Modeling of IGFC system

CO2 removal from the gas streams,

using membrane reactors

Raido Huberg
 MODELING OF IGFC SYSTEM

CO2 removal from the gas streams, using membrane reactors

Raido Huberg

A 30 credit units Master’s thesis

Supervisors:
Dr. Robert Braun (Project advisor)
Dr. David Dvorak (Academic advisor)
Prof. Thorsteinn I. Sigfusson (Academic advisor)

A Master’s thesis done at

RES │ the School for Renewable Energy Science
in affiliation with
University of Iceland &
the University of Akureyri

Akureyri, February 2009

Modeling of IGFC System

CO2 removal from gas streams, using membrane reactors

A 30 credit units Master’s thesis

© Raido Huberg, 2009

RES │ the School for Renewable Energy Science

Solborg at Nordurslod
IS600 Akureyri, Iceland
telephone: + 354 464 0100
www.res.is

Printed in 14/05/2009
at Stell Printing in Akureyri, Iceland
ABSTRACT

In the following work, the different capture concepts of carbon dioxide from an IGFC power
plant have been considered and analyzed. The main objective was to compare the net power
output according to the different tail-gas processing concepts (oxy-combustion, H2- and O2-
conducting membranes) and to compare the difference of output when CO2 is vented.

The first concept considered is an IGFC plant (integrated gasification gas combined cycle
plant with a fuel cell) with oxy-combustion for oxidizing the remaining fuel in the anode tail-
gas. The second and third concepts are H2-conducting membranes, one with N2 and the other
with air as sweep gas. The fourth concept involves an O2-conducting membrane in which O2
permeates from the cathode side to the anode side without mixing the two streams with each
other. Also a fifth concept was developed, where the anode and cathode flows are mixed and
no CO2 capture takes place. In the presented dissertation, a model with zero- and one-
dimensional (membrane model) computational parts was created to simulate and evaluate the
capability of the IGFC plant using different means to capture carbon dioxide.

The efficiency and net power of the different tail-gas concepts were compared, assuming an
IGFC plant with oxy-combustion for carbon dioxide capture as the baseline. The capture of
carbon dioxide proved to have an efficiency and probably an investment cost penalty. A
Carbon Tax (adopted in some countries like Sweden) proportional to the number of
kilograms of carbon dioxide released in the environment is necessary to make the carbon
dioxide capture economically feasible.

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PREFACE

This thesis report is a part of the Department of Energy National Energy Technology
laboratory and Colorado School of Mines project for ―Modeling, Analysis and Optimization
of IGFC Systems‖. The cooperation between The Colorado School of Mines and The School
for Renewable Science in Iceland allowed me, Raido Huberg, to participate in this project
and work on establishing the Solid Oxide Fuel Cell and the gas turbine (SOFC-GT) part of
the IGFC system.
The purpose of this thesis report was to quantitatively evaluate the SOFC-GT portion of the
IGFC system with different post-SOFC CO2 removal concepts. These were oxy-combustion
of the anode stream, H2-conducting membrane, O2-conducting membrane and also the mixing
of the anode and cathode stream, in which CO2 was vented. The goal of this thesis is to
evaluate what effect these different concepts have on the net-power production of the overall
system.
The project was done in The Colorado School of Mines in Golden, Colorado, USA; under the
supervision of Dr. Robert Braun, who was the project advisor. In addition there were two
academic advisors: Dr. David Dvorak, from the University of Maine, USA; and Dr.
Thorsteinn I. Sigfusson from the University of Iceland in Iceland.
In addition to the previous people mentioned the following people are acknowledged who
contributed to the thesis project:

Dr. Neal Sullivan, Colorado School of Mines

RES academic administration and faculty
Sigrún Lóa Kristjánsdóttir, RES
Students of RES
Students of RES
My family and friends

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TABLE OF CONTENTS

1 Introduction ........................................................................................................................ 1
1.1 Background Information ............................................................................................. 1
1.2 Recent Trends in Electrical Power Industry ................................................................ 3
1.2.1 CO2 taxation......................................................................................................... 3
1.3 Overview of IGCC Technology .................................................................................. 4
1.3.1 Large Commercial-Scale IGCC plants ................................................................ 5
1.4 Overview of SOFC technology ................................................................................... 7
1.4.1 Fuel Cell Systems ................................................................................................ 9
1.4.2 Thermal regulation of the fuel cell..................................................................... 10
1.5 Bottoming Cycles ...................................................................................................... 10
1.5.1 Regenerative Brayton Cycle .............................................................................. 10
1.5.2 Rankine Cycle .................................................................................................... 12
1.5.3 Combined Brayton-Rankine Cycle .................................................................... 13
1.5.4 Comparison of the different bottoming cycles................................................... 15
1.6 CO2 capture concepts ................................................................................................ 17
1.7 Membrane technologies ............................................................................................ 21
1.8 Aspen Plus [1.22] ...................................................................................................... 21
1.9 Objectives .................................................................................................................. 23
1.10 Methodology.......................................................................................................... 23
1.11 Chapter References ................................................................................................ 24
2 Modeling of various co2 capture strategies in the SOFC-gas turbine subsystem............. 26
2.1 SOFC modeling ......................................................................................................... 28
2.2 SOFC model verification .......................................................................................... 31
2.3 Modeling of air compression..................................................................................... 33
2.4 Modeling of CO2 preparation for sequestration ........................................................ 34
2.5 Gas turbine modeling ................................................................................................ 36
2.6 Steam cycle (Rankine cycle) modeling ..................................................................... 36
2.7 Modeling of H2-conducting membrane ..................................................................... 38
2.8 Modeling of O2-conducting membrane ..................................................................... 40
2.9 Parasitic losses from ASU ......................................................................................... 40
2.10 Modeling of oxy-combustion ................................................................................ 41
2.11 Modeling of H2-conducting membrane reactor with N2 as sweep gas .................. 42

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 2.12 Modeling of H2-conducting membrane reactor with air as sweep gas .................. 43
2.13 Modeling of O2-conducting membrane reactor ..................................................... 45
2.14 Net power output calculations ............................................................................... 46
2.15 Inputs to the model ................................................................................................ 46
2.16 Chapter References ................................................................................................ 47
3 Results .............................................................................................................................. 48
Appendix A ................................................................................................................................ 1
Methods to increase power .................................................................................................... 3
Methods to improve efficiency .............................................................................................. 4
Reverse Brayton cycle ........................................................................................................... 4
Description ............................................................................................................................. 5
Processes of the Rankine cycle .............................................................................................. 6
Real Rankine cycle (non-ideal) .............................................................................................. 6
Regenerative Rankine cycle ............................................................................................... 7
Appendix References ............................................................................................................. 8

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LIST OF FIGURES

Figure 1: Schematic of IGCC power plant [1.8] ....................................................................... 5

Figure 2: A integrated IGCC configuration [1.11] ................................................................... 7
Figure 3: Schematic of H2-O2 SOFC [1.13] .............................................................................. 8
Figure 4: Regenerative Brayton Cycle Fuel Cell Power System [1.12].................................. 11
Figure 5: Fuel Cell Rankine Cycle Arrangement .................................................................... 12
Figure 6: Rankine Cycle Thermodynamics.............................................................................. 13
Figure 7: Combined Brayton-Rankine Cycle Fuel Cell Power Generation System ................ 14
Figure 8: Combined Brayton-Rankine Cycle Thermodynamics .............................................. 14
Figure 9: SOFC-GT with pre-fuel cell CO2 capture [1.20] .................................................... 18
Figure 10: SOFC-GT with post-fuel cell hydrogen oxidation [1.20] ...................................... 19
Figure 11: SOFC-GT with OCM-afterburner [1.20] .............................................................. 19
Figure 12: Working principle of the WGSMR-afterburner [1.20] .......................................... 20
Figure 13: Hybrid cycle with WGSMR-afterburner [1.20] ..................................................... 20
Figure 14: Hydrogen transport through Pd membranes [1.21] .............................................. 21
Figure 15: Baseline IGFC System Configuration [2.1] .......................................................... 27
Figure 16: Fuel Cell model in Aspen Plus............................................................................... 28
Figure 17: Reactions in the Stoichiometric reactor (Aspen Plus) ........................................... 29
Figure 18: Specifications of the Stoichiometric reactor (Aspen Plus) .................................... 29
Figure 19: Fuel Cell model in Aspen Plus............................................................................... 32
Figure 20: Air compression for the fuel cell and for the ASU (Aspen Plus) ........................... 34
Figure 21: Specifications of the compressor model (Aspen Plus) ........................................... 34
Figure 22: Preparation of CO2 for storage (Aspen Plus)........................................................ 35
Figure 23: Gas turbine model (Aspen Plus) ............................................................................ 36
Figure 24: Gas turbine model specifications (Aspen Plus) ..................................................... 36
Figure 25: HRSG model (Aspen Plus) ..................................................................................... 37
Figure 26: H2 conducting membrane ...................................................................................... 39
Figure 27: O2 conducting membrane (Aspen Plus) ................................................................. 40
Figure 28: Oxy-combustor ....................................................................................................... 41
Figure 29: Concept of H2-conducting membrane reactor with N2 as sweep gas .................... 42
Figure 30: Concept of H2-conducting membrane reactor with air as sweep gas ................... 43
Figure 31: Concept of O2-conducting membrane reactor ....................................................... 45
Figure 32: Flow sheet of IGFC (CO2 capture)........................................................................ 48
Figure 33: Flow sheet of IGFC (venting of CO2) .................................................................... 49

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Figure 34: H2 recovery [%] ..................................................................................................... 50
Figure 35: CO2 fraction in the exhaust.................................................................................... 52
Figure 36: Net power production ............................................................................................ 52
Figure 37: Power production breakdown................................................................................ 53
Figure 38: Power consumption breakdown ............................................................................. 53
Figure 39: Efficiency breakdown............................................................................................. 54
Figure 40: Idealized Brayton Cycle [1.15]................................................................................ 2
Figure 41: Brayton Cycle (Gas Turbune) Efficiency ................................................................. 2
Figure 42: Brayton Cycle (Gas Turbine) Specific Power Output ............................................. 3
Figure 43: Engine with a Rankine cycle [1.18] ......................................................................... 5
Figure 44: T-s diagram of a typical Ramkine cycle operating between pressures of 0,06 bar
and 50 bar .................................................................................................................................. 6
Figure 45: Rankine cycle with superheat .................................................................................. 7
Figure 46: Regenerative Rankine cycle ..................................................................................... 8

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LIST OF TABLES

Table 1: Estimated emissions of CO2 from power generation using fossil fuels [1.6] .............. 2
Table 2: Stream properties of syngas after cleaning processes from a Destec entrained bed
gasifier [1.12] ............................................................................................................................ 4
Table 3: Comparison of efficiencies [1.12] ............................................................................... 5
Table 4: Table of Commercial-Scale coal/petroleum coke based IGCC power plants [1.5] .... 6
Table 5: Performance Computations for Various High Temperature Fuel Cell (SOFC) Heat
Recovery Arrangements [1.12] ................................................................................................ 15
Table 6: Input and comparison of anode outputs of the two SOFC models ............................ 33
Table 7: Flows of the cathode .................................................................................................. 33
Table 8: Heat duties and PDC................................................................................................... 33
Table 9: Content and other parameters of syngas and air fed to the system........................... 46
Table 10: Split fraction of cathode air recycled ...................................................................... 50
Table 11: Properties of to the gas turbine ............................................................................... 51
Table 12: CO2 for sequestration .............................................................................................. 51
Table 13: Overall efficiency [%] ............................................................................................. 54

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1 INTRODUCTION

Fuel Cell technologies are maturing and currently in a pre-commercial stage. The main
advantage of fuel cells is their ability to perform energy conversions with high efficiencies;
extending the limited amount of resources and decreasing energy-related emissions. In
addition to the higher efficiency fuel cells are scalable, making them suitable for a wide
variety of applications, from powering a mobile phone to power plants.
Fuel Cells have been studied extensively, but mainly from the electrochemical and materials
viewpoint. There is a lack of system level research especially for Integrated Gasification Fuel
Cell (IGFC) System applications with CO2 capture. When applying Fuel Cells in coal fired
power plants with the Integrated Gasification Combined Cycles (IGCC), high-energy
conversion efficiencies can be achieved. This can lead to higher maximum system efficiency
and cost effectiveness. In order to reach these goals, methodologies for system-level optimal
design must be developed.
The goal of this thesis report is to model and evaluate an Integrated Gasification Fuel Cell
(IGFC) combined cycle power system, which uses syngas from a coal gasification plant,
which captures and removes CO2 for sequestration. The focus of this work is on quantitative
evaluation of various CO2 capture strategies in the SOFC-gas turbine subsystem.
Chapter one gives a background overview for the IGFC, to explain the project. A summary of
the problem is presented (climate change caused by the CO2 emissions and one of the tools to
tackle that- the carbon tax- is explained). A short overview of integrated gasification
combined cycle (IGCC) and SOFC technology is given, and the concepts of different CO2
capture technologies are discussed. Various bottoming cycles are presented, and in addition,
background information about other important parts of the systems is given.
In chapter two the main focus is the description of the model. Emphasis is given to how the
model was created for the thesis, what assumptions were made, and in addition it is described
how the SOFC model was verified.
In chapter three the results of the model are presented. In addition the results are discussed
and possible improvements are suggested.

