317
Index 319
xv
Preface
The chemical process industry involves a broad spectrum of manufacturing

sectors and facilities around the world. With increased global competition,
escalating environmental concerns, dwindling energy, and material resources,
it is imperative for industry to seek continuous process improvement. Process
intensification and integration are among the most effective strategies leading
to improved process designs and operations with enhancement in cost effec-
tiveness, resource conservation, efficiency, safety, and sustainability. Process
integration is a holistic framework for designing and operating industrial facili-
ties with an overarching focus on the interconnected nature of the various pieces
of equipment, mass, energy, and functionalities. On the other hand, process
intensification involves efficiency improvement through effective strategies such
as increasing throughput for the same physical size or decreasing the physical
size for the same throughput, coupling units and phenomena, enhancing
mass and energy utilization, and mitigating environmental impact. There is a
natural synergism between process integration and intensification. For instance,
mass and energy integration (two key pillars of process integration) are ideal
approaches for enhancing mass and energy intensities.
This book is intended to provide a compilation of the various recent develop-
ments in the fields of process intensification and process integration with focus
on enhancing sustainability of the chemical processes and products. It includes
state-of-the-art contributions by world-renowned leaders in process intensifica-
tion and integration. It strikes a balance between fundamental techniques and
industrial applications. Both academic researchers and industrial practitioners
will be able to use this book as a guide to optimize their respective plants and
processes.
The 14 chapters in the book are classified into two broad areas: process inten-
sification and process integration. As expected, several intensification chapters
include integration and vice versa. These chapters may be read independently of
each other, or with no particular sequence. Synopses of all chapters are given as
follows.
xvi Preface
Section 1 – Process Intensification

The first section of the book consists of six chapters focusing on process
intensification. Chapters 1 and 2 focus on process intensification for the shale
gas industry. Chapter 1 entitled “Shale Gas as an Option for the Production of
Chemicals and Challenges for Process Intensification” (by Ortiz-Espinoza and
Jiménez-Gutiérrez) discusses alternatives to produce chemicals from shale gas,
and opportunities for process intensification. In Chapter 2 entitled “Design and
Techno-Economic Analysis of Separation Units to Handle Feedstock Variability
in Shale Gas Treatment” (by Bohac and coworkers), a systematic approach is
proposed for the design of a processing plant to treat raw shale gas with variable
composition. Chapters 3–5 focuses on various process intensification aspect
of membrane separation processes. In Chapter 3 entitled “Sustainable Design
and Model-Based Optimization of Hybrid RO–PRO Desalination Process”
(by Lu and coworkers), a dimensionless model-based optimization approach
was developed to evaluate the performance of a hybrid systems consisting of
reverse osmosis and pressure retarded osmosis processes. In Chapter 4, entitled
“Techno-Economic and Environmental Assessment of Ultrathin Polysulfone
Membranes for Oxygen-Enriched Combustion” (by Lock and coworkers), mul-
tiscale simulation was used for techno-economic feasibility study of ultrathin
polysulfone membrane for oxygen-enriched combustion; the multiscale simula-
tion covers molecular scale, mesoscale, and eventually process optimization and
design. Chapter 5, entitled “Process Intensification of Membrane-Based Systems
for Water, Energy, and Environment Applications” (by Md Nordin and cowork-
ers), outlined three important applications of membrane technology in process
intensification, i.e. membrane electrocoagulation flocculation for dye removal,
membrane diffuser in photobioreactor, and forward osmosis/electrolysis.
Chapter 6, entitled “Design of Internally Heat-Integrated Distillation Column
(HIDiC)” (by Harvindran and Foo), discussed the use of process simulation
software for the design of an internal HIDiC.
Section 2 – Process Integration

The second section of the book features eight chapters on process integration.
Chapters 7–9 present some latest advancements in heat exchanger network
(HEN) synthesis. While Chapters 7 and 8 are based on pinch analysis tech-
niques, Chapter 9 is based on mathematical programming technique. Chapter
7 entitled “Graphical Analysis and Integration of Heat Exchanger Networks
with Heat Pumps” (by Yang and Feng), presents pinch analysis-based strategies
for the integration with heat pumps as well as heat pump-assisted distillation
with HEN. In Chapter 8 that is entitled “Insightful Analysis and Integration of
Reactor and Heat Exchanger Network” (by Zhang and coworkers), a combined
multi-parameter optimization diagram (CMOD) is proposed to allow better
integration of reactors with the HEN, taking into consideration of energy
consumption, temperature, selectivity, and reactor conversion. Next, a new
methodology named as velocity optimization is proposed in Chapter 9, entitled
Preface xvii
“Fouling Mitigation in Heat Exchanger Network Through Process Optimiza-

tion” (by Wang and Feng). This new methodology allows the correlation of
fouling, pressure drop, and heat transfer coefficient of heat exchangers with
velocity; this allows velocity distribution to be determined among all the heat
exchangers in the HEN. Chapter 10 entitled “Decomposition and Implemen-
tation of Large-Scale Interplant Heat Integration” (by Song and coworkers)
proposed a three-step strategy for the decomposition of large-scale inter-plant
heat integration problem. The chapter also proposes a new pinch analysis
technique to identify the maximum interplant heat recovery potential, while
minimizing the corresponding flow rates of heat transfer fluids. Chapter 11
entitled “Multi-objective optimisation of integrated heat, mass and regeneration
networks with renewables considering economics and environmental impact”
(by Isafiade and coworkers) presents a mathematical programming method
for multi-period combined heat and mass exchange networks (CHAMENs) in
which a regeneration network is included; the latter consists of multiple recy-
clable mass separating agents and regenerating streams. In Chapter 12 entitled
“Optimization of Integrated Water and Multi-regenerator Membrane Systems
Involving Multi-contaminants: A Water-Energy Nexus Aspect” (by Abass and
Majozi), another mathematical approach was presented for the synthesis of
integrated water and membrane network; the latter consists of detailed models
of electrodialysis and reverse osmosis units that are embedded within a water
regeneration network. Chapter 13 entitled “Optimization Strategies for Integrat-
ing and Intensifying Housing Complexes” (by Núñez-López and Ponce-Ortega)
provides an overview of process integration and intensification for housing
complexes, the latter is typically a much larger scale as compared to industrial
processes. In the last chapter entitled “Sustainable Biomass Conversion Process
Assessment Contributing to ‘Process Intensification and Integration for Sus-
tainable Design’” (by Tan), a multi-objective process sustainability evaluation
methodology known as GREENSCOPE (Gauging Reaction Effectiveness for
ENvironmental Sustainability of Chemistries with a multi-Objective Process
Evaluator) is demonstrated to track process sustainability performance for a
biomass conversion process.
These 14 chapters cover some of the most recent and important developments
in process intensification and process integration. We hope the book will serve
as a useful guide for researchers and industrial practitioners who seek to develop
tools and applications for process improvement and sustainable development.
Kajang, Malaysia Dominic C. Y. Foo

College Station, United States Mahmoud M. El-Halwagi
January 2020
1
Shale Gas as an Option for the Production of Chemicals and

Challenges for Process Intensification
Andrea P. Ortiz-Espinoza and Arturo Jiménez-Gutiérrez
Tecnológico Nacional de México, Instituto Tecnológico de Celaya, Chemical Engineering Department,
Ave Tecnologico y Garcia Cubas, Celaya 38010, Mexico
1.1 Introduction
Shale gas is unconventional natural gas trapped or adsorbed in shale rock
formations. As opposed to conventional natural gas, shale gas is difficult to
extract because of the low porosity of the rock formations in which it is confined.
This particular characteristic implied a high cost for the extraction of this gas, so
that its production remained unfeasible until the development of more suitable
extraction technologies, such as hydraulic fracturing and horizontal drilling [1].
Hydraulic fracturing is a stimulation technique used to increase the flow rate
of gas and oil in low permeability reservoirs. This method consists in injecting
high-pressurized fluids into the well to create fractures and maintain them
opened to allow the flux of gas and oil [1, 2]. Hydraulic fracturing is generally
combined with horizontal drilling to increase the area covered with a lower
number of wells. These two technologies have led to an increase in the net
production of natural gas in the United States (US) for more than a decade,
which has been referred to as the shale gas revolution [1, 3].
The aim of this chapter is to give an overview of shale gas and its potential
to produce value-added chemicals. This chapter addresses the following aspects:
shale gas composition and places where deposits are located, effect of shale gas
discoveries on natural gas prices, alternatives to produce chemicals from shale
gas, and opportunities for process intensification.
1.2 Where Is It Found?

Although shale gas has been known for a while, the first shale gas well was
drilled in 1821 in Chautauqua, NY, its exploitation was possible only until the
development of hydraulic fracturing and horizontal drilling technologies. After
the oil crises of the 1970s, the US government and some oil and gas companies,
separately, initiated the investment in research projects to evaluate and make
shale gas extraction possible. From the beginning of the 2000s, technical
Process Intensification and Integration for Sustainable Design, First Edition.

Edited by Dominic C. Y. Foo and Mahmoud M. El-Halwagi.
© 2021 WILEY-VCH GmbH. Published 2021 by WILEY-VCH GmbH.
2 1 Shale Gas as an Option for the Production of Chemicals
Table 1.1 Major shale gas plays in the United States.
Percentage of dry shale gas

Shale play State(s) production in 2018
Marcellus PA, WV, OH, and 32.7

NY
Permian TX and NM 12.3
Utica OH, PA, and WV 11.3
Haynesville LA and TX 11.0
Eagle Ford TX 7.1
Woodford OK 5.0
Barnett TX 4.4
Mississippian OK 3.8
Niobrara–Codell CO and WY 3.4
Bakken ND and MT 2.7
Fayetteville AR 2.3
Rest of the United States “shale” 4.0
Source: Adapted from EIA 2018 [4].
and economic factors promoted the idea to produce natural gas from shale
formations. The Barnett shale play was the first basin to be exploited in a large
scale, with the hydraulic fracturing technology being tested there. Following the
success to extract natural gas from the Barnett shale play, shale gas extraction
began in other locations. Table 1.1 gives basic information about the major shale
gas plays in the United States.
Apart from US reserves, recoverable shale gas resources around the world have
been found in countries such as China, Argentina, Algeria, Canada, Mexico,
Australia, South Africa, and Russia [3, 5]. Despite these discoveries, several fac-
tors such as geological aspects and the lack of the necessary infrastructure have
curbed the development of the shale gas industry in those other countries [6, 7].
Table 1.2 Recent shale gas reserves and production in for the six countries with more shale
gas reserves.
Unproved recoverable Production in

Country reserves by 2013 (Tcf) 2018 (Bcf/yr) References
China 1115.20 353.15 [8]

Argentina 801.50 365.00 [9]
Algeria 706.90 No production [10]
United States 662.50 (by 2015) 7079.62 [4]
Canada 572.90 182.80 [11]
Mexico 545.20 No production [12]
Source: From EIA 2015 [13].