1.1 Background Information

Global climate change concerns associated with increasing anthropogenic CO2 concentration
in the atmosphere is providing the impetus for limiting green house gas emissions from
power generation sources. One way to accomplish a reduction in greenhouse gases is through
the introduction of a carbon tax. This will make coal fired power plants, the source of a
significant amount of CO2 and electric power, less competitive.
About 80% of the energy used world-wide comes from fossil fuels, and this is expected to
increase until at least year 2020. The combustion of fossil fuels leads to emissions of CO2
into the atmosphere, which is believed to contribute to undesired global warming.
The capture of CO2 is easier from large stationary fossil fuel based power generation than in
automotive applications, where emissions come from an enormous quantity of small, mobile

1
units. The current estimated, annual emissions of CO2 world-wide from power plants using
fossil fuels are shown in Table 1 [1.6]

Plant Type Mt CO2/year (2000)

Coal 6276
Oil 992
Gas 1689
Total 8958
Table 1: Estimated emissions of CO2 from power generation using fossil fuels [1.6]

The total recoverable reserves of coal around the world are estimated at 930 billion tons -
reflecting in 2006 a reserves-to-production ratio of 143 [1.1]. Compared to other fossil fuels
like oil and gas the reserves of coal are much more abundant and the prices are far less
volatile compared to the prices of oil and gas.
41 percent of electricity is being produced in coal fired power plants and this number is
predicted to increase slightly [1.2]. This growth is largely due to the rapid development of
China where 70% of electricity is produced in coal fired power plants [1.7]. Coal power
plants are the least carbon efficient power stations in terms of the level of carbon dioxide
produced per unit of electricity generated [1.4].
Coal is, and will be in the future, a key ingredient in the total energy mix but it is also a major
source of carbon dioxide, and in order to use these reserves without causing irreversible
climate change the carbon has to be captured.
There are two main ways to decrease the carbon dioxide emissions per MW of power
produced:
1. Increasing the overall efficiency of the plant
2. Capturing the CO2 from the exhaust
In this particular study both are applied. The efficiency of the plant will be increased by
applying gasifiers, a combined Brayton-Rankine cycle and an SOFC. The CO2 from the
exhaust can be captured in many ways; here oxy-combustion and different membranes are
used (H2- and O2-conducting membranes).
Solid oxide fuel cells would be more suitable for integration to power cycles, because of their
higher operating temperature, than some other fuel cells, proton exchange membranes (PEM)
for example. One question in the design of IGFC power plants is how to couple coal
gasification with the SOFC-gas turbine system. The SOFC (800-1000°C) and the gasifier
(1200°C) operate at different temperatures and before the syngas from the gasifier enters the
SOFC it goes through several cleaning processes during which the temperature is altered.
Thermal gradients within the ceramic SOFC stack must be relatively small (~150°C) to
minimize thermally-induced stress. In addition the cell may be poisoned by some of the
components (e.g., H2S) in the syngas, resulting in a fast and irreversible degradation in
performance.
Currently, CO2 removal is performed with a CO2-selective solvent at around 50°C. This
makes thermal integration more complex and diminishes the efficiency. Also, steam is

2
needed for desorption processes. This results in a high price per ton of CO2 removed. The
emerging high temperature technology of membrane reactors is expected to offer a higher
efficiency during gas separation.

1.2 Recent Trends in Electrical Power Industry

It has been realized that human caused CO2 emissions may increase the earth’s average
surface temperature, which affects the climate. In order to prevent this from happening, CO2
emissions have to be decrease significantly. One possible tool to accomplish that is the
introduction of a carbon tax. This should make the more polluting technologies more
expensive and make the less polluting technologies, which are more expensive, more
attractive. In addition this would motivate the coal fired power plants, for example, to do
something to reduce their CO2 emissions. If it is cheaper to capture the CO2 than to pay the
CO2 tax, the plants will work to implement coal capture technologies.
Recent trends in the world show that new coal fired power plants are built rapidly, especially
in China and India, where the economy is growing very fast. The reason for choosing coal is
that it is a cheap and abundant energy source. And developing countries will use coal, and are
already using it, extensively to meet the increasing demand for power.

1.2.1 CO2 taxation

A carbon tax is a tax on the carbon content of fuels — effectively a tax on the carbon dioxide
emissions from burning fossil fuels.

Carbon atoms are present in every fossil fuel — coal, oil and gas. When a fossil fuel is
burned the majority of the carbon is converted into CO2. Currently all carbon dioxide that is
produced is vented to the atmosphere and remains there for some 20 years, trapping heat re-
radiated from the Earth’s surface and causing the so-called greenhouse effect, which is
believed to be the main contributor to climate change.

A carbon tax (or CO2 tax) would motivate power plants and companies to decrease their
carbon dioxide emissions. There are several ways to decrease the carbon dioxide emissions
per MW of power produced:

1. More efficient energy conversion

2. Carbon capture and sequestration
3. The use of non-carbon based energy resources (wind, solar, geothermal etc)

The emissions from coal fired power plants are the ―dirtiest‖. This means that compared to
other fossil fuel technologies (gas turbine), significantly more CO2 is being emitted per MW
of power produced. At present there is very little taxation of carbon, thus the prices, for
example of electricity and gasoline, do not include the costs of climate change. A carbon tax
is considered an essential tool for taking action against climate change.

The reason for a carbon tax is simple: the levels of CO2 in the Earth’s atmosphere are
destabilizing established climate patterns and threatening ecosystems. Large and rapid
reductions in the world’s carbon emissions are essential to preventing irreversible climate
change and the resulting severe weather events, flooding of coastal areas etc.

3
So far carbon taxes have not been implemented widely. The first country to have a carbon tax
was Finland in 1991 [1.10]. Other countries have since followed suit. In the EU the carbon
tax is in the transition phase in order to prepare the energy sector.

1.3 Overview of IGCC Technology

The gasification of coal has been around since the end of the 18th century [1.11]. It was used
to produce town gas for lighting and cooking until being replaced by electricity and natural
gas by the beginning of the 19th century.. The main advantages of gasification are the
flexibility in feedstock (coal, biomass, coke etc) and the products (electricity, chemicals,
steam etc). Gasification of abundant coal can be an alternative to commercial coal based
combustion systems and can be more efficient and environmental friendly.
The first commercial IGCC plants in the U.S. were put into service through the DOE’s
cooperative Clean Coal Technology (CCT) program, and have proven to be capable of
exceeding even the most stringent emissions regulations currently applicable to coal-fueled
power plants. Very low levels of pollutant air emissions (NOx, SOx, CO, PM10) have been
achieved comparing to any other coal fueled power plant in the world. But IGCC plants are
considered to be a first-of-its-kind technology and it will take time for IGCC´s to experience
wide spread use.

The heart of any gasification-based system is the gasifier, which can process a wide variety of
feedstocks into gaseous products (mostly CO and H2) at high temperature and (usually)
elevated pressure in the presence of oxygen and steam. In a gasifier the feedstock is not
completely burned but only partially oxidized, and as a result the product, the syngas,
consists mainly of H2 and CO (Table 2). The same syngas was used in the developed model,
which is described later in this report.

Temp Pressure CH4 CO CO2 H2 H2O H2S

[°C] [atm] [%] [%] [%] [%] [%] [%]
399 15 0,3 42,3 9,6 35,8 10,3 trace
Table 2: Stream properties of syngas after cleaning processes from a Destec entrained bed
gasifier [1.12]

The content of the cleaned syngas is suitable to feed directly to an SOFC. At this point the
temperature of the gas has to higher at the anode inlet, in this study it was chosen to be
650°C.

IGCC technology is one of the most efficient and cleanest of available technologies for fossil-
based power generation. The core process, gasification, is a commercially proven technology
that has been deployed on a worldwide basis for the refining, chemical, and power industries.
There are at least 163 commercial gasification plants in operation, under construction, or in
planning and design stages around the world. The future holds that more gasification plants
are being planned for power production.

Although there are numerous gasifiers operating commercially worldwide, there is far less
experience with commercial operation of IGCC plants. In 2002 there were eleven major
IGCC plants operating internationally that use coal, petroleum coke, and refinery residue as
feedstock.

4
 Figure 1: Schematic of IGCC power plant [1.8]

The main technology drivers for gasification are the feedstock and product flexibility,
because all carbon-containing materials can be readily gasified and turned into clean syngas.
In addition the high-pressure operation makes the products from the gasifier more amenable
to cleaning. High-pressure also gives smaller volumes of flow with higher contents of species
for processing. In contrast, the volume of flue gas from a combustion-based power plant is
40-60 times greater.

Advantages compared to other coal combustion technologies include:

1. Less CO2 per unit of energy because of higher overall efficiency
2. Discharge of solid waste/by-products and wastewater is lower
3. Recovery of high-value-added by-products or co-products[1.12]

IGCC Plant PC Plant FBC Plant

Thermal Efficiency, % 38-50 34-42 36-45
(HHV Basis)
*PC – pulverized coal, FBC – fluidized bed combustion
Table 3: Comparison of efficiencies [1.12]

As we can see from table 3 the efficiency of the IGCC is comparable with the conventional
technologies. Nevertheless IGCC offers some additional advantages and makes IGCC the
technology of choice.

1.3.1 Large Commercial-Scale IGCC plants

Experience in operating IGCC has been gained through several commercial-scale
demonstration power plants in the United States and in Europe.

5
 PLANT NAME PLANT OUTPUT FEEDSTOCK GASIFIER POWER OPERATION
LOCATION (MWe) TYPE ISLAND STATUS
Texaco Cool Daggett, CA, 125 Bituminous Texaco CCGT-GE 1984-1988
Water USA Coal 7FE
(1000 tpd)
Dow Paquemine, 160 Subbituminous E-Gas CCGT- 1987-1995
Chemical/Destec LA, USA Coal (formerly Westinghouse
LGTI Project (2200 tpd) Destec) 501
Tampa Electric Polk County, 250 Bituminous Chevron CCGT-GE 1996-Present
Polk Plant FL, USA Coal Texaco 7FA
(2200 tpd)
PSI West Terre 262 Bituminous E-Gas CCGT-GE 1995-Present
Energy/Global Haute, IN, Coal and (formerly 7FA
Energy Wabash USA Petroleum Destec)
River Plant Coke
(2544 tpd)
NUON/Demkolec/ Buggenum, 253 Bituminous Shell CCGT- 1994-Present
Willem- The Coal Siemens
Alexander Netherlands V94.2
ELCOGAS/ Puertollano, 298 Coal and Prenflo CCGT- 1998-Present
Puertollano Spain Petroleum Siemens
Coke V94.3
(2500 tpd)
CCGT-Combined Cycle Gas Turbine, tpd-short tons per day
Table 4: Table of Commercial-Scale coal/petroleum coke based IGCC power plants [1.5]

The first two U.S. plants listed in the table, Cool Water and LGTI (Louisiana Gasification
Technology Inc Project), were important first-generation, large-scale IGCC projects that
demonstrated the major IGCC characteristics of low emissions and stable integrated control
of the gasification process with a combined cycle in a power utility setting. Both of these
projects were funded with guaranteed product price support and were shut down once the
duration of the price guarantee period expired.

The rest of the plants listed, are second-generation, which is the current generation. These
IGCC systems have been improved according to what was learned from the initial plants. The
plants in Europe make use of different gasifier designs and turbine vendors.

Each of the four major commercial-sized, coal/coke-based IGCC demonstration plants

currently in operation use a different gasification technology, gas cooling and gas cleanup
arrangement, and integration scheme between the plant units. All of the current coal based
plants integrate the steam systems of the gasification and power block sections.

The major difference between the plants in Europe and in the US is the degree of integration
between the gas turbine and the air separation unit (ASU). The different degree of integration
is derived from the different objectives of the plants. In Europe the main goal is to increase
the efficiency because of the higher prices of fuel, while in the US the main objective is the
availability of the technology.

The European demonstration plants are both highly integrated designs with all the air for the
ASU being taken as a bleed of extraction air from the combustion turbine compressor. In
contrast, the operating U.S. plants are less integrated, and the ASUs have their own separate
air compressors. A more tightly integrated ASU design, like that found in the European
plants, results in higher plant efficiency. However, there is a potential loss of plant
availability and operating controllability for the highly integrated system, and the higher
degree of integration requires a longer start-up time. Fig 2 presents a block flow diagram that
identifies the difference between the integration schemes.

6
 Figure 2: A integrated IGCC configuration [1.11]

In Europe efficiency is a major concern that has led to capital investment for the tightly
integrated plant because of the high prices of fuel. In the U.S., fuel prices are lower and
availability is a more important factor than efficiency. It is now the general consensus among
IGCC plant designers that the preferred design is an intermediate approach; one in which the
ASU derives part of its air supply from the gas turbine compressor and part from a separate
dedicated compressor. This provides the necessary flexibility for quicker start up, less usage
of expensive secondary fuels, and an auxiliary power load intermediate between the two
options.

1.4 Overview of SOFC technology

Solid oxide fuel cells (SOFCs) have a solid electrolyte, non-porous metal oxide, most
commonly it is made of yttria-stabilized zirconia (YSZ) which is an oxygen ion (oxygen
vacancy) conductor. Here the O2- is the mobile conductor and the anode and cathode
reactions are as follows:

Anode: H2+O2-→H2O+2e-

Cathode: 1/2O2+2e-→O2-

In the case of an SOFC, water is produced on the anode, rather than at the cathode side, as in
a proton exchange membrane fuel cell (PEMFC).

The cell operates at 600-1000 °C. The reason for this high operating temperature is that at
lower temperatures the solid electrolyte material does not conduct oxygen ions, or if it does it

7
happens at a low rate. The anode and cathode materials are different. Typically, the anode is a
Ni-ZrO2 cermet (must withstand highly reducing high-temperature environment) and the
cathode (must withstand highly oxidizing high-temperature environment) is Sr-doped
LaMnO3. There is no liquid electrolyte with its attendant material corrosion or electrolyte
management problems. The cell is constructed with two porous electrodes that sandwich an
electrolyte. Air flows along the cathode. When an oxygen molecule contacts the
cathode/electrolyte interface, it acquires electrons from the cathode. The oxygen ions diffuse
into the electrolyte material and migrate to the other side of the cell where they contact the
anode. The oxygen ions encounter the fuel at the anode/electrolyte interface and react
catalytically, giving off water, carbon dioxide, heat, and electrons. The electrons transport
through the external circuit, providing electrical energy.