1.4 Shale Gas Effect on Natural Gas Prices 3
Table 1.2 shows the production rates in 2018 for the six countries with more
unproved technically recoverable shale gas resources.
1.3 Shale Gas Composition

One particular characteristic of shale gas is its varying composition. Shale
gas composition depends heavily on the location of the sources, and it may
variate even within wells in the same play. The primary component of shale gas
is methane, but it also contains considerable quantities of natural gas liquids
(NGLs) such as ethane and propane. Apart from these components, shale gas
also contains acid gases such as CO2 , H2 S, and inorganic components such as
nitrogen [5, 14]. The separation of NGLs from methane has induced industries
to look for alternatives to transform them into more valuable products, but at
the same time the varying composition of shale gas represents a challenge for the
treatment plants, which have to be robustly designed to handle such variations
in the gas composition.
1.4 Shale Gas Effect on Natural Gas Prices

The high availability of natural gas, generated as a result of the increasing
production of shale gas, has caused a noticeable drop of its price in the United
States. Moreover, the ability to extract natural gas from deposits that are not
associated to crude oil reservoirs has uncoupled natural gas and crude oil prices
[1]. These facts have contributed to what has been defined as the new era of cheap
natural gas, in which it has been priced consistently under US$5 per million Btu
for almost a decade in the United States [15]. In particular, natural gas prices in
2019 have shown a decrease from 3.18 at the beginning of the year to US$2.07
per million Btu in September [16]. Even more, in an extreme situation, producers
at the Waha hub in the Permian basin in West Texas had to pay the pipeline to
take the excess of gas, showing a negative US$9 in April, which contributed to an
average price of only 73 cents per million Btu for the first eight months of 2019,
compared with an average market price of US$2.10 in 2018 (which is also lower
than the five year average from 2014 to 2018 of US$2.80) [17]. These trends create
an opportunity for the development of technologies to transform shale/natural
gas into value-added chemicals. One additional point to consider is the increas-
ing amount of liquefied natural gas that is being exported from the United
States [18]. As this quantity grows, international natural gas prices may also
get affected.
The main consumers of natural gas are the electricity generation indus-
try, the residential sector, the industrial sector, and the chemical industry.
Low natural gas prices have incentivized the electric power plants to switch
from coal to natural gas, with an impact not only on the economy of these
systems but also on the environment by reducing the total greenhouse gas
emissions [1].
Another sector that has shown interest in switching from oil-based feedstocks,
such as naphtha or crude oil, to natural gas is the chemical industry. The
availability of inexpensive natural gas and NGLs has boosted the chemical
industry to create new plants for the production of value-added chemicals using
methane and NGLs as feedstock [5, 19].
1.5 Alternatives to Produce Chemicals from Shale Gas

Due to the increasing availability of low-cost natural gas, the chemical industry
has started to invest in the research and development of chemical routes that
can transform methane into value-added chemicals. Some of the chemical com-
pounds that have received special attention are methanol, ethylene, propylene,
and liquid fuels obtained from syngas. Some of the processes to produce the
aforementioned chemicals are discussed next.
1.6 Synthesis Gas

Synthesis gas is a mixture of carbon monoxide and hydrogen typically needed
for the production of chemicals such as a methanol, ammonia, or gas-to-liquid
(GTL) products. The production process for synthesis gas varies depending
on the oxidizing agent selected for the reforming of the natural gas. The main
reforming processes are steam reforming (SR), partial oxidation (POX), and dry
reforming (DR) [20]. The characteristics of these processes are listed in Table 1.3.
Although these processes may be used separately, combinations of two or more
of the main reforming options have been proposed to enhance the overall per-
formance of the reforming task. One such process is the autothermal reforming
(ATR) in which the exothermic nature of the POX reforming is combined with
the endothermic SR [21].
In all of these reforming alternatives, energy and water usage and generation
are key points to consider when selecting the appropriate technology. Studies
regarding heat and mass integration potential for the SR, POX, and ATR options
can be consulted in the work of Martínez et al. [21] and Gabriel et al. [22].
Table 1.3 Reforming options and their characteristics.
Reforming Oxidizing
option agent Conditions Chemistry Type
Steam reforming H2 O Endothermic CH4 + H2 O → CO + 3H2 Catalytic

1
Partial oxidation O2 Exothermic CH4 + O
2 2
→ CO + 2H2 Catalytic/non catalytic
Dry reforming CO2 Endothermic CH4 + CO2 → 2CO + 2H2 Catalytic
Source: Adapted from Noureldin et al. 2014 [20].

1.7 Methanol 5
1.7 Methanol
Typically, methanol is used as an intermediate to produce other chemicals such
as acetic acid, formaldehyde, and MTBE, among others [23]. The production pro-
cess for methanol consists of three stages, reforming, synthesis, and purification.
In the first stage, the main goal is to transform methane into syngas. For this
purpose a reforming process is selected. One important factor to consider when
selecting the reforming process is that the ratio of H2 to CO to feed the methanol
synthesis reactor has to be equal to 2.
For the synthesis of methanol, compression of the syngas obtained from the
reforming stage is needed. Then, the compressed syngas is fed to a catalytic reac-
tor in which the following reactions take place:
CO2 + 3H2 → CH3 OH + H2 O
CO + 2H2 → CH3 OH
The synthesis reactor operates at 83 bar and 260 ∘ C. The outlet of the reactor is
cooled and sent to a flash unit to separate the unreacted syngas and recirculate
it. Additionally, a fraction of the recycled syngas is purged, with a potential use
as fuel. The crude methanol obtained from the flash unit is purified using one or
two distillation columns [23].
This process has been analyzed to assess its environmental impact and its safety
characteristics [23, 24]. The main drawbacks of the process are the high pres-
sure required for the operation of the synthesis reactor and the wasted fraction
of non-recycled syngas. Ortiz-Espinoza et al. [24] studied the effect of different
operating pressures for the methanol synthesis reactor on the safety, environmen-
tal, and economic characteristics of the methanol production process using POX
reforming. The high operating pressure is related to the profitability of the pro-
cess, but safety properties may be hindered by such operating conditions. Green-
house emissions are an additional item of relevance for consideration. Figure 1.1
shows the results of the analysis conducted by Ortiz-Espinoza et al. [24], in which
values of three metrics used for profitability, inherent safety, and sustainability are
reported for different reactor pressures and recycling fractions for the unreacted
syngas. Such metrics were the return on investment (ROI) for economic perfor-
mance, process route index (PRI) for inherent safety, and total emissions of CO2
equivalents for process sustainability. One can observe the gradual trend of the
three metrics that reflect their conflicting behavior. In summary, the economic
potential of the process is better at high pressures and high recycling fractions,
but if safety is of primary concern, a lower pressure would favor the process
characteristics.
It should also be noticed that the methanol synthesis reaction is exothermic;
therefore, heat integration options may be considered to further enhance the
environmental and economic performance of the process.
P = 83 bar P = 70 bar
ROI (%) PRI CO2-eq (T/T) ROI (%) PRI CO2-eq (T/T)
60.63
61.62
57.42
55.53
53.62
50.95
50.04
46.81
46.90
43.06
17.56
17.56
17.51
17.35
15.89
17.08
14.90
13.51
14.85
14.06
13.49
13.47
13.87
13.42
13.27
13.27
12.49
12.88
11.89
11.71
0.5 0.6 0.7 0.8 0.9 0.5 0.6 0.7 0.8 0.9
P = 60 bar P = 50 bar
ROI (%) PRI CO2-eq (T/T) ROI (%) PRI CO2-eq (T/T)
59.35
57.20
53.26
49.71
47.94
43.21
43.37
38.97
37.87
33.03
19.02
17.07
17.41
15.85
15.80
14.63
13.40
14.19
12.56
12.16
10.72
10.64
10.57
10.61
10.47
8.09
8.07
8.00
8.10
8.11
0.5 0.6 0.7 0.8 0.9 0.5 0.6 0.7 0.8 0.9
Figure 1.1 Safety, sustainability, and economic indicator for different pressures and recycling
fractions in the methanol production process.
1.8 Ethylene
Ethylene is a major building block used in the chemical industry to produce a
wide variety of important chemicals. The increasing availability of shale gas has
boosted the ethylene industry as several ethylene production plants have been
planned to be built in the United States [5]. The alternatives to produce ethylene
include processes that use NGLs as feedstock, such as ethane cracking or propane
dehydrogenation [25], and processes that transform methane to ethylene [26, 27].
Among the processes that convert methane to ethylene, two important options
are the oxidative coupling of methane (OCM) and the methanol to olefins (MTO)
technology. OCM is a direct process in which methane and oxygen are fed to a
catalytic reactor, with the products of the reaction being separated in a purifica-
tion stage that consists of the removal of water and CO2 and a cryogenic distilla-
tion train [26]. Although this process is known for the low yield achieved in the
reactor, which render a process option with low profitability, the development
of new catalyst structures has made possible the construction of demonstration
facilities for this technology that offer better economic perspectives [28].
The other alternative for ethylene production is MTO, which is a more com-
plex process as it involves several stages. First, the reforming of natural gas and
the production of methanol take place. After the methanol synthesis, the crude
methanol is sent to a catalytic reactor where low-weight olefins are produced. In
the reactor a variety of components are produced, such as ethylene and propy-
lene, butylene, C5 s, hydrogen, low-weight hydrocarbons, water, and CO2 . The
effluent of the reactor is then sent to separation and purification units, which
start with CO2 removal and dehydration units. Then, the remaining stream is sent
to a distillation train consisting of demethanizer, deethanizer, and depropanizer
columns, as well as C2 and C3 splitters. A column to separate C4 s and C5 s is also
1.10 Propylene 7
needed. The overall process is very energy intensive, as it involves a reforming