Figure 3: Schematic of H2-O2 SOFC. A solid state ceramic is the electrolyte. A nickel-YSZ
cermet anode and a mixed conducting ceramic cathode provide the required thermal,
mechanical, and catalytic properties at high SOFC operating temperatures. Water is
produced at the anode [1.13]

The high temperature of the SOFC, however, places stringent requirements on its materials.
The development of suitable low cost materials and the low-cost fabrication of ceramic
structures are presently the key technical challenges facing SOFCs [1.12]. On the other hand
their high operating temperature makes them more suitable for integration with Brayton,
Rankine or Brayton-Rankine cycles. Following are listed the challenges and advantages of
the high-temperature operation:

Advantages [1.14]:
Fuel flexibility (internal reforming could simplify the system)
Non-precious metal catalyst
High quality waste heat for cogeneration applications (overall system efficiency can
reach 90%)
Solid electrolyte
Relatively high power density
High efficiency (about 50-60%)

8
Challenges:
Significant high-temperature materials issues
Sealing issues
Relatively expensive components/fabrication
Very long start-up period
Conventional materials are easily fouled by sulphur

One possible way to overcome some of these challenges is an intermediate-temperature (400-

700°C) SOFC. This could help reduce the cost of the fuel cell by requiring less-expensive
materials and fabrication methods.

Solid oxide fuel cells (SOFC) allow the conversion of a wide range of fuels, including
various hydrocarbon fuels. The relatively high operating temperature allows for highly
efficient conversion to power, internal reforming, and high quality by-product heat for
cogeneration or for use in a bottoming cycle. Indeed, both simple-cycle and hybrid SOFC
systems have demonstrated among the highest efficiencies of any power generation system,
combined with minimal air pollutant emissions and low greenhouse gas emissions. These
exhibitions have made SOFC an attractive technology for stationary power generation in the
2 kW to100s MW capacity range.

1.4.1 Fuel Cell Systems

Fuel cells are not 100% efficient and there is heat produced which must be removed. The
excess heat can be utilized by integrating the SOFC into an energy system; there the heat can
be used in the following ways:

1. Production of steam
2. Production of hot water
3. Converted to electricity via a gas turbine or steam bottoming cycle

The production of steam and/or hot water is called cogeneration. Cogeneration is applied
when the rejected heat has low temperatures. For example, the steam produced by low
temperature fuel cells, PEMFC or phosphoric acid fuel cell (PAFC), which operate at 90-
210°C [1.14], will not have a very high pressure and this is not very suitable for a steam
bottoming cycle. SOFC on the other hand, which operate at temperatures from 400 to
1000°C, are capable of producing steam in excess of 540°C [1.12]. But if the amount of heat
is relatively small it is not reasonable to use it in a bottoming cycle, but it is reasonable to
produce hot water for example.

Another option is to use some bottoming cycle for utilizing the excess heat. The bottoming
cycle options are explained in chapter 1.5. Using a bottoming cycle makes sense when there
is a significant amount of rejected heat available at high-temperatures. Adding a bottoming
cycle can significantly increase the efficiency of electric generation. When the heat is
accumulated in a high-pressure and temperature gas stream then a gas turbine potentially
followed by a heat recovery steam generator and steam turbine should be considered. But if
the hot gas stream is at low pressure, then a steam bottoming cycle would be more logical.

In system design and optimization one must consider many questions, issues, and trade-offs.
For example having maximal electrical output may lead to lower overall efficiency and /or

9
higher operating and investment costs. The optimization depends on the objectives of the
specific system. The objectives can include the following, individually or combined: power
output, overall weight, fuel basis, emissions, cost etc. Site-and-application-specific criteria
and conditions may strongly influence the cycle design criteria and resulting design.

1.4.2 Thermal regulation of the fuel cell

An significant amount of heat has to be removed from the fuel cell stack. Heat removal from
fuel cells can be accomplished:

Directly through the flow of reactants to and products from them.

Indirectly through heat transfer surfaces in contact with the cell or included within a
battery.

Some elements in the fuel cell system have a fixed range of operating temperature, thus it is
necessary to remove heat in such a manner that temperatures are being kept within a certain
range. If the heat is removed directly, by reactant flows, the temperatures are regulated by the
quantity of flow of the reactants (usually air). In addition the cathode stream can be recycled
to achieve the desired inlet temperatures of the air stream; this is done to avoid the use of
excess energy for pre-heating the air. The recycling of the anode stream (fuel stream) is
possible as well, but in the model for this thesis report the recycling of the cathode stream
was used.

If heat is removed from the fuel cell indirectly, then the flow and temperature of the coolant
stream can be selected somewhat independent of the cell operating temperature.

If air flow is chosen for cell cooling the air flow will be increased significantly, by a factor of
4-8 above that required for oxidation of the fuel. This will also lead to increased power
consumed by the system because more air needs to be compressed. It is suggested to compare
the power demand of direct and indirect cooling of the fuel cell stack. As it turns out, the
optimization of the amount of air compressed for the system plays a big role on the overall
power output.

1.5 Bottoming Cycles

Basically there are three different kinds of bottoming cycles to choose from:
Regenerative Brayton Cycle
Combined Brayton-Rankine Cycle
Rankine Cycle

In the next chapters these different bottoming cycles are described and compared with each
other. All these bottoming cycles use methane (CH4) as fuel.

1.5.1 Regenerative Brayton Cycle

The regenerative Brayton cycle (Figure 4) shows a gas turbine compressor for the air (1) flow
to the cell. The flow (2) is then passed through a countercurrent, recuperative heat exchanger
to recover heat from the combustion product gases leaving the gas turbine (6). The air (3) and
the fuel streams then pass into the cathode and anode compartments of the fuel cell(s). The
air (4) and fuel streams leaving the cell(s) enter the combustor where they mix and the
10
residual fuel burns. The combustion products (5) enter the turbine, expand, and generate
additional power. The turbine exhaust gases (6) pass through the recuperative exchanger to
the stack. [1.12]

In addition the T-s diagram is presented in Figure 4. All the processes in different parts of
the system are described through the T-s diagram.

The most significant variables characterizing the cycle are:

the fuel cell operating temperature range

temperature and pressure at the gas turbine expander inlet

These variables are related to other operating variables in the system. Like the fuel utilization,
it is not optimal to react all the fuel in the fuel cell. The previous statement can be explained
as follows; the fuel cell operating temperature range is around 800°C and by burning the
unreacted fuel in a combustor the inlet temperature of the gas turbine can be raised.

Figure 4: Regenerative Brayton Cycle Fuel Cell Power System [1.12]

Some of the following aspects have to be kept in mind by modeling this cycle:
efficiency of the gas compressors
efficiency of the turbine expander
efficiency of the fuel cell
pressure losses as the gases flow through the system
the temperature differences
the difference in heat capacities of the streams flowing through the recuperative heat
exchanger

11
 aspects of the fuel cell operation (the need for fuel reforming, recycle products to get
necessary inlet temperatures and to avoid carbon composition)

Calculations [1.12] have shown that the efficiency of the overall power system, work output
divided by the lower heating value (LHV) of the CH4 fuel, was increased from 57 percent for
the fuel cell alone to 82 percent for the overall system with a 15°C difference in the
recuperative exchanger and to 76 percent for a 45°C difference.

1.5.2 Rankine Cycle

The fuel cell Rankine cycle arrangement in Figure 5 employs a heat recovery steam generator
operating on the exhaust combustion product stream from the fuel cell and combustor (15) at
atmospheric pressure. This exhaust stream (7) first provides the heat required to preheat and
reform the CH4 fuel, providing CO and H2 at temperature to the fuel cell. Partially combusted
fuel from the cell (5) is recycled to provide the H2O required for reforming the fuel. Depleted
air from the cell exhaust is recycled (12) to the air feed stream (10) to raise its temperature to
the desired value at the cell inlet (11). The flow sheet can be seen in Figure 5 and the T - S
diagram for the Rankine cycle is illustrated in Figure 7 [1.12]. The T – S diagram describes
the Rankine cycle.

Figure 5: Fuel Cell Rankine Cycle Arrangement

The efficiency of the overall system is increased from 57 percent for the fuel cell alone to 72
percent for the overall system.

12
 Figure 6: Rankine Cycle Thermodynamics

1.5.3 Combined Brayton-Rankine Cycle

The combined Brayton-Rankine cycle, Figure 7, again shows the gas turbine compressor for
the air flow to the cell (2). This flow passes through a heat exchanger in direct contact with
the cell; it removes the heat produced in cell operation and maintains cell operation at
constant temperature. The air (3) and fuel streams then pass into the cathode and anode
compartments of the fuel cell. The separate streams leaving the cell enter the combustor and
then the gas turbine (5). The turbine exhaust (6) flows to the heat recovery steam generator
and then to the stack (7). The steam produced (V) drives the steam turbine. It is then
condensed (I) and pumped (II) back to the steam generator [1.12].

The desired fuel cell operating temperature is achieved by changing the air/fuel ratio entering
the fuel cell; the same was done in the model created for this thesis report, where the air flow
was adjusted according to the cooling necessity. The gas turbine nozzle inlet temperature
(NIT) and pressure ratios (PR) are achieved by the selected fraction of the CH4 fuel
consumed. These are selected to correspond with those of a conventional, large-scale, utility
gas turbine.

The T-s diagrams of both the Brayton and the Rankine cycles are illustrated in Figure 8. The
pressure and temperature increase during fuel and air compression (1-2) in this combined
cycle will be significantly greater than in the regenerative Brayton cycle. The heating of the
air and fuel (2-3), the operation of the fuel cell (3-4), and the burning of the residual fuel (4-
5) are assumed to occur at constant pressure. The expansion of the combustion product gases
in the gas turbine (5-6) is represented as an adiabatic, reversible (constant S) process. Next,
heat is removed from these gases (6-7) at nearly constant pressure in the heat recovery steam
generator; and they pass out through the stack (7-1).

13
 Figure 7: Combined Brayton-Rankine Cycle Fuel Cell Power Generation System

Figure 8: Combined Brayton-Rankine Cycle Thermodynamics

One thermodynamic advantage the Rankine bottoming cycle offers is the lowered
temperature of heat rejection in the steam condenser, from the overall combined cycles.

14
The efficiency of the overall system is increased from 57 percent for the fuel cell alone to 75
percent for the overall system.

The link between the Brayton and the Rankine cycles is a heat recovery steam generator
(HRSG). The heat of the used gas from the Brayton cycle has to be transferred to the water-
steam inside the HRSG. The heat in the HRSG is utilized (Figure 8 Rankine cycle) in the
economizer evaporator and superheater.

1.5.4 Comparison of the different bottoming cycles

The regenerative Brayton cycle heat-fuel recovery arrangement is the simplest approach to
heat recovery compared to the Brayton-Rankine combined cycle and the Rankine cycle.

The Rankine cycle heat-fuel recovery arrangement is less complex but also less efficient than
the combined Brayton-Rankine cycle approach, and more complex and less efficient than the
regenerative Brayton approach. On the positive side there is no need for a large, high
temperature gas to gas heat exchanger and can provide a source of steam.

The combined Brayton-Rankine cycle heat-fuel recovery arrangement is significantly more

complex and less efficient than the simple regenerative Brayton cycle approach. It does,
however, eliminate the requirement for a large, high temperature gas to gas heat exchanger.

The effectiveness of the regenerative Brayton cycle performance will depend on the
efficiency of the fuel cell, compressor, and turbine units; the pressure loss of gases flowing
through the system; the approach temperatures reached in the recuperative exchanger; and,
most importantly, the cost of the overall system.

The combined Brayton-Rankine cycle depends on both the fuel cell and the gas turbine
components for conversion of the fuel and thus for its overall efficiency. The extent of
conversion of the fuel occurring in the fuel cell increases as the cell operating temperature
and the range of coolant temperature rise increase.

The fuel cell Rankine cycle arrangement has been selected so that all fuel preheating and
reforming are carried out external to the cell and air preheating is accomplished by mixing
with recycled depleted air. The air feed flow is adjusted so that no heat transfer is required in
the cell or from the recycled air. Consequently, the internal fuel cell structure is greatly
simplified, and the requirement for a heat exchanger in the recycled air stream is eliminated.
[1.12]
In table 5 the efficiencies of the different heat recovery arrangements are presented, in
addition to the efficiencies of the different power generating parts.

Heat Recovery Arrangement Work Output, %

Overall System
Fuel Gas Steam
Cell Turbine Turbine Eff., %
Regenerative Brayton Cycle 69,3 30,7 n/a 82,1
Regenerative Brayton Cycle 74,5 25,5 76,3
Combined Brayton-Rankine Cycle 75,3 10,3 14,3 75,6
Rankine Cycle 79,1 20,9 72,4
PR=pressure ratio of gas turbine, NIT=nozzle inlet temperature of the turbine expander
Table 5: Performance Computations for Various High Temperature Fuel Cell (SOFC) Heat
Recovery Arrangements [1.12]
15
General Conditions:
SOFC
Operating temperature, 925-1050 °C
Fuel cell output: 60% of theoretical maximum from CH4 fuel
Gas turbine compressor efficiencies: 83, 89%
Steam turbine efficiency: 90%

All three approaches are more suitable for application to high temperature fuel cells, solid
oxide fuel cell or molten carbonate fuel cell. Applying them for lower temperature fuel cells,
PEMFC or PAFC, will severely limit the power generation and make it impractical.