stage and a large distillation train.
Even when the MTO technology has been reported to be more profitable than
the OCM option [26], the latter technology is less complex and avoids the need to
transform the natural gas to intermediate products such as syngas. That provides
an incentive to develop improvements to this technology in order to enhance its
overall performance and profitability. Proposed ideas to achieve such improve-
ments include the use of membranes in the CO2 separation system and modi-
fications to the ethylene fractionation column to reduce heating and condenser
duties [29, 30].
1.9 Benzene
Benzene is an important starting molecule in the petrochemical industry. The
production of benzene from shale gas was considered in Pérez-Uresti et al. [31],
and a process based on the direct methane aromatization (DMA) route was
designed. In this process, methane is fed to a DMA reactor operating at 800 ∘ C
and atmospheric pressure. The main products of the reaction are benzene and
hydrogen. The effluent from the DMA reactor is sent to a membrane unit to
separate the hydrogen. Then, the remaining stream is cooled and compressed to
be separated in a flash tank. The gas stream obtained from the flash separator is
methane-rich and is recycled to the DMA reactor. The liquid stream is fed to a
distillation column where benzene is obtained as a top product. Although the
DMA process competes with the traditional production routes based on catalytic
reforming or steam cracking of liquid petroleum feedstocks, it represents an
attractive alternative given the low prices of natural gas.
1.10 Propylene
Propylene has typically been produced as a byproduct either from the steam
cracking of naphtha to produce ethylene or from the fluid catalytic cracking
to produce gasoline. With the shale gas boom and the excess of NGLs such as
ethane, the production of ethylene has switched the feedstock from naphtha to
ethane. This action has eliminated the production of propylene as a byproduct,
opening an opportunity for the development of on-purpose propylene produc-
tion processes. The alternatives to produce propylene from shale gas include two
options via methanol and one using the propane obtained from the purification
of shale gas [32, 33]. The processes to produce propylene via methanol are the
MTO route and the methanol to propylene (MTP) process [33]. The MTO pro-
cess is described earlier in the ethylene section. MTP follows a similar path. First,
natural gas is transformed into syngas gas using a reforming alternative, and then
the syngas is transformed into methanol. As opposed to the MTO process, where
crude methanol is sent to the MTO reactor, methanol has to be purified for its use
as feedstock for the MTP process. Therefore, the crude methanol obtained from
the methanol synthesis reactor is sent to a flash unit and purified using a distilla-
tion column. The purified methanol is then fed to a reactor, where it is converted
to dimethyl ether and water. Then, the outlet stream of the reactor is sent to a fixed
bed catalytic reactor to produce propylene. The effluent from the fixed bed reac-
tor contains propylene, gasoline, and LPG, as well as water. It is sent to a flash unit
to remove water and the remaining stream is purified using distillation columns.
Another alternative for the production of on-purpose propylene is the propane
dehydrogenation process, in which a depropanizer column is used to separate C4+
compounds that may be present in the fresh material. The purified propane enters
a cold box to refrigerate the effluent from the propylene production reactor. Then,
the propane stream is mixed with hydrogen and sent to a fired-heater before
being fed to a fluidized catalyst bed reactor. The reaction is highly endothermic.
The outlet stream of the reactor contains propylene, propane, light gases, ethane
and ethylene, and some heavier hydrocarbons. The reactor effluent is cooled,
compressed, and sent to a cool box where hydrogen is separated from the hydro-
carbons. The liquid stream from the cold box is sent to a selective hydrogenation
process (SHP) to further improve the production of propylene. The effluent from
the SHP is fed to a deethanizer column to remove light gases. Finally, the remain-
ing stream is fed to a C3 -splitter column to produce the propylene. The propane
obtained at the bottom of the splitter column is recycled to the depropanizer
column [32].
These processes represent an excellent opportunity for the independent pro-
duction of propylene instead of obtaining it as a byproduct of other processes.
1.11 Process Intensification Opportunities

The incentive for shale gas monetization can also be viewed as an opportunity to
develop intensified processes for shale gas transformation technologies. Recent
efforts to design intensified processes have been observed. Process intensification
is understood here as a search for more competitive process alternatives via the
development of more compact flowsheets (i.e. with fewer pieces of equipment
or smaller sizes of the same number of equipment units) and/or with a reduc-
tion on the consumption of basic resources (raw materials, energy) through more
efficient designs.
The first efforts to develop formal design methodologies for intensified pro-
cesses were due to the work by Gani and his research group [34–36]. Such initial
methodologies make use of the concepts of tasks and phenomena, giving rise to
the concepts of phenomena building blocks (PBBs), which represent the tasks
involved in a process unit such as reaction, heating, cooling, mass transfer, and
so forth; the combination of PBBs provides simultaneous phenomena building
blocks (SPBBs), which are used to model the operations involved in a process. For
instance, in a distillation column, the following SPBBs can be observed. Each tray
shows a mixture with two phases, with contact, transfer, and separation between
the two phases (vapor and liquid), while the condenser adds cooling and the
reboiler adds heating to the previous SPBBs, as shown in Figure 1.2 for a column
with five trays.
1.11 Process Intensification Opportunities 9
M = C = 2phM = PC(VL) = PT(VL) = PS(VL)
Distillate
M = 2phM = PC(VL) = PT(VL) = PS(VL)
Feed
M = H = 2phM = PC(VL) = PT(VL) = PS(VL)
Bottom
Figure 1.2 Simultaneous phenomena building blocks in a conventional distillation column.
Using these concepts, Lutze et al. [36] developed a methodology for process
design of intensified processes, consisting of three stages. In the first one, a basic
process flowsheet is synthesized. In the second stage, SPBBs are developed and
a superstructure that contains all the possible tasks of the system is formulated.
The problem is then solved as a mixed-integer nonlinear programming (MINLP)
model to obtain the intensified structure that minimizes a given objective
function such as the total annual cost of the system. Babi et al. [34] applied
an extended formulation of that model that included sustainability metrics to
a case study dealing with the production of dimethyl carbonate. In the work
by Castillo-Landero et al. [37], such a methodology was taken as a basis, but
instead of formulating an MINLP model to search for the optimal intensified
configuration, a sequential approach with gradual intensification of the process
was conducted until a final structure with a minimum number of equipment
units was obtained. One advantage of this procedure is that one can assess
individual levels of process intensification so that a structure that favors a given
metric of interest can be selected.
Interesting challenges arise when shale gas processes are considered for
process intensification. Let us take, for instance, the basic flowsheet for the
production of ethylene from shale gas, or natural gas, shown in Figure 1.3. As
discussed earlier, this process shows a fairly simple structure but an adverse
profitability, which poses a particular incentive to explore potential benefits that
an effective process intensification task could provide. Nonetheless, noticeable
challenges exist for its transformation into an intensified process that combines
CO2 Tail gas

Recycled methane
Ethylene
Natural gas
Oxygen
From air CO2
separation removal
OCM Reactor
unit
Comp-1 Comp-2
Cooler De-C1 C2-splitter
Ethane
Water
Figure 1.3 Basic flowsheet for ethylene production from shale/natural gas.
the process tasks, namely, reaction and several separation tasks. First of all,
the reactor performs a catalytic, gas-phase reaction task, which consists of
a complex reaction mechanism. Secondly, the separation tasks consist of a
combination of compression for water condensation and absorption for CO2
removal (typically carried out with an amine such as MEA). Combination of
absorption and membrane could possibly be considered. The distillation train,
finally, is highly energy intensive. Given the tasks identified for this process,
and the aim to intensify it, the use of membrane units would be of special
consideration. Membrane units could conceptually be designed first to carry out
the individual tasks. Then, combinations of reaction and separation tasks based
on such membrane units could be considered. The resulting structure would
include innovative gas-phase membrane-reactive-separation units. The design
of effective membranes that, among other things, could separate the gas mixture
that requires cryogenic distillation systems could provide a significant impact
on the process economics. It should be mentioned that some efforts to combine
reactive distillation with membrane separation have been reported (e.g. [38]).
However, the reaction for which the intensification with membrane units has
been considered has been typically implemented for liquid-phase reactions. In
such cases, membranes aid in improving the effectiveness of the process, for
instance, by releasing one of the products of the reversible reaction to improve
its yield. The problem posed by shale gas processes is the gas-phase reaction that
requires special membrane materials for its effective application. The aspects
outlined here taking the OCM transformation technology as an example provide
a clear incentive toward the design of more competitive alternatives based on
more compact, innovative shale gas-intensified technologies.
1.12 Potential Benefits and Tradeoffs Associated

with Process Intensification
Although intensification opportunities for shale gas technologies remain to be
explored, it is worthy of mention its potential benefits and possible tradeoffs
based on the results from research and applications of intensification method-
ologies. First, it could be mentioned that a direct economic impact that would
References 11
favor investment and operating costs could be observed. A notable example is the
intensified process design developed by Eastman Chemicals for the production
of 400 kT/yr of methyl acetate that transformed a flowsheet with 10 units (one
reactor and nine separation columns) into a single reactive-distillation piece
of equipment. The resulting intensified process had 1/5 of capital investment
and 1/5 of energy costs with respect to the original process [39]. One could
also expect improvements in other factors such as carbon footprint and global
warming metrics [37]. However, tradeoffs with other aspects such as process
inherent safety and process controllability remain to be assessed. In an initial
work to account for process inherent safety for a case study dealing with the
intensification of an isoamyl acetate process, it was found that a partially
intensified process could provide a better alternative in terms of inherent safety
expectations with respect to a fully intensified process [40]. On the other hand,
the effect of losing degrees of freedom for process control that arises from
intensifying an original process and how it affects the process operability and
controllability is an item that remains to be addressed.
1.13 Conclusions
An analysis of shale gas availability and its potential implications to support a
shale gas industry that expands its use as an energy source to include transforma-
tion processes into value-added chemical products has been presented. Designs
for shale gas transformation into valuable chemicals such as methanol and ethy-
lene are examples of current efforts to produce higher value-added molecules
particularly valuable as precursors of important end products. The development
of extraction technologies has provided the basis for the development of shale
gas monetization strategies. It has been shown how the profitability of shale gas
processes may be in conflict with other important considerations such as the
process safety, which sets the incentive for the development of multi-objective
optimization formulations to obtain designs that offer the best compromises
between such conflicting metrics. Another interesting challenge, in addition to
the development of efficient and profitable shale gas flowsheets, lies in the design
of intensified processes for flowsheets originally based on conventional reaction
and separation units. Current intensification methodologies could be taken as a
basis, with the challenge of its application for cases based on gas-phase reactions
that involve complex reaction mechanisms and different types of separation pro-
cesses. The development of membrane-based processes seems like a promising
alternative in the search for innovative shale gas intensified processes.
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A process intensification methodology including economic, sustainability and
safety considerations. Industrial and Engineering Chemistry Research 58 (15):
6080–6092. https://doi.org/10.1021/acs.iecr.8b04146.
15
Design and Techno-Economic Analysis of Separation Units

to Handle Feedstock Variability in Shale Gas Treatment
Eric Bohac 1 , Debalina Sengupta 2 , and Mahmoud M. El-Halwagi 1,2
1 Texas A&M University, Department of Chemical Engineering, University Drive at Spence Street,
College Station, 77840, USA

2
Texas A&M Engineering Experiment Station, Gas and Fuels Research Center, University Drive at Spence Street,
College Station, 77840, USA
2.1 Introduction
Over the past decade, the shale gas boom has caused significant industrial devel-
opment in the United States, with the promise of significant monetization oppor-
tunities for the manufacturing sector to produce various value-added chemicals
and fuels [1]. Shale gas is a form of natural gas where the gas is trapped within low
permeability shale formations [2]. One major challenge with shale gas however is
the wide variability in the composition and flow rate of the gas. The composition
and flow rate, both between wells and within the same well over time, can differ
significantly [3–5].
Dynamic and spatial variability in flow rate and composition pose major chal-
lenges when designing a gas processing plant of optimal size. In general, plants
with larger process equipment are more flexible and are able to handle a wider
range of inlet compositions. Nonetheless, these plants also have higher fixed and
variable costs. A gas processing plant is needed to purify and separate natural
gas and natural gas liquids (NGLs) and to isolate various possible containments
including water, sulfur species, carbon dioxide, mercury, and oxygen [6]. Such
separation operations may include acid gas removal, to remove sulfur species and
carbon dioxide, dehydration, nitrogen rejection, mercury removal, NGL recov-
ery, and NGL separation. One issue currently facing the gas production industry
is a lack of capacity to handle greatly increased production [7]. Another issue is
frequent unplanned shutdowns and a lack of efficiency in operations [8]. Regard-
less of the dynamic and spatial variability in shale gas flow rate and composi-
tion, gas processing facilities must have the ability to handle such variations and
render a set of products with consistent qualities to satisfy pipeline constraints
Process Intensification and Integration for Sustainable Design, First Edition.