All three of the heat recovery arrangements have calculated overall efficiencies greater that
70 percent as indicated in Table 5. None have been optimized in any sense - in terms of
efficiency, capital and operating costs, maintainability or availability. All the arrangements
have their advantages and disadvantages, which are described further in subsequent
paragraphs.

It seems that the regenerative Brayton cycle is the simplest of them and has highest potential
overall efficiency over the combined Brayton-Rankine and Rankine cycle approaches.
However in this thesis report the combined Brayton-Rankine cycle was used; the reason for
this was to get an idea of how much electric power could be produced.

Advantages and disadvantages of various fuel cell bottoming cycles [1.12]

Regenerative Brayton
Advantages:
Simple cycle arrangement, minimum number of components.
Relatively low compressor and turbine pressure ratio, simple machines.
Relatively low fuel cell operating pressure, avoiding the problems caused by
anode/cathode pressure differential and high pressure housing and piping.
Relatively low turbine inlet temperatures, perhaps 1065°C for solid oxide and 787°C
for molten carbonate fuel cell systems. Turbine rotor blade cooling may not be
required.
Relatively simple heat removal arrangements in fuel cells, accomplished by excess air
flow. No internal heat transfer surface required for heat removal.
Fuel conversion in cells maximized, taking full advantage of fuel cell efficiency.
Adaptability to small scale power generation systems.
Disadvantages:
Tailoring of compressor and turbine equipment to fuel cell temperature and cycle
operating pressure required. (It is not clear to what extent available engine
supercharging and industrial compressor and turbine equipment can be adapted to this
application.)
Large gas to gas heat exchanger for high temperature heat recuperation required.
Efficiency and work output of the cycle sensitive to cell, compressor, and turbine
efficiencies; pressure losses; and temperature differentials.

16
Combined Brayton-Rankine
Advantages:
Integrated plant and equipment available for adaptation to fuel cell heat recovery.
High efficiency system for heat recovery.
Disadvantages:
Complex, multi component, large scale system for heat recovery.
Adaptation of existing gas turbine required to provide for air take off and return of hot
depleted air and partially burned fuel.
High pressure operation of the bulky fuel cell system required.
Precise balancing of anode and cathode pressures required to prevent rupture of fuel
cell electrolyte.
Indirect heat removal required from fuel cells with compressed air, initially at low
temperature, to enable significant conversion of the fuel flow in the cells.

Rankine
Advantages:
Ambient pressure operation within the fuel cell.
Heat recovery in a boiler, avoiding the high temperature gas to gas exchanger of a
regenerative Brayton cycle.
No gas turbine required, only fans for air and exhaust product gas flow.
Steam available for cogeneration applications requiring heat.
Disadvantages:
Inherently lower efficiency than regenerative Brayton and combined Brayton-Rankine
cycles.
Requirement for cooling and feed water.
Greater complexity than regenerative Brayton cycle arrangement.

1.6 CO2 capture concepts

For CO2 capture several technologies like gas turbines, membranes and solid oxide fuel cells
can be used. Commercially available CO2 capture technologies for power conversion are in
general post-combustion technologies; i.e. the CO2 is captured from the flue gases after the
conversion of fuel into power. Post-combustion CO2 capture, however, results in a significant
drop in efficiency and an increase in plant investment and operating costs. Typically, CO2
capture with an amine absorption/desorption unit in a gas fired combined cycle results in an
efficiency drop of 9%-points (steam is needed for the desorption process), an investment
increase of more than 50% and a rise in cost per CO2 captured. For coal fired power plants
the penalties are even bigger. If the CO2 stream is diluted (mainly with N2) the removal of
CO2 is much more complex.
In order to make CO2 capture feasible the efficiency and financial penalties have to be
reduced significantly. To achieve this new concepts are required. These concepts will have to
make use of one or probably a combination of the technologies (gas turbines, membranes and
fuel cells) mentioned above. In this work all these technologies are put together and different
tail-gas concepts are evaluated.
The gas turbine is a well established technology mostly used to utilize natural gas. It can also
be implemented to gasification-based power plants and used to burn H2. However, a physical
or chemical absorption step is still required to separate the CO2 from the hydrogen (separator
on Figure 9).
17
Membranes may offer the potential for high-efficiency gas separation. Ceramic and metallic
membranes are in focus because of their high operating temperature and pressure.

Membranes can be used not only as separation devices but possibly also as chemical reactors
and may also act as heat exchangers; in this case they are called membrane reactors (MR).
Membrane activity supports chemical reactions. For example a water-gas shift reaction is
promoted when one of the products, hydrogen, is withdrawn constantly.

A drawback in membrane applications is that a difference in the partial pressure is required

for species to permeate through the membrane and thus 100% recovery of hydrogen, for
example from syngas, is not possible. To integrate a membrane and reactor into one device,
syngas from a coal gasifier can be converted to hydrogen using a water-gas shift membrane
reactor (WGSMR) which is then used for fuelling a gas turbine. A more integrated approach
is also possible: integrating reforming, shift and membrane separation in one module, which
is then placed in a gas turbine cycle.

Fuel cells, of which the SOFC is the most relevant to this study, offer high-efficiency power
production. A special property of the SOFC, which makes it attractive for CO2 separation, is
that the fuel conversion takes place without the dilution of CO2 with nitrogen and a high CO2
content stream is formed. In addition to the high efficiency of the SOFC (50-60%), an
additional gain in efficiency can be achieved by combining the SOFC with a gas turbine to
form a hybrid system. Numerous approaches to achieving this result are possible.

A pre-fuel cell CO2 capture concept can be seen in figure 9. If we have syngas coming from a
gasifier as fuel, the reforming step can be left out. If we want to separate the CO2 and H2
before the SOFC, the entire CO in the syngas has to be shifted in the water-gas shift reaction.
In this case a stream of H2 and H2O enters the anode of the SOFC. The use of an amine based
CO2 removal is necessary. After separation the CO2 can be compressed and stored. In
addition, instead of the shift reactor and the separator a water-gas shift H2-selective
membrane reactor can be used. A pre-fuel cell CO2 capture concept will not be investigated
in this work.

Figure 9: SOFC-GT with pre-fuel cell CO2 capture [1.20]

The basic concept of post-fuel cell CO2 capture is shown in Fig. 10. The anode off-gas has a
high CO2 content, but also contains H2O, CO and H2. The water can easily be removed by
conventional techniques (cooling, knock-out, additional drying). Oxidizing the H2 and CO
from the SOFC anode with air will result in a high dilution of the stream with nitrogen.

18
 Figure 10: SOFC-GT with post-fuel cell hydrogen oxidation [1.20]

To avoid dilution with nitrogen pure oxygen can be used for oxidation, but this will probably
result in significant additional costs and energy consumption if oxygen is not available. In the
system used for the project an air separation unit and thus the oxygen for oxy-combustion is
available. In case no oxygen is available the use of an oxygen-conducting membrane reactor
(OCM-reactor), placed after the SOFC, could be integrated into the scheme (figure 11). The
anode off-gas is fed to one side of the membrane while the cathode off-gas is fed to the other
side of the membrane. The membrane is selective to oxygen, which permeates from the
cathode off-gas stream to the anode off-gas. In the membrane unit, H2 and CO are oxidized.
The retentate of the membrane unit consists of CO2 and water. The water can be removed
using conventional techniques.

There is almost no need for after treatment of the CO2 rich stream, only compression for
storage. Both of these concepts, oxy-combustion and the oxygen conducting membrane, are
investigated in the next chapters. The exact configuration is yet to be decided due to the fact
that the exact configuration depends on how the membrane can be integrated into the system.

Figure 11: SOFC-GT with OCM-afterburner [1.20]

Another concept for CO2 capture in SOFC and hybrid systems uses a water-gas shift
membrane reactor afterburner (WGSMR-afterburner). The working principle is shown in
figure 12. Air is fed to the SOFC cathode and fuel is fed to the SOFC anode. The cathode off-
gas is fed to the permeate side of the membrane reactor and the anode off-gas is fed to the
feed side of the membrane reactor. On the feed side the water-gas shift reaction takes place
producing H2 and CO2. The H2 permeates through the hydrogen selective membrane in the
WGSMR-afterburner. On the permeate side this hydrogen is burned with O2 present in the
SOFC cathode off-gas. This results in a very low hydrogen partial pressure on the permeate
side, thus resulting in a high H2 permeation rate.

19
 Figure 12: Working principle of the WGSMR-afterburner [1.20]

The WGSMR-feed side products are CO2 and H2O, and small amounts of H2 and CO, which
can be removed by (catalytic) oxidation with air resulting in only a small dilution with
nitrogen. The water can be removed easily e.g. with cooling. The resulting CO2 can be used
for sequestration without the need for further treatment. The WGSMR permeate side products
are N2, H2O and O2.

The WGSMR concept has the same advantages as the OCM-afterburner concept. A pure CO2
stream is available after water knock-out, without the requirement of large, complex and
steam-consuming CO2 scrubbing equipment. Thus, the system offers the prospect for power
production with CO2 capture. Moreover, the system has some additional advantages above
the OCM-afterburner concept:

The flux through the membrane is towards the gas turbine side. Thus, the mass flow
through the expander is increased (higher power production), and the dilution of CO2
with water is decreased.
With the projected membrane materials higher fluxes may be achieved without the
necessity for imposing a current on the membrane material as might be required with
OCM membranes.

Figure 13: Hybrid cycle with WGSMR-afterburner [1.20]

The pressurized hybrid cycle with a WGSMR-afterburner is shown on figure 13. Air is fed to
the gas turbine compressor, heated and fed to the SOFC cathode. Fuel is heated, mixed with
steam and fed to the SOFC anode. The anode off-gas is fed to the feed side of the WGSMR.
Cathode off-gas is used as a sweep gas for the permeate side of the WGSMR. The retentate
stream from the WGSMR-afterburner is cooled and flows to the CO2 compression and
storage section. The permeate stream from the WGSMR-afterburner passes an optional
combustion chamber for additional firing to increase the temperature at the gas turbine inlet.
It is then expanded in the gas turbine. The additional combustion of fuel will completely
remove emissions of CO2, but compared to just venting the CO2, the amount vented in this

20
case is relatively small. The concept with additional combustion of fuel is not a subject of this
thesis report. But two concepts using a H2-conducting membrane are investigated, one with
N2 as sweep gas and the other with air as sweep gas.

1.7 Membrane technologies

Membranes are devices which offer the possibility of selectively remove some species from a
gas mixture. There are porous membranes where entire molecules pass through the
membrane. This allows easier permeation but has a negative effect on selectivity. Solid
(metallic) membranes offer very high selectivity but the permeation rates are much lower due
to the fact that atomic permeation takes place and this involves numerous processes like those
seen in figure 14.
In this thesis report two kinds of membranes were used:
H2-conducting membrane (Palladium based membrane)
O2-conducting membrane (Perovskite based membrane)

Figure 14: Hydrogen transport through Pd membranes [1.21]

The H2-membrane has more emphasis here because of the reason the membrane is used in the
first place: to withdraw as much H2 from the depleted anode side as possible. Using
membranes does not allow removing all the H2 from the retentate side, because the partial
pressure difference of the species on each side is the driving force for the permeation process.

1.8 Aspen Plus [1.22]

Conceptual design of chemical processes

Aspen Plus is a market-leading process modeling tool for conceptual design, optimization,
and performance monitoring for the chemical, polymer, specialty chemical, metals and
minerals, and coal power industries. Aspen Plus is a core element of AspenTech’s
aspenONE™ Process Engineering applications.

21
Features

Efficient workflow for process design, equipment sizing, and preliminary cost
estimation within one environment through integration with other aspenONE Process
Engineering tools including Aspen Process Economic Analyzer cost modeling
software and Aspen HTFS+® heat exchanger design tools.
Online deployment of models as part of an open-loop operator advisory system or in
closed-loop, real-time optimization/advanced process control applications when used
with Aspen Online Deployment™ and Aspen Simulation Workbook™.
Unique equation-oriented architecture. Aspen Plus’s unique combination of
sequential-modular and equation-oriented solution technologies facilitates the
simulation of wide-scale, integrated chemical processes.
Best-in-class physical properties methods and data. Aspen Plus includes extensive
databases of pure component and phase equilibrium data for conventional chemicals,
electrolytes, solids, and polymers. Ongoing collaboration with the U.S. National
Institute of Standards and Technology ensures easy access to the best available
experimental data and methods.
Comprehensive library of unit operation models to address a wide range of solid,
liquid, and gas processing equipment. The open architecture lets you build your own
libraries of unit operation models with Aspen Custom Modeler® or programming
languages. CAPE-OPEN compliant models can be also be used with Aspen Plus.
Workflow automation. Aspen Plus models can be linked to Microsoft Excel® using
Aspen Simulation Workbook or Visual Basic® and used to automate the engineering
workflow and deploy the model to a wider range of end users in the field.
Links to third-party tools. Aspen Plus includes links to several well-known tools
including the OLI’s electrolyte package and Technip’s SPYRO ethylene cracker
models.

Options

A number of optional extensions are available to enhance the value of Aspen Plus:

Aspen Plus Dynamics® is used for safety and controllability studies, sizing relief
valves, optimizing transition, start-up, and shutdown policies.
Aspen Rate-Based Distillation improves the rigor and accuracy of the distillation
models using proven rate-based technology.
Aspen Batch Distillation is a dynamic batch distillation modeling tool that can be
run stand-alone or inside an Aspen Plus flow sheet.
Aspen Polymers Plus® extends Aspen Plus with a complete set of polymer
thermodynamics methods and data, rate-based polymerization reaction models, and a
library of industrial process models.
Aspen Distillation Synthesis is used for the conceptual design of distillation schemes
for separation of mixtures with non-ideal vapour liquid equilibrium behaviour.