Edited by Dominic C. Y. Foo and Mahmoud M. El-Halwagi.
© 2021 WILEY-VCH GmbH. Published 2021 by WILEY-VCH GmbH.
16 2 Design and Techno-Economic Analysis of Separation Units
and downstream-processing requirements [9–12]. In this chapter, the aim is to

determine a method to find the optimal size of a plant and a strategy to process
wellhead gas when feeds of various compositions are available to the facility. Pro-
cess synthesis, simulation, and techno-economic analysis were used to determine
the optimal configuration and capacity of the gas treatment plant.
The approach will also incorporate safety into the early stages of process design,
before changes in design become more costly and difficult to make [13–15]. The
concept of inherent safety is that, by eliminating or reducing the sources of haz-
ards in a chemical plant, the severity and likelihood of process safety incidents
will be reduced [8]. One challenge of implementing inherent safety is the lack
of information in early design stages. Most existing safety assessment tools are
used retroactively, after the process design is completed or near completion [16].
In order to quantify the inherent safety of alternative process designs during the
early design stages, a number of safety indices have been developed [14, 15, 17].
In this work the safety of different process designs will be compared using a mod-
ified version of the process route index (PRI) [18]. This safety index was chosen
because the chemicals involved in natural gas processing are highly flammable
and explosive [18, 19].
Another important consideration is environmental impact. While natural gas
is considered to be cleaner than coal and oil (from an emissions and energy con-
sumption standpoint), there is potential for further reduction in environmental
impact [20, 21]. However to the author’s knowledge fluctuating feedstock com-
positions have not been considered in literature for shale gas processing.
2.2 Problem Statement

The problem to be addressed in this work is stated as follows:
• A set of shale gas wells with anticipated profiles for variable flow rates and
compositions and known, temperature, and pressure
• A known set of feedstock and product prices
It is desired to develop a systematic design and optimization approach for gas
treatment plant. Although the processing steps for treating raw shale gas can vary
depending on the composition of the wellhead gas, a common process flowsheet
(shown by Figure 2.1) is considered. First, condensates and free water are sepa-
rated. Then, acid gases (CO2 and H2 S) are removed. Acid gas content must be
lowered to permissible levels to prevent corrosion issues during additional pro-
cessing and/or during pipeline transport [6]. Dehydration is then carried out to
remove bound water. This water must be removed to low levels because (i) it may
form hydrates with natural gas components such as methane, ethane, and carbon
dioxide, and (ii) it may freeze in later processing steps. In either case, the formed
solids may plug piping and separation units [6]. Next, methane (sales gas) is sep-
arated from the other NGLs. Finally the latter is fractionated into their individual
components as they typically have high economic value.
2.4 Case Study 17
Acid gases Bound

water
Acid gas
Sweet gas Dehydration
removal
Sour gas Dry gas

Ethane
Condensate and
Wellhead Fractionation
free water NGL recovery NGLs Propane
gas train
removal
Butanes
Condensate Free water Sales gas
Figure 2.1 Shale gas treatment process.
2.3 Methodology
Figure 2.2 gives an overview of the proposed approach. First, a statistical analysis
is carried out for the composition data. Several feeds are chosen, and process
simulations are performed using a set of given assumptions to meet product
specifications. Then, a process design is developed for each feed. Next, fixed and
variable costs are estimated using simulation results, which include equipment
sizing, mass and energy balances, operating conditions, and utility consumption
as well as detailed cost data. Finally economic calculations are performed, and
when combined with revenue information enable analysis of economic results.
2.4 Case Study

To illustrate the applicability of the proposed approach, a case study is solved
based on representative data for the Barnett Shale Play in Texas. The key objec-
tives of the case study include:
• Design of a base case and several additional process designs for different feed
compositions
• Economic evaluations of the proposed designs
• Process safety evaluation of the proposed designs
• Sensitivity analysis where product and feedstock prices are varied based on
standard deviations from historical price data
To streamline the study, the following assumptions are made:
• Average flow rate, temperature, and pressure: Although the flow rate, temper-
ature, and pressure of shale gas coming out of the well can vary significantly,
it was assumed that wellhead gas is sent to a centralized processing facil-
ity where these values on average would be relatively constant, and only
composition would vary. Additionally it is common for gas to be saturated
Compositional data
Statistical analysis of
feeds
Selection of feeds
Assumptions
Process simulation to meet specifications
Process designs for different feeds
Equipment Mass and Operating

Utilities
sizing energy balances conditions
Detailed cost data Fixed and variable cost estimation
Economic
calculations
Revenue Analysis of economic results
Figure 2.2 Overview of the methodology.
with water because water is sent down the well to maintain well pressure. It
is not uncommon for there to also be free water in the incoming gas stream;
however this is easily removed using a knockout drum on the front end of the
process at minimal cost.
• Inlet feeds enter the processing plant at a standard vapor volumetric flow of
150 million standard cubic feet per day (MMSCFD), 100 ∘ F, and 1000 psig. The
Peng–Robinson equation of state was used in the process simulation model.
• The gas feedstock is saturated with water.
2.4.1 Data
First, compositional data was obtained for the Barnett Shale region (located in
the Dallas, TX, area) [3]. Next, minor components such as nitrogen, oxygen, and
hydrogen were removed from the data sets so that only the major components
(CO2 and the hydrocarbons) were considered. The compositional data sets were
classified into different types. This was done based on the methane composition
in each data set. There were five types of data sets as shown in Table 2.1. Table 2.1
also shows the probability of each feed type as determined from the literature
data [3].
2.4 Case Study 19
Table 2.1 Feed types as determined by methane composition.
Methane Probability of
Feed type composition (mol%) feed type (%)
1 >87 7.50
2 81–87 28.33
3 75–81 28.33
4 69–75 28.33
5 <69 7.50
Table 2.2 Selected cases.
Composition (mol%) Feed #1 Feed #2 Feed #3 Feed #4 Feed #5
Methane 94.11 83.62 77.78 71.94 56.34

Ethane 2.59 7.54 9.42 11.55 16.13
Propane 0.02 4.68 7.26 9.60 16.06
n-Butane 0.25 2.11 2.65 3.15 4.96
i-Butane 0.26 1.08 1.27 1.61 2.62
n-Pentane 0.02 0.30 0.60 0.82 1.60
i-Pentane 0.03 0.30 0.53 0.76 1.44
Neopentane 0.00 0.00 0.00 0.02 0.04
Carbon dioxide 2.71 0.38 0.49 0.56 0.81
Next, one case from each feed type was selected from among the data sets. The
case chosen for each feed type was a case found near the middle of the distribu-
tion. A total of five cases were selected (see Table 2.2). From among these cases,
the base case was selected as type 3 case since it falls nearest to the middle of the
distribution and is representative of the most commonly found composition in
this region.
Finally one additional case is considered. As mentioned in the introduction,
sulfur species, predominately hydrogen sulfide, may also be found in shale gas
[6]. The goal of considering this case is to determine if the additional processing
needed for a gas with a high acid (HA) loading would significantly affect the eco-
nomics of treating such a stream. This inlet composition of this case was chosen
such that the methane and NGL content would be similar to that of the base case
(Feed #3) (Table 2.3).
2.4.2 Process Simulations and Economic Evaluation

Process simulation was performed to meet the required specifications (sales gas
gross heating value of 950–1150 Btu/SCF [British thermal unit/standard cubic
feet], 1000 psig, and CO2 content of 2–3 mol% maximum, 0.3 g H2 S/100 SCF gas)
Table 2.3 High acid (HA) gas feed composition.
Composition (mol%) HA feed
Methane 74.35
Ethane 9.00
Propane 6.94
n-Butane 2.54
i-Butane 1.22
n-Pentane 0.57
i-Pentane 0.51
Neopentane 0.00
Carbon dioxide 4.78
Hydrogen sulfide 0.10
[22, 23], and process designs were developed for each feed. ProMax simulation
software [24] was used to simulate this process.
The simulation results were then used to size process equipment, develop mass
and energy balances, and determine operating conditions and utility consump-
tion of process equipment. Aspen process economic analyzer [25] was used to
estimate the equipment purchase costs. The Hand factor was utilized to account
for installation and other costs. The fixed capital investment (FCI) for each pro-
cessing unit was then estimated [26].
Nequipment
∑
FCIi = fqHand CqPurchased (2.1)
q=1
where FCIi , fixed capital investment for a given processing unit; fqHand , Hand fac-
tor for equipment q; and CqPurchased , the purchased cost of equipment q.
Table 2.4 shows the values and assumptions used to estimate the variable costs
(raw material costs were considered separately):
The only additional equations used were those to estimate the number of work-
ers based on the number of processing steps [28]:
∑
Nnp = Equipment (2.2)
where N np , the number of non-particulate processing steps, which is related with
the number of operators per shift (N OL ), given as in Eq. (2.3):
NOL = (6.29 + 31.7 × P2 + 0.23 × Nnp )0.5 (2.3)
where P, the number of processing steps where particulate solids are handled.
2.4.2.1 Changes in Fixed and Variable Costs

Additional cases were fed through the base case process design, and any needed
modifications were made to meet product specifications. Therefore, fixed and
variable costs were first estimated as before, and then only the change in each of
2.4 Case Study 21
Table 2.4 Parameters used for the techno-economic analysis.
Parameter Values Units References
Variable cost parameters

TEG price 0.93 $/lb [27]
Refrigerant price 13.11 $/GJ [28]
Electricity price 0.049 $/kWh [29]
Fuel price 2.98 $/MSCF [30]
Plant operator rate 32.74 $/h [31]
Plant supervisor rate 68.13 $/h [32]
Maintenance 5 % of FCI [25]
Operating charges 25 % of operating labor [25]
cost
Plant overhead 50 % of operating [25]
labor + maintenance
cost
General 8 % of all other operating [25]
administrative costs
Stream factor 0.96 — —
Table 2.5 Price of different commodities.
Commodity Units Base case
Heat valuea) $/MMBtu 2.98

Ethane $/gal 0.262
Propane $/gal 0.632
n-Butane $/gal 0.691
a) Methane and wellhead gas are priced in terms of their heat

value ($/MMBtu).
these costs was used in the subsequent calculations. For fixed costs, the change
was only used in cases where the costs were higher, since the need for smaller
equipment does not result in any savings for an existing plant.
2.4.2.2 Revenue
Table 2.5 shows the price of each component [33]:
2.4.2.3 Economic Calculations

The next step was to calculate the return on investment (ROI) [26]:
ROI = Annual Net Profit∕TCI × 100% (2.4)
where TCI, total capital investment.
First, the quantities in Eqs. (2.5)–(2.11) must be calculated.

∑
FCI = FCIi (2.5)
where FCI, total fixed capital investment:
TCI = FCI + WCI (2.6)
where WCI, working capital investment (assumed to be 15% of FCI):
AFC = (FCI − FCIS )∕N (2.7)
where AFC, annualized fixed cost (depreciation); FCIS , the salvage value of the
FCI (assumed to be 10% of FCI); and N, plant lifetime (assumed to be 10 years):
∑
AOC = VCi (2.8)
where AOC, annual operating cost; VCi , total variable cost for each process unit:
TAC = AFC + AOC (2.9)
where TAC, total annualized cost:
Annual income = Annual sales of methane + Annual sales of NGLs

(2.10)
Annual Net Profit = (Annual Income − Depreciation − AOC)

× (1 − Tax Rate) + Depreciation (2.11)
where the tax rate is assumed to be 30%.
For the other cases, the calculations are similar, except instead of fixed and vari-
able costs only the additional costs were determined. This is done because we are
considering only the additional costs for processing a new composition. Similarly
instead of ROI, incremental return on investment (IROI) is calculated instead:
IROI = Annual Net Profit∕ΔTCI × 100% (2.12)
where ΔTCI, the change in total capital investment for a given additional case.
Finally, the total ROI can be determined for treating multiple feeds from the
following:
∑
5
Total ROI = pf × Annual Profitf ∕TCItotal (2.13)
1
where p, probability or likelihood of obtaining a particular feed, and the subscript

f denotes feed.
2.4.3 Safety Index Calculations

A modified version of the PRI was used to evaluate each case in order to incorpo-
rate safety considerations into the design process. These calculations were done
2.5 Discussion 23
following the method of Leong and Shariff [18], but the flow rate of each stream
was incorporated as follows:
̇
PRI = [(HVm ) × (𝜌) × (P) × (ΔFLmix ) × (m)]∕108
(2.14)
̇ mass flow rate (kg/h); HVm , average mass heating value (kJ/kg); 𝜌, aver-
where m,
age fluid density (kg/m3 ); P, average pressure (bar); and ΔFLmix , average explo-
siveness (%), where the explosiveness for each stream is given as the difference
between UFLmix and LFLmix :
( n )
∑
UFLmix = 1∕ yi ∕UFLi (2.15)
( ni=1
)
∑
LFLmix = 1∕ yi ∕LFLi (2.16)
i=1
2.5 Discussion
First the process simulation for the six cases is discussed. Specifically the dehydra-
tion, the turboexpander, and the fractionation train processes are discussed for
all cases. Additionally acid gas removal is considered for the high acid gas case.
Acid gas removal is not needed for Feeds #1–5 as acid gas levels (CO2 and H2 S)
already meet specifications. Free water removal is not needed, as it is assumed
only bound water is present (see Section 2.4).
2.5.1 Process Simulations

2.5.1.1 Dehydration Process
For all five cases, the first unit operation of the gas treatment process is dehy-
dration. The typical dehydration process used in natural gas processing is glycol
dehydration, with the flowsheet shown in Figure 2.3. As mentioned previously,
the goal of the glycol dehydration process is to remove thermodynamically bound
water from the gas to permissible levels. Triethylene glycol (TEG) is the most
commonly used solvent in industry for water removal. This process contains two
loops, i.e. the contactor loop (where wet gas is contacted with TEG to remove
water) and the regenerator loop (where water is removed from TEG in order to
recycle the TEG back to the contactor).
2.5.1.2 NGL Recovery Process

Figure 2.4 shows a typical NGL recovery process used in natural gas processing.
In all cases except for Feed #1 (for reasons discussed later), NGL recovery is
done via the turboexpander process. This process is used to separate methane
from the NGLs. A key feature of this process is the turboexpander, which is used
to recover some recompression work done by the gas (see Figure 2.4). Another
key feature of the process is the compact (brazed aluminum) heat exchanger.
These exchangers can achieve much closer approach temperatures and can oper-
ate at much lower temperatures than can shell-and-tube exchangers [34].
22 23 Dry gas
XFS1 Makeup
Gas/glycol HEX
Makeup pump
Makeup tank
1 21 20 19 18
Glycol contactor
RCYL-1 13 Water gas
Blowdown
Q-4
Reflux coil (outside)
QRCYL-1
Q3 Q1
11
1 3 wet gas 2 12 1 Glycol regenerator
SAT-1 7 Flash gas 17
–2 water 4 5 6 2
Reflux coil (inside) VLVE-100 8

3
10
Rich flash
9
4 15
Lean/rich glycol exchanger Reboiler
14
Q2
16 Lean TEG
Figure 2.3 Glycol dehydration process.

20 21 Residue gas
Booster compressor Residue compressor

Q-Residue
19 15
13 1
Q-Expander
4 To gas 6
2 Demethanizer
Gas/gas exchanger
Turboexpander 3
Q-2 LTS
3 Dry gas Feed splitter Feed mixer 9 10 4
Q3 Chiller 5
1 Reboiler tubes Side reboiler 8 12 14
2 JT valve 6
XFS1 DVDR-1 5 To reboiler 7
Q-SideReb 7
17 10
Reboiler
16
Q RebA
Frac pump
22
18 NGL
Q1 To frac train
Figure 2.4 Turboexpander process (stream 19 shows the recovery of recompression work).
2.5.1.3 Fractionation Train

As seen in Figure 2.5, NGLs may be further separated into their components
using this distillation column sequence. This distillation column sequence is
chosen such that components are removed in order from lightest to heaviest.
This enables easy separation because it reduces the flow rate sent to subsequent
columns more than would separate the components in the opposite order. The
columns operate at very high pressure (from 120 to 285 psig) because at low
pressures all of these components are gases. This is done for all cases except for
Feed #1.
2.5.1.4 Acid Gas Removal

The acid gas removal unit simulated for this case is shown in Figure 2.6. This
unit is similar to the dehydration unit (Section 2.5.1.1). The solvents (methyl
diethanolamine [MDEA] and piperazine) are used to remove acid gases, CO2 and
H2 S, from the incoming sour gas in the absorber column, and the solvents are
stripped of the impurities in the stripper.
2.5.2 Profitability Assessment

Figure 2.7 shows the annual revenue associated with the five feeds and compares
the revenue with the composition of methane in the feed.
The total revenue increases with increasing quantity of NGLs in the feed,
despite the fact that each feed is primarily methane (Figure 2.7).
Methane sales prices (heat value) are typically reported in $/MMBtu (see
Table 2.5), which may be converted into an average price of US$0.02 gal/yr as
shown in Table 2.6. This price is significantly less than the price of the NGLs as
listed in Table 2.6. Thus, feeds with high NGL content generate higher revenue.
Table 2.7 shows the results from the economic calculations for the base case.
The ROI exceeded 10%, meeting the minimum criteria for potential profitability
(ROI > 10%).
As discussed previously, the base case was considered an existing plant. Addi-
tional cases were considered from a standpoint of whether needed modifications
were justified by amount of additional revenue made. This was assessed by cal-
culating the IROI. The results are displayed in Figure 2.8. Figures 2.8 and 2.10 do
not include the base case (Feed #3) as they examine only additional cases.
Higher methane composition feeds generally require fewer modifications to the
existing plant. As a result, the TCI change for these feeds is very low (Figure 2.8).
However, the additional annual net profit for these feeds is also low. The necessary
modifications are justified economically, using the criteria of IROI > 10%, for all
the cases except for the high methane case (Feed #1).
We next explain the condition for Feed #1. The content of NGLs in Feed #1
is very low (see Table 2.2), such that the gas already meets pipeline quality,
except for the quantity of water in the gas. Therefore the turboexpander and
fractionation train separation units are not needed. NGLs are very valuable, and
therefore it is worth considering keeping these separation units. However this
is determined to be infeasible, due to the fact that for the given inlet pressure
of 1000 psig, the stream can never be in the two-phase region regardless of the
12
4
C4 condenser iC4 condenser

Q-1
C3 condenser Q-5 Q-7
C2 reflux drum
3 17
Q-3 25
C2 condenser
2 10 16 24
5 18
1 6 1 11 1 19 23 C4 1 26
27 IC4
Depropanizer
Q-11 Q-10
7 18 30 30
C4 splitter
1 Y-grade feed
Deethanizer Debutanizer
35 8 36 14 60 21 60 29
C2 reboiler C3 reboiler C4 reboiler 28 NC4 reboiler

7 13 20
To frac train
Q-2 Q-4 15 Q-6 Q-8
9
22
30 NC4
Figure 2.5 Fractionation train.

FAXR-100
XFS2
1 2
4–Sweet gas
Q-1 18–Makeup
Circulation pump MDEA makeup
22 21
20 Recycle
Trim cooler 17–Recycle guess
12–Acid gas
19–Blowdown
Absorber P-1
Condenser
1–Dry basis sour gas 3-Sour feed
6–Flash gas
Q condenser
Saturator
2–Saturant (water) 5–Rich amine 16 10
Flash tank 9
1 11 P-2
Lean/rich exch
7 8 2 Reflux pump
3
4
5
6
Stripper
7
8
9
10 14
Reboiler
15–Lean amine 13
Q reboiler
Steam tubes
51–Steam 52–Condensate
Figure 2.6 Acid gas removal unit.