Benefits

Aspen Plus is a proven, industry-standard solution with over twenty years of use in the field.
Customers have recognized and reported:

Up to $15M per year in incremental profitability from process optimization

22
 Up to $10M per year in capital savings resulting from improved designs
Up to $1M per year of reduced labour costs from improved conceptual engineering
workflow

1.9 Objectives
Several CO2 capture system concepts can be integrated with fuel cell systems, but the
selection of one over another requires detailed study of long-term technical and economic
performance [1.23].

The primary objectives of the present study can be viewed as answering the following
questions through the modeling and simulation of various SOFC tail-gas configurations:

1) How do different tail-gas concept configurations affect mass flows?

2) Where and how much heat is needed for heating/cooling the gas streams?
3) Is it necessary to use any external heat sinks for heating/cooling of the gas streams?
4) Comparing the net energy production of the modeled systems and the breakdown of
where and how much energy is produced and consumed.
5) How much of the cathode flow should be recycled to have the needed air temperature
at the cathode inlet?
6) Is it necessary to vary the air flow going to the cathode of the SOFC with different
tail-gas processing concepts (fraction of air recycled)?
7) What effect does the increased/decreased flow of air have on the net-power produced
(more power to compress the air, more power produced by the gas turbine due to the
increased mass flow)?

1.10 Methodology
The research methodology for the present study was carried out in the steps listed below. In
practice, the sequence of the steps did not occur in the exact order presented below. Instead,
some of them occurred simultaneously and some of the later steps were done earlier [1.23].

1) To find from the literature the content and parameters of syngas after the cleanup
processes
2) To develop a fuel cell (SOFC) model using components available in Aspen Plus
3) If possible validate the SOFC model with an existing model
4) Find out how membranes work, what are the driving forces of permeation
5) Model the membrane function in an Excel spreadsheet and then connect it with
Aspen Plus, importing the parameters and content of gas streams from aspen and
then export the results back to Aspen Plus
6) Development of different tail-gas concepts
7) Calculating the parasitic losses (compression of air/CO2, water knock-out from
CO2, compression permeate streams etc) and power produced in the system
8) Calculate the overall efficiencies of the different concepts, using the higher and
lower heating value of the coal fed to the gasifier, with and without CO2 capture

23
 9) Compare the efficiencies of the different concepts with each other and with just
mixing the cathode and anode streams, where CO2 is vented
10) Analyze the results and discuss why the results occured
11) Possible suggestions as to what could be done to improve the performance of
different concepts or some parts of them

The goal of the modeling is to provide a sufficiently realistic model which is able to meet the
research objectives and answer questions like:

How much power was generated and consumed by the whole system?
How to demonstrate the chemical reactions taking place in the fuel cell?
What were the temperature changes of reactant flows?
How much is the mass transfer from the cathode side to the anode side and how much
power was produced by the SOFC?
How much heat is produced in the tail-gas from combusting the fuel not reacted in the
SOFC?
How does mass transfer between the depleted anode and cathode streams?
How does heat change between the anode and cathode streams take place?

To meet the objectives, all components in the system have the ability to predict performance
at a steady state. It is also apparent that different levels of modeling will be required to
simulate different parts of the system. For example, the H2-conducting membrane model is
capable of resolving the distribution of composition (H2 molar flow and partial pressure) of
the gas stream along the length of the membrane (one-dimensional) while simulation of other
equipment employs relatively simple (zero-dimensional) steady-state thermodynamic models.

In order to maintain focus on the research objectives, the scope of the project was limited by
an analysis of the systems using the same amount and content of syngas and air fed to the
system. The only parts that were changed were the tail-gas processing and CO2 separation
concepts.

1.11 Chapter References

1.1 http://www.eia.doe.gov/oiaf/ieo/coal.htm - Web-page
1.2 http://www.eia.doe.gov/oiaf/ieo/ieorefcase.html - Excel-file (Table A2)
1.3 http://www.eia.doe.gov/cneaf/coal/page/acr/table26.html - Web-page
1.4 http://en.wikipedia.org/wiki/Fossil_fuel_power_plant - Web-page
1.5 U.S. Department of Energy (2002) Final Report: Major environmental aspects of
gasification-based power generation technologies. U.S. Department of Energy, Office of
Fossil Energy, National Energy Technology Laboratory.
1.6 Bredesen, Jordal, Bolland, High-temperature membranes in power generation with CO2
capture. Chemical Engineering and Processing 43 (2004) 1129-1158
1.7 http://www.parl.gc.ca/information/library/PRBpubs/prb0704-e.htm#future – web page
1.8 http://www.netl.doe.gov/technologies/coalpower/cctc/summaries/pinon/images/pinon_sc
hematic.jpg - web page

24
1.9 http://en.wikipedia.org/wiki/Gasification - web page
1.10 http://en.wikipedia.org/wiki/Carbon_tax - web page
1.11 Stiegel, Maxwell, Gasification technologies: the path to clean, affordable energy in
the 21st century, Fuel Processing Technology 71 (2001) 79-97
1.12 U.S. Department of Energy (2004) Fuel Cell Handbook (Seventh Edition). U.S.
Department of Energy, Office of Fossil Energy, National Energy Technology
Laboratory.
1.13 Dr. Neal Sullivan (2008), FC 602: Types of Fuel Cells, Neal Sullivan, RES FC602
1.14 O´Hayre, Cha, Colella, Prinz, Fuel Cell Fundamentals, John Wiley & Sons (2006)
1.15 http://en.wikipedia.org/wiki/Brayton_cycle - web page
1.16 http://www.grc.nasa.gov/WWW/K-12/airplane/Images/braytonts.gif - web page
1.17 www.chrisbence.com/.../braytoncycle.jpg web page
1.18 www.taftan.com/thermodynamics/PLANT1.GIF - web page
1.19 http://www.mhtl.uwaterloo.ca/courses/me354/lectures/pdffiles/c8.pdf - web page
1.20 Djikstra, Jansen, Novel concepts for CO2 capture. Energy 29 (2004) 1249-1257
1.21 Al Raisi, Gardner, Surface and fluid phase transport effects on hydrogen permeability
through palladium-based membranes, AlChE Annual Meeting, Salt Lake City, Utah,
November 2007
1.22 http://www.aspentech.com – web page
1.23 R.J. Braun, Optimal design and operation of solid oxide fuel cell systems for small-
scale stationary applications, Ph.D. Thesis, University of Wisconsin-Madison (2002)

25
2 Modeling of various CO2 capture strategies in the SOFC-gas
turbine subsystem

Modeling of fuel cells systems can proceed at numerous levels of detail ranging from stack
design levels to overall systems levels. As this project is concerned with sub-system design of
an IGFC, the level of modeling detail required for most system components is more general
and will not be too detailed (overall mass and energy balances and incorporation of
component performance characteristics). In addition, in the beginning no SOFC model was
available and what was done to simulate the fuel cell in the system is described later in this
chapter. The created SOFC model was verified using an existing SOFC model from NETL.

In this chapter, an overview of the approach for modeling an IGFC-GT with different tail-gas
processing concepts is presented. The associated assumptions and modeling simplifications
are then discussed. The following was modeled:
A fuel cell model
A membrane model
The incorporation of the membrane model to the system
The Brayton and Rankine cycles
CO2 preparation for storage

On Fig. 15 the IGFC system configuration with the baseline tail-gas concept (oxy-
combustion) can be seen. In this work only a part of this system is modeled (SOFC-GT, CO2
separation, and preparation for sequestration).
For the baseline configuration oxy-combustion of tail-gas has been chosen. This choice is
based on the fact that this technology is already commercially available and in addition there
is already an air separation unit (ASU) for producing oxygen for the gasifier in this system,
and for it to supply oxygen for the oxy-combustion is a question of sizing the ASU. The
additional energy needed to compress additional air and for separating extra O2 has to be
taken into consideration.
For comparison three other concepts are being modeled, these are:
1. Tail-gas combustor without CO2 capture, where the CO2 is being vented
2. Water-gas shift (H2-conducting) membrane reactor (WGSMR)
a. Nitrogen as sweep gas
b. Air as sweep gas
3. O2-conducting membrane reactor
All these concepts alter the system configuration of the mass flows and thermal integration.
Possible examples of these configurations; oxy-combustion, H2 and O2 conducting
membranes reactors, can be seen in chapter 1 (Fig. 10-13).

26
 Figure 15: Baseline IGFC System Configuration [2.1]

The gas turbine in Fig. 15 produces power but also compresses air for the cathode of the
SOFC. In addition some air goes to the air separation unit (ASU). The ASU provides oxygen
for the gasifier and also for the oxy-combustor.

In the gasifier the coal slurry is turned into a synthetic gas (syngas), consisting mainly of CO
and H2. Before entering the anode of the fuel cell the char, tar and sulphur have to be
removed from the syngas. The CO is shifted to H2 and CO2 in the cathode side and around
80% of the H2 content in the syngas is reacted electrochemically with O2. There are two main
reasons for not reacting all of the H2 in the syngas:

1. To maintain a sufficient rate of reaction in the end of the fuel cell

2. To be able to increase the temperature of the depleted syngas by combusting the fuel
(H2, CO and some CH4) left in the depleted syngas

After combusting the fuel residues in the syngas, the heat created is transferred to the cathode
stream exiting the SOFC. In addition the anode stream is used to pre-heat the air stream
entering the cathode and if possible additional heat is utilized in the heat recovery steam
generator (HRSG). After these processes water knock-out and compressing of the anode
stream takes place, and after that the content of the anode stream should be almost entirely
made up of CO2.

27
2.1 SOFC modeling
An SOFC model was created using elements available in Aspen Plus 2006. The following
processes had to be taken into account:
1. Pre-heating of the reactant streams
2. Chemical reactions (electrochemical ―burning‖ of H2, shifting of CO and CH4)
3. Fuel utilization
4. Changes in mass flows
5. Temperature changes of the reactant flows
6. Power generated by the SOFC
The fuel cell model is presented on Fig. 16. The fuel cell itself is surrounded by the red line.
In addition the pre-heater of the anode stream and the recycling loop of the cathode stream
can be seen.

Figure 16: Fuel Cell model in Aspen Plus

The reactant streams have to be at 650°C when entering the fuel cell. The syngas can be
heated to 650°C using the anode-out stream, which is at 750°C. For the cathode stream a
different approach was chosen: the recycling of the cathode stream, which is at 800°C on the
outlet of the cathode. The split fraction needed to be recycled depends on the temperature of
the compressed air before the recycling loop.

28
Two chemical reactions were simulated using a stoichiometric reactor (the stoichiometric
reactor allows determining which reactions take place and what is the fractional conversion
of the species). In figure 17 the reactions are presented. As can be seen the reactions no. 1
and 4 are identical. The reason for reacting H2 with O2 twice can be explained like this: if
reaction no. 1 is discarded, some of the CO and CH4 will not be shifted because there is not
sufficient water available to conduct these reactions. And if reaction no. 4 is left aside the
amount of H2 produced during the water-gas shift reaction will not be reacted and the desired
fuel utilization is not achieved. It is also important to indicate that the reactions have to occur
in sequence (like seen in Fig. 17). The fractional conversion for H2 is 1 in both reactions and
0,8 for CO and CH4. These numbers do not determine the fuel utilization in the fuel cell. The
reason for this is explained further on in this chapter.

Figure 17: Reactions in the Stoichiometric reactor (Aspen Plus)

Syngas and pure oxygen are fed to the reactor. The operating conditions of the reactor were
set as seen on Fig. 18. The operating temperature that was set is important because then the
heat duty of the reactions in the reactor can be calculated. The total heat duty of the reactions
heats up the anode stream to 750°C (in the reactor element) and the cathode stream to 800°C
(in the cathode HX). What is left is the heat duty, or ―POWER‖. Later this heat duty
(―POWER‖) can be used to determine the right mass flow of air into the SOFC cathode by
comparing the heat duty (―POWER‖) with the PDC produced in the SOFC.

Figure 18: Specifications of the Stoichiometric reactor (Aspen Plus)

In addition, the reactions and the reaction fractions of species in the reactor have to be
determined. This is done in the reactor setup → reactions, as seen in Fig. 17. Here H2 reacts
with O2; CO and CH4 are shifted to CO2 and H2 by reacting them with H2O. Although the
water-gas shift reaction may go to the reactants side at higher temperatures (reverse water-gas
shift reaction), the fact that H2, one of the products, is constantly withdrawn from the anode
side causes an electrochemical reaction with O2 and the reaction is shifted to the product side.

The fuel utilization was determined by the molar flow of oxygen flowing to the reactor. To
control the fuel utilization and the oxygen going through the electrolyte of the fuel cell a user

29
defined model was created. The user defined model can be in FORTRAN or an Excel
spreadsheet. An Excel spreadsheet was used for this model.

The input parameters to the spreadsheet are:

Content of syngas entering the SOFC anode

Content and temperature of air entering the SOFC cathode
Temperature of air at the SOFC cathode outlet

and the returns used the following calculated parameters:

Content and flow of the air exiting the SOFC cathode

Flow and temperature of oxygen entering the reactor

The temperature of the oxygen flow to the reactor is calculated with the following formula:

The flow of pure oxygen into the reactor takes into account the hydrogen content (including
how much can be produced from CO and CH4) in the syngas and oxidizes the desired
amount. Parallel to the oxidation of H2, the shifting of CH4 (the CH4 is assumed to be shifted
directly to CO2 and H2) and CO takes place. In this research the fuel utilization was chosen to
be 80%.

According to the chemical reactions shown, one mole of CH4 can produce four moles of H2;
and to oxidize four moles of H2, two moles of O2 is needed. One mole of CO can produce one
mole of H2. So to oxidize one mole of H2, half a mole of O2 is needed. Taking this into
account the formula for the molar flow of oxygen to the reactor is:

Where the UF is the fuel utilization and this is determined by the user in the Excel
spreadsheet. The user defined fuel utilization is valid even if the reaction fractions for all the
reactions in the reactor are 1. This is because the Excel sheet will overwrite the molar flow of
pure oxygen to the reactor and this will be only as much as needed for oxidation of the
fraction of fuel determined by the user.