2.5 Discussion 29
100.00 350.00
90.00
300.00
80.00
Composition (mol%)
Revenue (MM$/yr)
70.00 250.00
60.00
200.00
50.00
150.00
40.00
30.00 100.00
20.00
50.00
10.00
0.00 0.00
Feed Feed Feed Feed Feed
#1 #2 #3 #4 #5
Feed #
Methane composition NGL compostion Methane revenue NGL revenue
Figure 2.7 Comparison of gas composition with revenue.
Table 2.6 Effective prices for products ($/gal).
Commodity Units Base case
Heat value $/gal 0.02

Ethane $/gal 0.262
Propane $/gal 0.632
n-Butane $/gal 0.691
stream temperature. Thus it is not possible to remove the NGLs from the gas in
a profitable way (see the phase envelop in Figure 2.9). Besides, the sales gas and
wellhead gas have the same price (the heat value price), and almost the same
heat value (approximately 1015 Btu/SCF), so there is no way to make a profit.
Some feeds are more likely to occur than others. To obtain a more accurate
picture of whether or not each stream is worth treating, its IROI is multiplied by
the probability for it to occur (see Table 2.2 for details). Next, the IROI based on
probability of occurrence was calculated (Figure 2.10).
As can be seen all of the listed feeds are still worth treating based on the
IROI > 10%. Despite the fact that Feed #5 generates the most additional revenue,
it is only barely worth making the additional needed capital investment because
the probability of this feed occurring is very low (7.50%).
The total ROI calculated for these five feeds based on their likelihood to occur
is determined from Eq. (2.13).
The total ROI is found to be 24.4%, which is greater than the 15.9% for treating
only the base case.
Table 2.7 Return on investment for the base case.
Base case
Total fixed cost (MM$) 29.5

Total variable cost (MM$/yr) 13.6
Feedstock cost (MM$/yr) 204
Total revenue (MM$/yr) 225
Annual net profit (MM$/yr) 5.50
Total capital investment (MM$/yr) 34.6
ROI (%) 15.9
45.0
4109.10
40.0 4000
Annual net profit or total capital investment
35.0 3500
30.0 28.23 3000
Incremental ROI (%)

25.0 2500
(MM/yr)
19.47
20.0 2000
16.82
11.85
15.0 1500
0.29
10.0 1000
4.48 434.74
5.0 500
167.86
–0.03 0.03 –76.96
0.0 0
Feed #1 Feed #2 Feed #4 Feed #5
–5.0 –500
Feed #
ΔAnnual net profit (MM$/yr) ΔTotal capital investment (MM$/yr) Incremental ROI (%)
Figure 2.8 Economic metrics for the additional cases.
2.5.3 High Acid Gas Case Economics

Figure 2.11 shows the revenue for the base case and high acid gas case. There
is only a slight decrease in revenue compared with the base case for the high
acid case. This is because only a small percentage of the incoming gas is acid
gases, while the remainder of the feed composition is similar to that for the base
case feed.
As shown in Table 2.8, the additional TCI required to treat this stream is not
significant, as compared with the additional revenue, and therefore this stream is
clearly worth treating (IROI > 10%).
2.5.4 Safety Index Results

PRI is a relative comparison. The exact values from the calculations are not mean-
ingful, only the relative comparison between different process routes, or in this
2.5 Discussion 31
1000 VF = 0%
VF = 100%
Critical point
800 Stream condition
Pressure (psig)
600
400
200
0
–280 –240 –200 –160 –120 –80 –40
Temperature (°F)
Figure 2.9 Phase envelope for Feed #1 before the demethanizer column (generated from
process simulation).
1400
1164.11
IROI based on probability (%)
1200
1000
800
600
400
123.16
200
–5.77 12.59
0
Feed #1 Feed #2 Feed #4 Feed #5
–200
Feed #
Figure 2.10 IROI based on feed probability.
case different incoming feeds. Only streams where a significant change in com-
position, pressure, or fluid density occurs were included in the calculation.
One significant weakness of PRI is that is uses the overall average value of each
property for all the streams, effectively treating every stream considered as if it
has the same flow rate (and thus same potential risk). This leads to misleading
results; to give a more truthful picture, the values of each of the four properties
used to calculate PRI (mass heating value, fluid density, pressure, and explosive-
ness) were multiplied by their flow rates as presented in Table 2.9.
The lower methane cases are less safe to process. This is because the flows
are generally larger in these designs because dehydration is more difficult, and
because the fractionation process has higher flow rates due to higher NGL
content. Nonetheless there is really not a significant difference in these process
designs from a safety perspective. Therefore economic criteria should be the
main concern for deciding whether or not to treat streams.
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wire or tacked at right angles to a stick small enough to pass easily
between the wires of the cage. Cages with bottom attached should
be provided with a sand tray that slides in and out through a slot in
the front. This serves to catch droppings, seed hulls, and other
waste, and may be easily pulled out, cleaned, and refilled with fresh
sand.
INDOOR AND OUTDOOR AVIARIES.
Those who keep birds for pleasure, and who do not care to breed
them for exhibition or to maintain any particular standard, may
receive much enjoyment from aviaries in which numbers of canaries
are kept in one inclosure. The size of the aviary or bird room will be
governed wholly by circumstances, as it may range from an entire
room to a small screened inclosure or part of a conservatory. A room
large enough for the owner to enter without unduly frightening the
occupants makes an ideal indoor aviary, and where space permits it
may be fitted up without great expense. The floor should be covered
to the depth of half an inch to an inch with clean sand or sawdust.
Small evergreen trees planted in large pots furnish suitable
decorations, and may be replaced from time to time as they are
destroyed by the inmates of the aviary. A branching dead tree and
one or two limbs nailed across corners at suitable heights furnish
more artistic perches than straight rods. In addition, pegs 4 or 5
inches long may be driven or nailed to the walls to furnish resting
places.
Seed should be supplied in self-regulating hoppers, preferably
attached to the wall, and water given in self-feeding fountain
containers. These become less dirty than open dishes placed on the
floor. Sand must be furnished in a box or dish where it is not used on
the floor. Soft foods and green foods may be supplied on little
shelves or a small table. At the proper season nesting boxes may be
hung on the walls, and nesting material supplied in racks or in open-
mesh bags hung to some support. A shallow pan of water may be
kept constantly on the floor or, better, may be inserted for an hour
each day for bathing. A screened flying cage may be built on the
outside of a window and the birds admitted to it in pleasant weather.
Perches, if of natural wood, should have smooth bark or should be
peeled, as crevices often harbor mites. Plants and other decorations
should not be placed so near the wall that birds may be trapped
behind them.
Aviaries constructed out of doors, like bird rooms, may be made
simple or elaborate, large or small, according to circumstances.
Where there is sufficient ground available a small frame structure
may be built and covered with strong galvanized wire screen of
small-sized mesh. Part, at least, of the roof should be covered as a
protection against stormy weather, and two sides should be boarded
up to afford protection from cold winds. Where the winter climate is
severe it is necessary to build a closed addition with board or cement
floor and a connecting door, in which the birds may be protected
during the cold season. Canaries when acclimatized, however, can
withstand moderately cold weather as well as native birds.
The open portion of the aviary should have a board or cement
base sunk to a depth of 8 to 10 inches around the bottom to prevent
entrance of rats, mice, or larger animals. If a fence with an overhang
at the top is not constructed to keep out animals, it is best to make
the screen walls double by nailing screen wire to both sides of the
wooden frame, so that birds clinging to the wire may not be injured
by cats or dogs. Where space does not permit an elaborate structure
a lean-to may be built against another wall to make an inclosure
large enough for a number of birds. Where needed, the sides of the
aviary may be fitted with windows that can be put in place in winter.
The entrance to the outdoor aviary should be through a small porch
or anteroom that need be merely large enough to permit entrance
through an outside door, with a second door leading into the aviary
itself. The outside door should be closed before the inner one is
opened, so that none of the birds can escape.
The fittings of the outdoor aviary may be adapted from those
described for the indoor bird room. With an earth floor it is possible
to grow evergreen and deciduous shrubs for shelter and ornament.
Where space permits a hedge of privet along the open side of the
aviary furnishes a shelter in which birds delight to nest. To avoid
overheating in hot weather shade should be provided for part of the
structure.
In aviaries birds pair more or less at random. To avoid constant
bickering or even serious fighting in the breeding season it is usual
to regulate the number of males so that the females outnumber them
two to one.
FOOD.
The food requirements of canaries are simple. Canary seed to

which have been added rape seed and a little hemp is a staple diet
that persons who keep only a few birds usually purchase ready
mixed. Canary seed alone does not furnish a balanced food, but
forms a good combination with hemp and summer rape. Much of the
rape seed in prepared seed sold in cartons is of a species that even
wild birds do not eat, as it is pungent and bitter in flavor, but all relish
the mild taste of true summer rape. Seed is given in little cups that
are fastened between the wires of the cage.
In addition to a seed supply lettuce or a bit of apple should be
placed between the wires of the cage frequently. And those properly
situated may, in season, vary this menu by the addition of
chickweed, dandelion heads, thistle and plantain seeds, and the
fruiting heads and tender leaves of senecio and shepherd’s purse.
Watercress, wild oats, knot grass, and other grasses are relished,
especially in spring and early in summer.
Bread moistened in scalded milk, given cold at intervals, is
beneficial. Soft foods must not be made too wet. With bread, enough
liquid to soften the food but not to run or render it a paste is
sufficient. Supplies of moist foods must be kept strictly fresh and
clean or sickness may result. Special dishes, known as food holders,
or slides that slip through the wires of the cage are often used in
giving softened bread and similar supplies. Cuttle bone should
always be available.
When canaries do not seem to thrive it is well to crack open a few
of the seeds to make certain that empty husks alone are not being
fed. Hemp, while a valuable addition to the diet, should not be given
in excess, as it is fattening and may make birds so lethargic that they
cease to sing, or in exceptional cases may even cause death. When
canaries cease to sing from the effects of overfeeding it is well to
supply some of the stimulating foods known as song restorers, or
other prepared foods that may be obtained from dealers.
During the time of molt a few linseeds added to the seed supply
are believed to give gloss and sheen to the new feathers. Linseeds
should be given in small quantity, as they are injurious if eaten in
excess. Meal worms fed occasionally are beneficial for birds that are
not thriving. A craving for animal food may be satisfied by bits of raw
steak, but it is not well to continue feeding raw meat for any length of
time, as it may cause a foul odor about the cage. Delicate birds may
be fed canary, rape, and hemp seed soaked in cold water for 24
hours, rinsed, and then drained. Maw seed (poppy seed) is favored
by English canary fanciers as a stimulant, but its use must be
guarded, as it may be poisonous to other animals, including man.
During the breeding season egg food must be given daily as soon
as the birds are paired. This is prepared by mincing an entire hard-
boiled egg or passing it through a sieve, and adding to it an equal
quantity of bread or unsalted cracker crumbs. This may be given to
unmated birds as well at intervals of a week or so. When female
canaries begin to incubate, egg food may be fed every three or four
days or even less frequently. Addition of brown sugar in small
quantity to the egg food is supposed to prevent egg-binding in young
females. When the young hatch, egg food should be supplied at
once. Some recommend that the yolk of a hard-boiled egg be given
alone for the first day. Bread crumbs are added to this daily until on
the third day egg food as ordinarily prepared is supplied. Attempt
should be made to regulate the supply of egg food or other soft food
so that it will be eaten without waste. The actual quantity will vary in
individual cases. The usual seed supply should be present, no
matter what other food is given. Egg food must be given until the
young are fully grown and able to crack seed for themselves.
Cracked seed may be fed to lighten the labor of the parents, but it is
well to eliminate hemp from such a supply, as the hull of hemp seed
contains a poisonous substance that occasionally kills young birds.
Drinking water should be available to canaries at all times.
BATHING.
Under normal conditions most birds probably bathe daily, and

canaries in captivity should be allowed the same opportunity. In open
wire cages in common use for singing birds the base is removed and
the cage placed over a small dish containing water. In open-front
cages in which the bottom is not detachable small bath cages which
fasten at the open door are used. These are only a few inches wide
but serve to hold a dish for water. Many birds are notional in bathing
and at times ignore the offered bath. Usually the process of cleaning
the cage and renewing the seed and water will excite in them a
desire for bathing, and often when a bath is not provided the bird will
do its best to perform its ablutions in the small supply of water in the
drinking cup. When individual birds obstinately refuse to enter the
water, if enough clean sand to cover the bottom is placed in the dish
they bathe more readily. After the bath the water may be drained
carefully and the sand left to dry in the dish for use another time.
Birds brought into strange quarters may refuse to bathe for the first
few days. When water is offered they either ignore it or sitting on a
perch go through the motions of bathing and drying, fluttering wings
and tail with a great whirring of feathers. The bath should be offered
whenever the cage is cleaned, and if left alone the birds will act
normally after a few days.
Small china or earthenware dishes that are not too deep make
good bathing pans. When a bird becomes accustomed to one dish it
will usually refuse to bathe in another of different shape or color. In
winter the water should be warmed until tepid. Even in warm weather
very cold water is not advisable. If the room, ordinarily warm,
becomes cold temporarily, birds should not be allowed to bathe. With
the plumage wet and bedraggled there is increased susceptibility to
cold drafts. During molt the bath should be given not more than twice
each week. If the bird is molting on color food, one bath each week
is sufficient. The female canary should not be allowed to bathe from
the time the eggs hatch until the young are 3 or 4 days old.
MOLT.
Canaries renew their covering of feathers once each year. In

adults this molt occurs late in summer, and the first sign of it may be
the presence of a wing or tail feather on the bottom of the cage.
These large feathers are shed in pairs, so that one from either wing
or from either side of the tail is dropped at approximately the same
time. Never in ordinary circumstances does the canary have the
wing and tail entirely devoid of large feathers. This provision is of no
particular significance in a cage bird, but enables wild birds to
maintain their powers of flight. The bodily covering is renewed
piecemeal as well, so that except about the head there is normally
no extensive area wholly devoid of feathers at any time. Some birds
drop a few of the body feathers all through the year, a symptom that
need cause no anxiety.
With breeding birds the molt usually comes immediately after the
breeding season and may begin as early as the latter part of July.
Normally it comes during August, and on the average should be at
its height in September. Young birds molt the juvenal body plumage
after leaving the nest, but retain the first growth of wing and tail
feathers for a year. In healthy birds the entire molt requires about two
months.
Canaries usually need no special care during molt. Though in an
abnormal bodily state at this time, healthy individuals will come
through the period in good condition. Birds are somewhat dull and
stupid when molting and should be disturbed as little as possible.
Bathing may be permitted once or twice each week, but if birds do
not wish to bathe they should not be sprayed with water. It is well to
add egg food or moistened bread to the ordinary fare once or twice
each week during molt. For ailing birds a very slight quantity of
sulphur may be added to the egg food, or a weak saffron tea given
instead of pure drinking water. A few linseeds in the seed supply give
a gloss and sheen to the new feathers not otherwise obtainable.
When canaries fail to molt at the proper season molt may
sometimes be induced by covering the cage with a dark cloth and
placing it in a warm protected place where the bird will not be
disturbed.
Old birds or those weak in physical vigor often fail to renew their
entire feather covering, a condition for which little remedy may be
offered. Usually this incomplete molt is a sign of extreme age or
breakdown, though if the bird lives, a supply of nutritious, easily
assimilated food and careful protection during the next molt may
result in improvement.
A great change in temperature or a sudden chill may check the
progress of molt and occasionally cause serious trouble. If a bird
shows signs of distress, it should be placed at once in a warm,
protected place. Ten drops of sweet spirits of niter and a few shreds
of saffron added to the drinking water are beneficial.
COLOR FEEDING.
That the color of canaries may be deepened or intensified by

certain foods given during the molt is well known and has attracted
much interest. Turmeric, marigold flowers, saffron, cochineal,
annatto, mustard seed, and other agents rich in natural color are
often used for this purpose, ordinarily in combination with red pepper
as a base. For a long time methods of preparing and feeding color
foods were kept secret, but now they are outlined in many manuals
on canary feeding.
In selecting canaries for experiments in color feeding preference
should be given to strong, vigorous, male birds. During digestion and
assimilation the concentrated food used puts more or less of a strain
upon the system, and birds that are old or constitutionally weak may
not thrive, or may even succumb under the treatment. Color food
may be given young canaries at the age of 7 or 8 weeks to produce
a deep color at their first molt. Birds with color that is naturally full
and rich should be selected. Those having greenish markings or
those descended from a male parent well marked with green are
preferable. Pale birds seldom color well.
A standard color food may be prepared as follows: To the ordinary
egg food (one hard-boiled egg chopped fine with an equal bulk of
bread crumbs or unsalted cracker crumbs) add a teaspoonful of
ground sweet red pepper. Mix until the food shows an even reddish
tint throughout. Care should be taken to see that the supply of
ground sweet pepper used is fresh and clean and that it is not
artificially colored. Each bird to be experimented upon should receive
one small teaspoonful of the prepared food daily. The quantity of
pepper in the mixture is increased gradually, until two heaping
teaspoonfuls are used. Addition of a little brown sugar and a few
drops of pure olive oil is beneficial, and a small quantity of hot red
pepper gives a better flavor. The food should be prepared fresh each
day, and in mixing allowance must be made for variation in the size
of eggs used.
Some breeders increase the proportion of sweet red pepper until 4
teaspoonfuls are added to the usual quantity of egg food. Half a
teaspoonful of this concentrated food is allowed each bird. This
method may be used during a short, quick molt. The usual supply of
seed must be kept in the cage, for canaries can not subsist on the
color food alone.
Those who do not care to use such an elaborate preparation in
color feeding may substitute pieces of the common sweet red
peppers sold in fresh vegetable markets for the bits of lettuce
ordinarily given as green food. Canaries eat these readily, and from
the effect of this food eaten during molt become noticeably deeper
and richer in color.
Color feeding to be successful must be started as soon as the
canaries are ready to molt, and feeding must be continued until no
more pin feathers can be found anywhere on the body when the
feathers are carefully blown aside. The color food actually supplies
an enriched color element that otherwise is lacking. Until the artificial
color is firmly fixed in the matured feather it fades easily when
exposed to strong light. The birds chosen for color feeding should be
kept in a dim light away from the windows and with the cages
shaded. Open-front cages are easily provided with a screen of paper
or cloth, but care must be taken to leave space for ventilation. Direct
sunlight must be avoided. Bathing must not be permitted more often
than once a week, and the birds should be disturbed as little as
possible.
Should a bird refuse the color food, the seed supply may be
removed for a short time morning and evening and the color food
substituted. Usually in a day or two the stimulating food will be eaten
eagerly. Linseeds should be given (as during the regular molt) to
impart a gloss to the new feathers. With proper care there will be
little trouble in producing fine, healthy birds with rich, highly colored
plumage. The enhanced color lasts only during the continuance of
the growth of feathers, and if color feeding is not resorted to at the
next molt the canary will again be plain.
BREEDING.
The breeding season for canaries begins properly in March.

Though birds often show signs of its approach as early as January, it
is better, because of the effect of changing weather conditions upon
callow young, to postpone nesting activities until later, if possible.
Some canary fanciers keep canaries paired throughout the year, but
the more common practice is to separate the sexes except when
breeding. The beginning of the mating season is marked by ringing,
vigorous song among male birds, accompanied by much restless
activity. Females, indifferent until now, respond with loud call notes,
flit their wings, and otherwise evince their interest. Birds may be
paired without these preliminary signs, but usually this tends only to
lengthen the breeding season without material benefit. The instinct to
breed may be stimulated when necessary by the addition of egg food
and green stuff to the diet.
Canaries in captivity are polygamous when opportunity offers, and
many breeders place two or even three females with each male.
Others, however, keep canaries in pairs, as they are more readily
handled, and when the young are hatched the male is able to assist
in caring for them. Where two females are kept with one male the
birds should be placed in a cage divided by slides into three
compartments. The male is placed in the middle, and a female on
either side. During half the day the male is thrown with one female
and during the remainder with the other. This arrangement
necessitates the use of three sets of seed and water cups in each
cage. When the females begin to incubate the male is removed or
excluded from both.
A cage suitable for one pair of canaries should be equipped with a
sliding wire partition. The male and the female are placed one in
either compartment and the two left to make acquaintance. The male
will begin to feed the female through the wires in a day or two, or
perhaps at once, and when this is observed the slide may be
withdrawn and the birds kept together. If a cage is used that has no
slide, there is usually some bickering between the birds at first, but
birds are rarely found that do not in the end agree. A cage thus used
without a slide should be new to both birds, in order that neither may
resent the presence of an intruder in a cage which it has been
accustomed to consider its own.
Soon after pairing the female will be seen carrying feathers in her
bill or searching about the bottom of the cage. If a little nesting
material is given her she will be content to arrange and rearrange it
for a few days. As soon as she shows serious intention of building,
enough material for actual nest construction may be supplied. If a
considerable quantity is furnished at first it is merely wasted. The
material may be held in a small wire rack suspended on the outside
of the cage or placed inside. Bits of string, cotton, slender blades of
dried grass, dried moss, cow’s hair, or other soft material will serve
well. No long strings or long hairs should be given, as these may
cause trouble later by entangling the feet and legs of mother and
young. Everything furnished should be clean and free from dust.
Some canaries are expert nest builders, while others construct a
slovenly structure that barely serves to contain the eggs. Some
fanciers prefer to construct nests for their birds, and with certain
birds this is necessary as some females may refuse to build.
Canaries build in anything that offers support. A nest box of wood,
or, better, an earthenware nest pan, may be fastened to the side or
back of the cage midway between the two perches. The rush or
willow nests sold by many dealers, while serviceable, may harbor
vermin. The earthenware nest pan is best, as when the breeding
season is over it is readily cleaned and put away for another year.
Failing this, a box 1¼ inches or more deep made of thin wood may
be used. The nest box or pan should have a lining or bottom
covering of felt. This may be pasted in the earthenware pan, and
may be soaked loose without trouble when it is desired to renew it.
The nest receptacle, of whatever description, should be suspended
an inch above the level of the perches. This prevents the young from
leaving the nest too soon. The receptacle should not be near enough
to the top of the cage to interfere with the movements of the
occupants. If the nest is not too near the perches the male is not so
likely to be obtrusive during incubation.
The first egg will be deposited from a week to a month after the
birds are paired. Normally it is laid in about two weeks. The number
of eggs in a sitting may vary from three to six, with four or five as the
usual number. The eggs should be removed as soon as laid. This
may be done readily with a teaspoon, with care not to injure the
delicate shells. They should be kept in a cool place, slightly
embedded in fine corn meal or bran or cared for in some other
manner that does not allow them to roll about or touch each other.
On the evening of the day on which the third egg is laid all may be
returned to the nest.
Removing the eggs and then replacing them postpones incubation
and development in those first laid and makes the time of hatching
more even. The normal period of incubation is 14 days.
Egg binding sometimes causes trouble and may be dealt with as
follows: The vent may be oiled carefully with a drop or two of
warmed castor oil and the bird returned to the cage. If the egg is not
deposited within half an hour the canary should be held for a few
minutes with the vent over the steam of hot water. A good method is
to fill a narrow-necked jar or bottle with hot water and cover the
mouth of the receptacle with cheese cloth; the female is then held
carefully for a minute or two in the rising steam. Often the egg will
drop at once and be caught in the cheesecloth, or it may be
deposited in the normal manner after the bird is returned to the cage.
The male canary is ordinarily a model husband and parent, giving
no trouble, but if he should annoy the female during incubation or
attempt to injure the young he should be removed at once. It is the
natural instinct of an incubating bird to conceal itself as much as
possible, and though canaries are tame, this tendency should be
recognized and respected. This does not mean that they are to be
neglected. Each breeding cage should be equipped with a sand tray
which should be cleaned at least every other day. In no other way
can it be hoped to rear numbers of birds successfully. Except for this
necessary care and the provision of food, water, and bathing
facilities, the birds should be bothered as little as possible.
Sometimes trouble is caused by inability of the young to free
themselves from the shell or egg membrane, a condition for which
there is usually no remedy at the time. With succeeding settings the
difficulty may be obviated by sprinkling the eggs slightly with water
each evening. Some breeders when the young canaries are 8 days
old place them in a new nest, a practice that may be necessary
when the old nest is infested with parasites. In such instances a little
insect powder should be sprinkled over the body before the young
birds are placed in their new quarters.
The young birds leave the nest when 20 to 30 days old. They may
be left with the parents as long as they are fed and should never be
removed entirely until it is found that they are able to crack the seeds
upon which they must feed. It is advisable to continue the use of egg
food for a time and gradually to decrease the amount given to get
the birds accustomed to a diet of seed alone.
Canaries often rear two or three broods a season and the female
may be ready to breed again when the young are three weeks old. It
is only necessary to provide a second nest and nesting material and
let her proceed. The care of the young will then devolve on the male.
Nesting material should be provided at once or the female may pluck
the feathers from her growing young. If this can not be stopped the
young should be placed in a small nursery cage suspended from the
side of the breeding cage in a manner that will allow feeding
between the wires. When the young are finally removed they must
not be placed with birds older and stronger for a time. They should
be watched carefully the first day, and if any one does not feed it
must be returned to the parents at once. Though most of the losses
among canaries come at this time, with care in food and cleanliness
there should be little trouble.
SEX AND AGE.
To determine sex and age in living canaries is difficult and is to be