To have a mass balance on the cathode side the molar flow of oxygen in the outlet of the
cathode must be smaller than in the inlet by the amount fed to the reactor. The mass balance
is provided by the following relations:

30
To get the power output of the SOFC the following formula was used:

Where the vfuel is the molar flow of fuel reacted in the fuel cell [mol/s], i is the current
produced by the electrochemical reaction [A], n is the number of electrons released during
the reaction and F is the Faradays constant F=96485 C/mol. The vfuel was calculated through
the oxygen flow to the reactor using the following relationship:

Power output calculations:

Where the V is the cell voltage, which was chosen to be 0,7V.

The calculated DC power of the SOFC should be equal to heat duty ―POWER‖ (Figure 18).

Where Pin is the power input of H2 (including H2, which could be produced by shifting all the
CO and CH4) in syngas reacted [kW]; PDC is the DC power generated by the SOFC [kW];
is the heat duty to increase the temperature of air from 650°C to 800°C [kW];
is the heat duty to increase the temperature of syngas from 650°C to 750°C [kW];
mAIR is the mass flow of air [kg/s]; is the heat needed to increase the temperature of 1 kg
of air 1 by degree [kJ/(kg°C)]; is the temperature change caused by adding or removing
heat [°C].

For PDC to be equal to the heat duty in stream ―POWER‖ only the heat added to the air stream
( ) can be changed, PDC is constant and also the heat added to the syngas is limited
because the content, flow rate and temperature change are constant.

The mass flow of air is adjusted in such a way that the will be equal to PDC:

This assumption is based on the first law of thermodynamics which is the law of conservation
of energy (The increase in the internal energy of a system is equal to the amount of energy
added by heating the system, minus the amount lost as a result of the work done by the
system on its surroundings) [1.26].

2.2 SOFC model verification

To verify the created SOFC model an SOFC model, operating at 1 bar, created in the
National Energy Technology Laboratory (NETL) was available. The principals of the two
models were similar but in the NETLS model instead of the cathode the anode stream was
recycled.

31
To compare these two models the data from between the recycling loop was taken, that way
the recycling does not have any effect on the results, this is being illustrated in Fig. 19. This
was also done with the anode streams of the NETL SOFC model. Both models have a fuel
utilization of 80%.

The inlet pressure of the reactants was increased from 1 bar to 15,1 bars. Then the NETL
model was run. The syngas content was taken from between the anode recycling loop and the
anode inlet of the NETL SOFC model. Also the air content and parameters were taken from
the NETL model; this is because the NETL model adjusts the air flow in a way that the heat
duty ―POWER‖ (Figure 19) is equal to the calculated direct current (DC) power.

Figure 19: Fuel Cell model in Aspen Plus

On table 6 the inputs and outputs of the SOFC models are presented:

Anode inlet Anode outlet Anode outlet

(NETL)
Mole flow [kmol/hr] 14818 14836 14832
Temperature [°C] 649 750 750

32
Pressure [bar] 15 15 15
CH4 8,8 0,02 1,7
CO 1454 257 290
CO2 6235 7440 7406
H2 1295 298 259
H2O 5604 6617 6654
N2 221 221 221
O2 - - -
Table 6: Input and comparison of anode outputs of the two SOFC models

As seen in table 6, if both of the syngas have the same content and other parameters of the
inlet of the anode the outlet is also almost the same; only slight variation is noticed. The H2
left in the anode stream (including in CO and CH4) is the same.

Cathode inlet Cathode outlet Cathode outlet

(NETL)
Mole flow [kmol/hr] 37939 36825 36825
Temperature [°C] 650 800 800
Pressure [bar] 15 15 15
Oxygen flow 1113 1113
[kmol/hr]
Table 7: Flows of the cathode

NETL SOFC model SOFC model

Heat duty of reactor 124 125
[Gcal/hr]
Heat duty of SOFC [Gcal/hr] 81 80
Heat duty of cathode 43 45
[Gcal/hr]]
PDC of SOFC [kW] 94241 83819
Table 8: Heat duties and PDC

As seen in table 8, and also in all the previous tables, all the results are comparable and only
slight differences are noticeable, except for the PDC of the SOFC´s. The reason for this may
be the selected cell voltage. For the current model it was chosen to be 0,7 V. To make these
powers equal the cell voltage has to be 0,797 V. To make sure that the cell voltage does not
change, the flow of syngas was varied. In all cases the power outputs (PDC) of the two SOFC
models were equal if the cell voltage the SOFC model created was 0,787 V.

The comparison of the two SOFC models showed that the one created has the same
performance as the one from NETL. Except that the PDC generated were different, in order to
get equal power outputs the cell voltage has to be 0,79 V; which, compared to the cell voltage
usually used, 0,7 V, is relatively high. To have a compromise the average value of these two
was chosen to be – 0,745 V.

2.3 Modeling of air compression

In the IGFC system compressed air needs to be supplied to two places: the air separation unit
(ASU), which supplies pure oxygen for the gasifier, and the cathode of the pressurized
33
SOFC. For this there is only one compressor, and to supply this compressed air to two places
a splitter was used to split the stream into two, where the split fraction of air going to the
ASU was set to be 0,1667 and the split fraction of air heading to the cathode of the SOFC is
0,8333. These split fractions are subject to change according to how much air needs to be
supplied to the ASU (Oxygen for the gasifier and the oxy-combustion) and to the cathode of
the SOFC.

Figure 20: Air compression for the fuel cell and for the ASU (Aspen Plus)

The configuration of this system is shown in Fig. 20. The specifications of the compressor are
shown in figure 21. The compressor works as isentropic and the discharge pressure is set to
be 15,1 bars, with the isentropic efficiency of 88% and the mechanical efficiency of 0,98.

Figure 21: Specifications of the compressor model (Aspen Plus)

2.4 Modeling of CO2 preparation for sequestration

After the tail-gas processing a CO2 rich stream, at relatively low pressures, is created
consisting mainly of CO2 and water (with some N2 and H2, traces of CO and CH4). This
stream has to be compressed up to 150 bars and the water has to be knocked out of the
stream. The water knock-out takes place via a refrigeration plant, and to model this, a simple
heat exchanger is used which cools the CO2-rich stream down to -30°C. In addition the

34
cooling keeps the temperature at the outlet of the compressor reasonable. To find out how
much power is needed for the refrigeration plant to work the following equation was used:

[2.2]

Where β-coefficient of performance, it was chosen to be 2; Qin – amount of energy received

by the system, heat duty [Gcal/hr]; Wcycle – net work into the system to accomplish this
effect. The power input to the refrigeration plant was calculated in an Excel spreadsheet
where the input is the heat duty of the heat exchanger and the output is the electrical power
input to that plant. This value was used later to calculate the net-power of the system. The
specifications of the compressor are the same as the air compressor, except the discharge
pressure is 150 bars.

Figure 22: Preparation of CO2 for storage (Aspen Plus)

35
2.5 Gas turbine modeling

Figure 23: Gas turbine model (Aspen Plus)

The SOFC uses a combined Brayton-Rankine cycle as a bottoming cycle. For the Brayton
cycle, gas turbine cycle, the type of the turbine is isentropic, the isentropic efficiency is 90%,
the mechanical efficiency, like the compressors, is 98% and the discharge pressure was said
to be 1,01 atm. The modeling of the gas turbine is fairly simple, an expander was used. After
gases are expanded they are sent to the heat recovery steam generator, and the produced
steam will be utilized in a steam turbine.

Figure 24: Gas turbine model specifications (Aspen Plus)

Only air will go to the gas turbine. After the SOFC the temperature of the air is around
800°C. The additional heat comes from burning the fuel left in the depleted syngas, directly
in the air stream or transferring the heat to the air stream via a heat exchanger. Net-power at
the power output of the expander is due to the fact that a user defined model sums up all the
power generated and consumed in the system and overwrites that number with the net-power
produced. This is explained further on in this chapter.

2.6 Steam cycle (Rankine cycle) modeling

The role of the steam turbine will be taken into account in a simplified way. Heat exchangers
are placed at the exhaust of the gas turbine (Fig. 25), before the knock-out of water from the

36
CO2-rich stream takes place and at some other places (compressor with intercooling)
depending on the system configuration. The power output of the Rankine cycle is calculated
using the heat duties of these heat exchangers.

Where ηRankine is the efficiency of the Rankine cycle and is set here 0,3; is the sum of
heat sources in the system which could be used for steam generation and the temperature of
the cycle exhaust will be 126°C [1.12].
For converting Gcal/hr into kW the following relationship was used:

Figure 25: HRSG model (Aspen Plus)

37
2.7 Modeling of H2-conducting membrane
It has been found that H2 permeates through the membrane via a solution-diffusion
mechanism, and the rate of H2 permeation per unit area of the membrane, , is
proportional to the partial pressure difference. The calculations for the membrane were done
using an Excel spreadsheet. Inputs to the membrane model are taken from Aspen Plus, which
are the contents and parameters of the retentate and permeate streams; the membrane model
then conducts the calculations and exports the results to Aspen.
The H2 flux through the membrane is calculated as follows:

Where A is the surface area of the membrane [m2]; k is the apparent permeability of the
membrane material [mol/(m2Pa0,5)]; is the partial pressure of H2 on the retentate side
[Pa]; is the partial pressure of H2 on the permeate side [Pa].
This formula applies when the limiting process of the H2 permeation through the membrane
is the bulk diffusion in the membrane material. The bulk diffusion is the limiting process only
if the membrane is thick enough. If the membrane is very thin, some other processes of the
permeation will be the limiting ones.
Because we have a solid metal membrane and only hydrogen atoms diffuse through the
membrane the exponent n is 0,5. In contrast if there would be a microporous membrane
where only hydrogen molecules pass through the membrane the exponent n would be 1.
The flux of H2 through the membrane depends on the partial pressure difference of the H2 on
either side of the membrane. The partial pressure depends on the total pressure on each side
of the membrane and also on the molar fraction of H2 in the gas. These parameters can be
controlled. Permeation of H2 to the permeate side is favored if the pressure on the retentate
side is big and is low on the permeate side. In addition a sweep gas can be used on the
permeate side. This has two effects: first, it carries away the H2, and second, it dilutes the H2,
lowering the partial pressure of the H2 in the stream. This also has a negative effect: the H2
stream is diluted and lower temperatures will be achieved in the combustor later on.
Several different gases can be used as sweep gas, for example: air, nitrogen, argon and even
with no sweep gas. In this study air and nitrogen were used.
The membrane was divided into 30 stages to simulate the partial pressure changes of H 2
along the length of the membrane and thus the changes in the permeation flux. A co-current
flow was chosen. For every step the flux, molar flow of H2, total molar flow, mole fraction
and partial pressure of H2, and the total pressure were recalculated for both the retentate and
permeate side:

Retentate side
Molar flow of H2:
Total molar flow:
Mole fraction of H2:
Partial pressure of H2:
Total pressure:

38
Permeate side
Molar flow of H2:
Total molar flow:
Total pressure:

Due to the fact that there is a partial pressure difference needed for the permeation process to
take place, the recovery of 100% of the H2 from the retentate stream is not likely to happen
(unless a constant vacuum is created on the permeate side and the surface area of the
membrane is very large).
The imported values from Aspen are the temperature, pressure and the molar flows of species
of the retentate and sweep gas (if there is one) streams on the inlet. The exports to Aspen are
the same values but on the outlet of the membrane.
It is assumed that a pressure change takes place on both sides of the membrane; this is based
on the fact that a mass transfer takes place in the form of H2 permeating through the
membrane but the volume stays same. The pressure on the retentate side decreases as much
as the partial pressure of H2 changes across the retentate side of the membrane, and the
pressure on the permeate side increases as much as the partial pressure of H2 changes across
the permeate side of the membrane.

Figure 26: H2 conducting membrane

As seen on Fig. 26, the membrane results in a CO2- and H2O-rich stream and a mixture of
sweep gas (if used) H2. The H2-rich gas stream can later be fed into a combustor. The
combustion product of H2 is water, and this way emissions are eliminated and water from the
CO2 stream can be relatively easily knocked out via cooling.

39
2.8 Modeling of O2-conducting membrane
The approach to simulating the O2 conducting membrane is finding out how much fuel (CH4,
CO and H2) is left in the tail-gas and withdrawing as much O2 from the depleted air stream,
from the cathode of the SOFC, as needed to oxidize all of it. The amount of O2 is calculated
as follows:

The actual membrane operation was not calculated, because the changes in mass flows are of
interest. The concept is similar to the oxy-combustor; the only difference is that the O2 is
taken from the depleted air stream, which comes from the SOFC cathode.
The inputs to the O2 membrane model are the molar flows of fuel species in the tail-gas
stream and the species of depleted air from the SOFC cathode. In addition the temperature
and pressure of these streams are read to import them to the streams exiting the membrane.

Figure 27: O2 conducting membrane (Aspen Plus)

2.9 Parasitic losses from ASU

The power needed for the air separation unit (ASU) was taken into account. From the
literature the power needed to separate 1 kg of O2 from air in 1 second was 0,424 MW/(kgs).
It is assumed that this includes also the power for compression. To get the power
consumption in the ASU, the power needed to compress 1 kg of O2 per second was
calculated:

Where is the power needed to compress 1 kg of [Mw/(kg/s)]; is the

power needed to compress all the air (to ASU and SOFC cathode) [MW]; is the total
mass flow of air entering the compressor [kg/s]; is the weight fraction of O2 in the air.
The previously calculated value is subtracted from the value mentioned in the beginning of
this chapter:

40
Where is the power needed in the ASU [MW/(kgs)]; is the power needed in
the ASU and compressor to get 1 kg of O2 [MW/(kgs]; is the power to compress 1
kg of O2.
The previous calculations are made in order to get values which do not depend on the flows.
This becomes handy when, for example, an oxy-combustor is integrated into the system, and
then extra O2 needs to be produced in the ASU and extra air needs to be compressed to be
sent to the ASU. By knowing the needed amount of extra O2 the parasitic losses can easily be
calculated.