attempted only by one who has had long experience as a canary
fancier. The external characters denoting sex are not easily
described. In nearly all cases a male may be recognized by his
proficiency as a songster, but occasionally female birds also possess
a clear, full song. When in breeding condition the sex may be
determined readily by examining the vent. In males it is protuberant,
while in females it does not project below the level of the abdomen.
By daily observation the canary breeder is generally able to
distinguish the sexes through slight differences in carriage and
mannerisms not apparent to one not familiar with them.
In judging age the feet offer the only characters easily seen, but
even these can not always be relied upon. Birds a year old or less
usually have the skin and scales covering the feet and tarsi smooth
and of fine texture. In older birds they appear coarser and
roughened. Very old birds usually have had the claws trimmed until
they appear blunt or rounded rather than sharp and pointed (see p.
19).
Canaries have lived many years when cared for regularly. Dr. C.
W. Richmond, Associate Curator of Birds in the United States
National Museum, relates that two birds, hatched in the same brood
and kept entirely separated after they left the nest, lived 18 years,
dying within a few weeks of each other. Another case is on record in
which a canary was known to be at least 34 years old when it died,
and even this advanced age may have been exceeded. Usually with
advancing years birds molt irregularly or lose part of the feathers
entirely. Often their eyesight is impaired. It is said that canaries that
have not been paired live much longer than those allowed to breed.
VERMIN.
Canaries are affected by two forms of external parasites. The

larger of these, a bird louse[2] known usually as the gray louse, is an
insect with a slender, elongate body and a large head armed with
strong jaws. This pest feeds upon the feather structure of the bird’s
outer covering, and though it does not suck the blood of its host, its
sharp claws irritate the skin and cause discomfort to the bird. The
eggs of the gray louse are attached to the feathers by a gum and are
not easily removed. The young insects resemble the adults and in a
few weeks after hatching are fully grown. They are best combated by
blowing insect powder (pyrethrum) into the plumage of the affected
bird with a small bellows or blower. This treatment should be
repeated two or three times at intervals of a week to insure the
destruction of any young lice hatching in the meantime.
The other parasite of canaries is a small mite,[3] a minute
spiderlike creature that when fully grown is barely visible to the
unaided eye. Its natural color is whitish, but nearly always it is filled
with blood sucked from the body of the unfortunate bird harboring it,
so that it appears bright red. These mites are nocturnal, and except
in cases of severe infestation are seldom found upon the body of
their host during the day. They are often found in the slits at the ends
of the perches or in the round piece of metal forming the support at
the top of the ordinary wire cage. In wooden cages they hide in
cracks, nail holes, or crevices, and their presence is betrayed upon
close examination by minute white spottings. If unnoticed, they
multiply rapidly and sap the strength of the bird by sucking its blood.
When their presence is suspected a little coal oil, or kerosene,
applied freely to the cage with a brush may be sufficient to kill the
pests. Or the bird may be removed temporarily and the cage cleaned
thoroughly with a solution of 1 ounce of commercial carbolic acid in a
gallon of water, applied with a small brush, taking care to reach all
crevices. In severe infestations it may be necessary to immerse the
cage for several minutes in water that is boiling hot. Insect powder
may be used as for the gray louse.
Where facilities for frequent bathing are offered and the cage is
kept clean, there is usually little trouble with either mites or bird lice.
When a bird is sick and neglects its customary bathing, cleaning,
and preening, it is surprising to see how rapidly these pests multiply.
With care, however, they may be completely eradicated, though
fresh outbreaks are likely to occur when new birds are obtained. In
wooden cages cracks in the boards that have harbored mites may
be closed with glue to prevent a return of the pests.
FOOTNOTES:
[2] Docophorns communis Nitzsch. Order Mallophaga.

[3] Dermanyssus avium De Geer, closely allied to the chicken
mite D. gallinae De Geer.
CARE OF FEET AND BILL.
As a canary grows old it will be noticed that its claws become long
and catch on the perches and wires as it hops about the cage. In a
state of nature the activities of the bird as it moves about on the
ground or among twigs and limbs keep the claws properly worn
down. Confined in a cage the canary is less active, and while the
claws have the same rate of growth they are here subject to much
less abrasion. It is necessary, therefore, to trim them with a pair of
sharp scissors every few months. It is important to watch the
condition of the claws carefully, as by catching they may cause a
broken leg. In each claw a slender blood vessel extends well down
toward the tip. This is indicated in Figure 6 by the letter A, and may
be seen on close examination through the transparent sheath of the
bird’s claw. In trimming cut well beyond this canal (at the point B in
the figure) and take special care not to break the leg while handling
the bird.
Fig. 6.—Diagram of foot of canary with

overgrown claws. A, Terminal blood
vessel; B, point at which claw may
be trimmed without injury.
In cage birds the horny covering of the bill, as well as the claws,
sometimes becomes distorted through growth without sufficient
wear. The tips of the mandibles may be pared down with a sharp
knife, but care must be taken not to cut deep enough to reach the
quick.

Process Intensification and Integration For Sustainable Design Dominic C Y Foo Editor All Chapter

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Process Intensification and Integration

for Sustainable Design Dominic C. Y.

Mahmoud M. El-Halwagi Library of Congress Card No.:

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Print ISBN: 978-3-527-34547-2

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1 Shale Gas as an Option for the Production of Chemicals and

2 Design and Techno-Economic Analysis of Separation Units to

2.5.1 Process Simulations 23

3 Sustainable Design and Model-Based Optimization of Hybrid

4 Techno-economic and Environmental Assessment of Ultrathin

4.3.1 Simulation and Elucidation of Mixed Gas Transport Properties of

5 Process Intensiﬁcation of Membrane-Based Systems for Water,

6 Design of Internally Heat-Integrated Distillation Column

7 Graphical Analysis and Integration of Heat Exchanger

8 Insightful Analysis and Integration of Reactor and Heat

9 Fouling Mitigation in Heat Exchanger Network Through

9.2.2 Fouling Threshold Model 171

10 Decomposition and Implementation of Large-Scale Interplant

11 Multi-objective Optimisation of Integrated Heat, Mass and

11.2.1 Regeneration in Process Synthesis 222

12 Optimization of Integrated Water and Multi-regenerator

13 Optimization Strategies for Integrating and Intensifying

14 Sustainable Biomass Conversion Process Assessment 301

The chemical process industry involves a broad spectrum of manufacturing

Section 1 – Process Intensiﬁcation

Section 2 – Process Integration

“Fouling Mitigation in Heat Exchanger Network Through Process Optimiza-

Kajang, Malaysia Dominic C. Y. Foo

Shale Gas as an Option for the Production of Chemicals and

1.2 Where Is It Found?

Process Intensiﬁcation and Integration for Sustainable Design, First Edition.

Table 1.1 Major shale gas plays in the United States.

Percentage of dry shale gas

Marcellus PA, WV, OH, and 32.7

Source: Adapted from EIA 2018 [4].

Unproved recoverable Production in

China 1115.20 353.15 [8]

Source: From EIA 2015 [13].

1.3 Shale Gas Composition

1.4 Shale Gas Eﬀect on Natural Gas Prices

1.5 Alternatives to Produce Chemicals from Shale Gas

1.6 Synthesis Gas

Table 1.3 Reforming options and their characteristics.

Steam reforming H2 O Endothermic CH4 + H2 O → CO + 3H2 Catalytic

Source: Adapted from Noureldin et al. 2014 [20].

needed. The overall process is very energy intensive, as it involves a reforming

1.11 Process Intensiﬁcation Opportunities

M = C = 2phM = PC(VL) = PT(VL) = PS(VL)

M = 2phM = PC(VL) = PT(VL) = PS(VL)

M = 2phM = PC(VL) = PT(VL) = PS(VL)

M = 2phM = PC(VL) = PT(VL) = PS(VL)

M = H = 2phM = PC(VL) = PT(VL) = PS(VL)

Figure 1.2 Simultaneous phenomena building blocks in a conventional distillation column.

CO2 Tail gas

1.12 Potential Beneﬁts and Tradeoﬀs Associated

2 EPA (2018). The Process of Unconventional Natural Gas Production. U.S.

16 Business Insider. (2019). Natural gas (Henry hub) prices. https://markets.

28 Peplow, M. (2017). How fracking is upending the chemical industry. Nature

Design and Techno-Economic Analysis of Separation Units