2.10 Modeling of oxy-combustion

To model oxy-combustion a Gibbs reactor was used, which is based on rigorous reaction
and/or multiphase equilibrium based on Gibbs free energy minimization. In order to supply
the amount of pure oxygen to the reactor for oxidizing all the fuel left in the depleted anode
stream an Excel spreadsheet was used. Inputs to the Excel spreadsheet are the molar flows of
H2, CO and CH4 in the anode stream. The flows of species and the total oxygen flow to the
reactor are calculated as follows:

Figure 28: Oxy-combustor

The combustion products will not be fed directly to the gas turbine; instead a heat exchanger
is used to raise the temperature of the depleted air from the SOFC cathode.

41
2.11 Modeling of H2-conducting membrane reactor with N2 as
sweep gas

Figure 29: Concept of H2-conducting membrane reactor with N2 as sweep gas

In Fig. 29 the concept of an H2-conducting membrane with N2 as sweep gas is presented.

The following processes take place in the membrane reactor:
Water-Gas Shift Reaction
Transfer of H2 from the retentate side to the permeate side
Heat transfer
It was assumed that all the CO and CH4 in the depleted syngas shifts on the inlet of the
membrane, allowing the use of a stoichiometric reactor where the fraction of reactants reacted
can be determined.
The inputs to the membrane reactor were adjusted in such a way that the recovery of the H2
from the retentate stream is 90%.
In addition the membrane works as a heat exchanger, because the membrane itself is very
thin (much less than 1 mm). To model the heat exchanger function in front of the membrane
model the retentate and sweep gas streams flow through a heat exchanger and the difference
between the outlet was set 20°C.
N2 from the ASU was used as the sweep gas. The sweep gas from the ASU is at relatively
high pressure (3,6 bar) and to avoid high partial pressure of H2 on the permeate side, which
has a negative effect on the permeability, the total pressure must be lowered, thus an
expander was used.

42
Using an expander requires heating the gas before and after the expander due to the fact that
the temperatures may drop too low (N2 from ASU is at 7°C) and dangerous thermal gradients
may occur in the membrane. After the membrane the mixture of H2 and sweep gas, the
permeate stream, has a low pressure (0,1-0,2 bar) but the tail gas combustor operates at 14,7
bars. The permeate stream must be compressed at least to the pressure at which the
combustor is operating. A compressor with intercooling was used because of the temperature
constraints of the compressor, here set to be 450°C. The heat from the intercooling is used to
produce steam for the Rankine cycle.

2.12 Modeling of H2-conducting membrane reactor with air as

sweep gas

Figure 30: Concept of H2-conducting membrane reactor with air as sweep gas

The model for the H2-conducting membrane with air as sweep gas is presented on Fig. 30.
Several processes happen at the same time:
Water-Gas Shift Reaction
Transfer of H2 from the retentate side to the permeate side

43
 Oxidation of H2
Heat transfer
It is assumed that all the CO and CH4 are shifted in the entrance of the membrane reactor. To
simulate this, a stoichiometric reactor was placed before the membrane model. The fractional
conversion of both CO and CH4 is 1.
In the membrane model around 90% of the H2 in the retentate stream is transferred to the air
side of the membrane. The membrane model is described in chapter 2.7.
After this the mixture of air and H2 is fed to another reactor (Gibbs free energy reactor) where
the combustion of H2 takes place and the temperature of air rises.
The membrane reactor also acts as a heat exchanger, and to model this, two heat exchangers
are used (Fig. 30): one is between the water gas shift reactor and the membrane and the
second one is after the combustor. The heat exchangers are needed because otherwise the
heat transfer to the retentate side is not taken into account and the temperature of the air on
the outlet of the MR is higher than it should be.
These simplified approaches are justified because the temperature and pressure affects only
how much surface area of the membrane is needed to permeate a certain amount of H2, and
the aim is to look at the problem from a system point of view to compare flows and power
output of different concepts.
The advantage of this concept, compared to using N2 as sweep gas, is that the system is less
complex. All the processes take place in one unit and the following components do not have
to be used:
compressors
expanders
heat exchangers
external source of sweep gas
On the negative side it can be mentioned that the temperature during oxidizing the H2 in air
may raise the temperatures higher than the membrane material is able to withstand.

44
2.13 Modeling of O2-conducting membrane reactor

Figure 31: Concept of O2-conducting membrane reactor

The concept of an O2-conducting membrane reactor is presented in Fig. 31. The following
takes place in the membrane reactor:
Transfer of O2 from the air side to the depleted fuel side
Heat transfer
Oxidation of CO, CH4 and H2
In the O2-conducting membrane, O2 from the air is permeating through the membrane
without mixing the two streams from the cathode and anode, and by oxidizing the CO, CH4
and H2 in the depleted syngas a high purity CO2 stream is created.
The oxidation takes place in a Gibbs free energy reactor. The membrane reactor model also
has two heat exchangers in it because the thickness of the membrane separating the two gas
streams is very thin and, thus, heat transfer takes place.
The advantage of this concept compared to oxy-combustion is that no additional energy is
spent on compressing additional air for the ASU and separating O2 in the ASU. On the other
hand, oxy-combustion is a fairly simple and developed technology while oxygen conducting
membranes are in the phase of development, and some R&D has to be done in order for this
to be commercially feasible.

45
Currently the flux of O2 through the oxygen conducting membranes is relatively low and the
stability in the aggressive environment of syngas at elevated temperatures and pressures is
questionable. If these can be solved the O2 conducting membranes would improve the
efficiency of the plants. In addition the O2 conducting membrane may replace the ASU.

2.14 Net power output calculations

For the net power calculations the power is generated in the:
SOFC
Gas Turbine
Rankine Cycle
Expansion of sweep gas
And consumed in the:
Air Compressor
Refrigeration plant for water knock-out from CO2 rich stream
Compression of CO2 for storage
Compression of permeate stream
ASU
Those which are taken into account for a certain concept depends on the system configuration
(Table 14).
After the net-power calculations have been done the efficiencies are calculated. This is done
by dividing the net-power with power (based on the LHV and HHV) from the coal slurry fed
to the gasifier. In addition, the efficiencies without the power needed for water knock-out and
compressing the CO2 for storage are calculated in order to compare the power production of
each concept and to compare the drop in efficiency caused by the CO2 preparation for
storage.

2.15 Inputs to the model

There are two inputs to this model: the syngas and the air flow to the compressor. The content
and flows of the syngas and air are presented in table 9. The syngas and air content, and other
parameters, were taken from the Fuel Cell Handbook [1.12], p 67. The mass flow of syngas
to the fuel cell that was taken was half of what was in the Fuel Cell Handbook. The air flow
was chosen to be 9 times the flow of syngas.

Description T P Mass Mole CH4 CO CO2 H2 H2 H2S N2+ NH O2

Flow Flow O Ar 3

°C bar t/h kmol/hr % % % % % % % % %

Clean 399 15 56,5 2950 0,3 42,3 9,5 35,8 9,6 trace 1,5 0,2
Syngas
Air 20 0,98 TBS* TBS* trace 1,1 78,1 20,8
*TBS – to be specified

Table 9: Content and other parameters of syngas and air fed to the system

46
2.16 Chapter References
2.1 R.J. Braun, "Modeling, Analysis, and Optimization of IGFC Systems (Task I-C),
presentation prepared for the U.S. Department of Energy, National Energy
Technology Laboratory, Pittsburgh, PA October (2008)
2.2 Moran, Shapiro, Fundamentals of Engineering Thermodynamics 6th Edition,
Wiley 2007 p 67
2.3 Iyoha, H2 Production in Palladium & Palladium-Copper Membrane Reactors at
1173K in The Presence of H2O, Ph.D. Thesis, University of Pittsburgh – 2007
2.4 http://en.wikipedia.org/wiki/First_law_of_thermodynamics - web page

47
3 Results

In Fig. 32 the flow sheet of the IGFC is presented. In the empty square the different tail-gas
concepts can be applied. Only the simple tail-gas combustor where the anode and cathode
streams are mixed is different and is presented on Fig 33.

Figure 32: Flow sheet of IGFC (CO2 capture)

1. Air compressor
2. Air pre-heater
3. Syngas pre-heater
4. SOFC
5. SOFC anode
6. SOFC cathode
7. Tail-gas concept
8. Gas turbine
9. HRAG 1
10. Exhaust (air)
11. HRSG 2
12. Water knock-out and compression of CO2
13. CO2 storage
If the CO2 is vented some of the components (water knock-out and compression of CO2),
compared to if CO2 is captured, are not needed.

48
 Figure 33: Flow sheet of IGFC (venting of CO2)
1. Air compressor
2. Syngas pre-heater
3. SOFC
4. SOFC anode
5. SOFC cathode
6. Tail-gas combustor
7. Gas turbine
8. HRSG
9. Exhaust (Air)
The following results are presented:
1. Air compressed and split fractions going to the ASU and the SOFC cathode
2. Fraction and flows of depleted air needed to be recycled in order to have 650°C in the
SOFC cathode inlet
3. H2 recovered and/or combusted in the anode stream
4. Temperature and properties of air going to the gas turbine
5. The content and properties of the CO2-rich stream sent to storage
6. Net power of the system and the breakdown of where and how much power is
produced/consumed
7. Overall efficiencies of the system with capture and without capture
8. Drop in efficiency caused by the preparation of CO2 for storage

Tail-gas Oxy- H2-MR, H2-MR, O2-MR

combustor combustion N2-sweep air sweep

49
 Split 0,63 0,53 0,60 0,53 0,53
fraction
recycled
kg air 1,62 1,08 1,43 1,09 1,09
recycled per
kg air inlet
Temp. 399 483 428 482 482
before
recycling
[°C]
Table 10: Split fraction of cathode air recycled
In all cases the air enters the compressor at ambient temperature (20°C) and pressure (0,98
bar), and is compressed to 15,1 bars. The temperature rises to 399°C. In every concept,
except the tail-gas combustor, the air is pre-heated with the heat from the CO2 rich stream,
but this heat is not sufficient to increase the temperature of air up to 650°C. To overcome this
by not using external heat sources, the recycled cathode stream is used.
As shown in table 10, the lower the temperature of the air before the cathode, the more
cathode outlet air per kilogram of air fed to the cathode has to be recycled. It can also be seen
that the higher the air temperature is before the recycling the more air has to be compressed
for the cathode.

Figure 34: H2 recovery [%]

In figure 34 the H2 recovery is presented. The recovery percentage shows how much H2 is
reacted in a useful way, the H2 that was not recovered was stored together with the CO2; this
is in the case of H2-conducting membranes due to the nature of H2-membranes, where the
recovery of 100% of H2 is not easily achievable.
Regarding the higher H2 recovery for the H2-conducting membrane with air as sweep gas
(figure 34), the reason for this is the fact that there is air on the permeate side and H 2 reacts
with O2 right after permeation. It was assumed that the partial pressure of H2 on the permeate
side remains close to zero along the whole membrane and thus higher permeation rates occur,
compared to when N2 is used as sweep gas.

50
 Tail-gas Oxy- H2-MR, H2-MR, O2 -
combustor combustion N2- air MR
sweep sweep
Temperature inlet 937 920 954 897 922
[°C]
Temperature outlet 425 388 411 374 385
[°C]
Mass flow to GT 538000 579900 514400 589700 575700
[kg/hr]
Power generated 90400 95600 88300 96600 94900
[kW]
Power for 62900 80900 68500 78200 77600
compressing air
Net power from GT 27500 14700 19700 18300 17400
Table 11: Properties of to the gas turbine
On table 11 the properties of the media flowing through the gas turbine are presented and in
addition the power generated and consumed by the gas turbine is presented. The power
generated and consumed is directly related to the amount of air flowing through the gas
turbine. Temperature has less effect.

Tail-gas Oxy- H2-MR, H2-MR, O2 -

combustor* combustion N2- air MR
sweep sweep
Temperature [°C] 126 126 174 188 91
Pressure [bar] 1,023 150 150 150 150
Mass flow [kg/hr] 538000 69300 69100 69100 69000
Molar flow [kmol/hr] 18500 1600 1600 1600 1600
Table 12: CO2 for sequestration
The parameters of the CO2-rich stream going to storage are presented in table 12. It can be
seen that the temperature in all cases is in the range of 91 to 188 °C. These temperatures are
relatively moderate but still have to be taken into account when designing the storage
facilities.

51
 Figure 35: CO2 fraction in the exhaust

If a simple mixing of anode and cathode streams is used to burn the fuel in the tail gas, the
molar fraction of CO2 would be below 10% (figure 35). If we use the other tail-gas concepts
the molar fraction of CO2 reaches 94-97%. Concentrations this high make it possible to
directly capture and prepare this CO2 for storage. Only water knock-out and compressing is
required.

Figure 36: Net power production

The highest net power is achieved when the CO2 is vented (figure 36). With CO2 capture
additional power is required for water knock-out and compression of CO2 for storage. The
DC power from the SOFC is 74,7 MW in all cases because the fuel parameters and utilization
are the same. What varies is power output from the gas turbine, due to the different mass
52
flows and inlet temperatures of working fluid. The net power generated by the systems with
CO2 capture are almost equal, the difference is up to 6 MW.
The power generated by the systems with CO2 capture is around 80% compared to when CO2
is vented. But no CO2 is captured.

Figure 37: Power production breakdown

The power production breakdown of the created power system is presented in figure 37. As is
visible, the bulk of the power is generated with the gas turbine and the SOFC. The Rankine
steam cycle produces around 10 per cent of the total power. It should be considered whether
it is reasonable to add the Rankine cycle to the system. That consideration is not possible for
this thesis report because no cost estimates have been done.

Figure 38: Power consumption breakdown

53
The breakdown of the power consumption (figure 38) shows that the majority of the overall
power consumption of the plant comes from compressing the air. Some of it is used for the
ASU but the main part is utilized for cooling the SOFC. The reason for compressing that
much air is that that is how direct cooling with the air flow takes place. For future work the
indirect cooling of the stack should be considered. This would decrease the amount of air
needed to be compressed. The other places where power is needed play a significantly
smaller part in the overall power consumption. It has to be kept in mind that changing the air
flow to the stack may have affected the overall operation of the system e.g. flow of air is
smaller and thus higher temperatures at the inlet of the gas turbine are achievable.

Tail-gas Oxy- H2-MR, H2-MR, O2 -

combustor* combustion N2- air MR
sweep sweep
Overall efficiency 55 47 45 46 44
(LHV)
Table 13: Overall efficiency [%]

Figure 39: Efficiency breakdown

From the CO2 capture concepts oxy-combustion shows the highest overall efficiency (table
13), but the others are not far behind, only up to 3 per cent points less. In the net power
produced the difference is around 6 MW (figure 36). The highest efficiency is achieved when
the CO2 is vented; the efficiency is 8 per cent points higher compared to the concept using
oxy-combustion.
The efficiencies of the different concepts are compared without taking into account the losses
involved with water knock-out and compression of CO2 (figure 39). Also, the highest
efficiency belongs to the concept when CO2 is vented. No water knock-out and compression
of CO2 takes place, but the difference between other concepts is only 3 per cent points
compared to the most efficient one, which is the H2-conducting membrane with N2 as sweep
gas.

54
The highest penalty in efficiency, because of CO2 capture, belongs to the systems which have
an H2-conducting membrane with N2 as sweep gas and the O2-conducting membrane, -7 per
cent points (Figure 39).
As is seen in the results (figure 39), CO2 capture has a penalty on the overall efficiency of the
IGFC power plant. In addition, even if the power losses connected to CO2 capture are not
taken into account the overall efficiencies are lower compared to when CO2 is vented. This is
because if CO2 is sent to storage, the mass flow through the gas turbine will be smaller (table
11), and even though the mass flow through the gas turbine of the CO2 venting case is one of
the smallest, it is compensated by the fact that less air has to be compressed and the net value
of power produced/consumed by the gas turbine is bigger.
By comparing the penalties associated with CO2 capture (table 13), the overall efficiency is
some 8-11 per cent points lower. It is a significant difference, but this penalty may possibly
be compensated with the implementation of a carbon tax because the reason for the drop in
the efficiency comes mostly from the water knock-out and compression of CO2.
It has to be noted that in the Rankine cycle the heat source temperatures are in the range of
350-450°C. The efficiency of the Rankine cycles, which was chosen to be 30%, should be
revised and set according to the temperatures of the heat sources.
From the different concepts available today the oxy-combustion for burning the tail-gas is the
most promising one. This is because it is a mature and well-proven technology, and
membranes are still being developed. On the other hand, if an O2-conducting membrane
technology will prove itself it may take away the need for an ASU and thus decrease the
investment costs of the plant. The membrane technology is promising and allows for
simplification of the system, but as seen in figure 29 the flow sheet can get quite complex, if
the temperature and operating pressure of the devices is different.

55
APPENDIX A

Brayton cycle [A.1]

The Brayton cycle is a thermodynamic cycle that describes the workings of the gas turbine
engine, basis of the jet engine and others. It is named after George Brayton (1830–1892), the
American engineer who developed it, although it was originally proposed and patented by
Englishman John Barber in 1791. It is also sometimes known as the Joule cycle.

A Brayton-type engine consists of three components:

A gas compressor
A mixing chamber
An expander

In the original 19th-century Brayton engine, ambient air is drawn into a piston compressor,
where it is compressed; ideally an isentropic process. The compressed air then runs through a
mixing chamber where fuel is added- a constant-pressure isobaric process. The heated (by
compression), pressurized air and fuel mixture is then ignited in an expansion cylinder and
energy is released, causing the heated air and combustion products to expand through a
piston/cylinder- another ideally isentropic process. Some of the work extracted by the
piston/cylinder is used to drive the compressor through a crankshaft arrangement.

The term Brayton cycle has more recently been given to the gas turbine engine. This also has
three components:

A gas compressor
A burner (or combustion chamber)
An expansion turbine

Ideal Brayton cycle:

isentropic process - Ambient air is drawn into the compressor, where it is pressurized.
isobaric process - The compressed air then runs through a combustion chamber,
where fuel is burned, heating that air—a constant-pressure process, since the chamber
is open to flow going in and out.
isentropic process - The heated, pressurized air then gives up its energy, expanding
through a turbine (or series of turbines). Some of the work extracted by the turbine is
used to drive the compressor.
isobaric process - Heat Rejection (in the atmosphere).

Actual Brayton cycle:

adiabatic process - Compression.

isobaric process - Heat Addition.

A-1
 adiabatic process - Expansion.
isobaric process - Heat Rejection.

Figure 40: Idealized Brayton Cycle [1.15]

Since neither the compression nor the expansion can be truly isentropic, losses through the
compressor and the expander represent sources of inescapable working inefficiencies. In
general, increasing the compression ratio is the most direct way to increase the overall power
output of a Brayton system.

Figure 41: Brayton Cycle (Gas Turbune) Efficiency

A-2
Here are two plots, Figure 42 and Figure 43, for the ideal Brayton cycle. One plot indicates
how the cycle efficiency changes with an increase in pressure ratio, while the other indicates
how the specific power output changes with an increase in the gas turbine inlet temperature
for two different pressure ratio values.

In 2002 a hybrid open solar Brayton cycle was operated for the first time consistently and
effectively with relevant papers published, in the frame of the EU SOLGATE program. The
air was heated from 570 K to over 1000 K in the combustor chamber.

Figure 42: Brayton Cycle (Gas Turbine) Specific Power Output

Methods to increase power

The power output of a Brayton engine can be improved in the following manners:

Reheat, wherein the working fluid—in most cases air—expands through a series of
turbines, then is passed through a second combustion chamber before expanding to
ambient pressure through a final set of turbines. This has the advantage of increasing
the power output possible for a given compression ratio without exceeding any
metallurgical constraints (typically about 1000°C). The use of an afterburner for jet
aircraft engines can also be referred to as reheat, it is a different process in that the
reheated air is expanded through a thrust nozzle rather than a turbine. The
metallurgical constraints are somewhat alleviated enabling much higher reheat
temperatures (about 2000°C). The use of reheat is most often used to improve the
specific power (per through put of air) and is usually associated with a reduction in
efficiency. This is most pronounced with the use of after burners due to the extreme
amounts of extra fuel used.

A-3
Methods to improve efficiency

The efficiency of a Brayton engine can be improved in the following manners:

Intercooling, wherein the working fluid passes through a first stage of compressors,
then a cooler, then a second stage of compressors before entering the combustion
chamber. While this requires an increase in the fuel consumption of the combustion
chamber, this allows for a reduction in the specific volume of the fluid entering the
second stage of compressors, with an attendant decrease in the amount of work
needed for the compression stage overall. There is also an increase in the maximum
feasible pressure ratio due to reduced compressor discharge temperature for a given
amount of compression, improving overall efficiency.

Regeneration, wherein the still-warm post-turbine fluid is passed through a heat

exchanger to pre-heat the fluid just entering the combustion chamber. This directly
offsets fuel consumption for the same operating conditions, improving efficiency. It
also allows results in less power lost as waste heat.

A Brayton engine also forms half of the combined cycle system, which combines
with a Rankine engine to further increase overall efficiency.

Cogeneration systems make use of the waste heat from Brayton engines, typically for
hot water production or space heating.

Reverse Brayton cycle

A Brayton cycle that is driven in reverse, via net work input, and when air is the working
fluid, is the air refrigeration cycle or Bell Coleman cycle. Its purpose is to move heat rather
than produce work. This air cooling technique is used widely in jet aircraft.

Rankine cycle [A.2]

The Rankine cycle is a thermodynamic cycle which converts heat into work. The heat is
supplied externally to a closed loop, which usually uses water as the working fluid. This
cycle generates about 80% of all electric power used throughout the world, including all solar
thermal, biomass, coal and nuclear power plants. It is named after William John Macquorn
Rankine, a Scottish polymath. A Rankine cycle describes a model of the operation of steam
heat engines most commonly found in power generation plants.

A-4
 Figure 43: Engine with a Rankine cycle [1.18]
Description

A Rankine cycle describes a model of the operation of steam heat engines most commonly
found in power generation plants. Common heat sources for power plants using the Rankine
cycle are coal, natural gas, oil, and nuclear.

The Rankine cycle is sometimes referred to as a practical Carnot cycle as, when an efficient
turbine is used, the TS diagram will begin to resemble the Carnot cycle. The main difference
is that a pump is used to pressurize liquid instead of gas. This requires about 100 times less
energy than that compressing a gas in a compressor (as in the Carnot cycle).

The efficiency of a Rankine cycle is usually limited by the working fluid. Without the
pressure going super critical, the temperature range the cycle can operate over is quite small.
Turbine entry temperatures are typically 565°C (the creep limit of stainless steel) and
condenser temperatures are around 30°C. This gives a theoretical Carnot efficiency of around
63% compared with an actual efficiency of 42% for a modern coal-fired power station. This
low turbine entry temperature (compared with a gas turbine) is why the Rankine cycle is
often used as a bottoming cycle in combined cycle gas turbine power stations.

The working fluid in a Rankine cycle follows a closed loop and is re-used constantly. The
water vapor often seen billowing from power stations is generated by the cooling systems
(not from the closed loop Rankine power cycle) and represents the waste heat that could not
be converted to useful work. Note that steam is invisible until it comes in contact with cool,
saturated air, at which point it condenses and forms the white billowy cloud seen leaving
cooling towers. While many substances could be used in the Rankine cycle, water is usually
the fluid of choice due to its favorable properties, such as nontoxic and unreactive chemistry,
abundance, and low cost, as well as its thermodynamic properties.

One of the principal advantages it holds over other cycles is that during the compression
stage relatively little work is required to drive the pump, due to the working fluid being in its
liquid phase at this point. By condensing the fluid to liquid, the work required by the pump
will only consume approximately 1% to 3% of the turbine power and give a much higher
efficiency for a real cycle. The benefit of this is lost somewhat due to the lower heat addition

A-5
temperature. Gas turbines, for instance, have turbine entry temperatures approaching 1500°C.
Nonetheless, the efficiencies of steam cycles and gas turbines are fairly well matched.

Processes of the Rankine cycle

There are four processes in the Rankine cycle, each changing the state of the working fluid.
These states are identified by number in the diagram to the right.

Figure 44: T-s diagram of a typical Ramkine cycle operating between pressures of 0,06 bar
and 50 bar

Process 1-2: The working fluid is pumped from low to high pressure, as the fluid is a
liquid at this stage the pump requires little input energy.
Process 2-3: The high pressure liquid enters a boiler where it is heated at constant
pressure by an external heat source to become a dry saturated vapour.
Process 3-4: The dry saturated vapour expands through a turbine, generating power.
This decreases the temperature and pressure of the vapour, and some condensation
may occur.
Process 4-1: The wet vapour then enters a condenser where it is condensed at a
constant pressure and temperature to become a saturated liquid. The pressure and
temperature of the condenser is fixed by the temperature of the cooling coils as the
fluid is undergoing a phase-change.

In an ideal Rankine cycle the pump and turbine would be isentropic, i.e., the pump and
turbine would generate no entropy and hence maximize the net work output. Processes 1-2
and 3-4 would be represented by vertical lines on the Ts diagram and more closely resemble
that of the Carnot cycle. The Rankine cycle shown here prevents the vapor ending up in the
superheat region after the expansion in the turbine, which reduces the energy removed by the
condensers.

Real Rankine cycle (non-ideal)

In a real Rankine cycle, the compression by the pump and the expansion in the turbine are not
isentropic. In other words, these processes are non-reversible and entropy is increased during

A-6
the two processes. This somewhat increases the power required by the pump and decreases
the power generated by the turbine.

Figure 45: Rankine cycle with superheat

In particular the efficiency of the steam turbine will be limited by water droplet formation. As
the water condenses, water droplets hit the turbine blades at high speed causing pitting and
erosion, gradually decreasing the life of turbine blades and efficiency of the turbine. The
easiest way to overcome this problem is by superheating the steam. On the Ts diagram above,
state 3 is above a two phase region of steam and water so that, after expansion, the steam will
be very wet. By superheating, state 3 will move to the right of the diagram and hence produce
a dryer steam after expansion.

Regenerative Rankine cycle

The regenerative Rankine cycle is so named because after emerging from the condenser
(possibly as a subcooled liquid) the working fluid is heated by steam tapped from the hot
portion of the cycle. On the diagram shown, the fluid at 2 is mixed with the fluid at 4 (both at
the same pressure) to end up with the saturated liquid at 7. The Regenerative Rankine cycle
(with minor variants) is commonly used in real power stations.

A-7
 Figure 46: Regenerative Rankine cycle

Another variation is where 'bleed steam' from between turbine stages is sent to feed water
heaters to preheat the water on its way from the condenser to the boiler.

Appendix References
A.1 http://en.wikipedia.org/wiki/Brayton_cycle - web page
A.2 http://en.wikipedia.org/wiki/Rankine_cycle - web page

A-8
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