Reactor HYSYS PDF

REPORT INDEX
Report index .............................................................................................1

RESUM.....................................................................................................3
RESUMEN.................................................................................................3
ABSTRACT................................................................................................3
ACKNOWLEDGMENTS.................................................................................5
Chapter 1: INTRODUCTION .................................................................. 6
1.1. Objectives ..................................................................................7
Chapter 2: INTRODUCTION TO FISCHER-TROPSCH............................... 8
2.1. Fischer-Tropsch ...........................................................................8
2.1.1. History .................................................................................8
2.1.2. Process ............................................................................... 12
2.2. Raw Materials............................................................................ 15
2.2.1. Sources of Carbon Dioxide..................................................... 15
2.2.2. Sources of Hydrogen ............................................................ 19
2.2.3. Production of Syngas ............................................................ 24
2.3. RWGS Reaction ......................................................................... 25
2.3.1. Reaction ............................................................................. 26
2.3.2. RWGS Reaction in Microreactors ............................................. 27
2.3.3. Catalyst Selection................................................................. 27
2.3.4. Reaction Kinetics.................................................................. 30
Chapter 3: INTRODUCTION TO MICROREACTORs ............................... 32
3.1. Definition.................................................................................. 32
3.1.1. Microsystems termed microreactor ......................................... 32
3.1.2. Structural hierarchy of microreactors ...................................... 32
3.1.3. Functional Classification of Microreactors ................................. 34
3.1.4. Dividing line between Analysis and Reaction systems ................ 34
3.2. Fundamental Advantages of Microreactors..................................... 35
3.2.1. Fundamental Advantages of miniaturized analysis systems......... 35
3.2.2. Fundamental Advantages of nano-scale reactors....................... 35
3.2.3. Advantages of microreactors due to decrease of physical size. .... 36
3.2.4. Advantages of microreactors due to increase of number of units. 37
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Pau Gerard Ribas Vendrell i Anna RubioPelegrín
3.3. Process Intregration/Intensifications............................................. 39

3.3.1. Introduction to Distributed generation ..................................... 39
3.3.2. Traditional combustion generators .......................................... 40
3.3.3. Non-traditional generators..................................................... 42
Chapter 4: EXPERIMENTAL DESIGN .................................................... 48
4.1. Experimental set-up ................................................................... 48
4.2. Microreactor main parts .............................................................. 49
4.3. Proposed of micro reactor designs. ............................................... 50
4.4. Material of construction .............................................................. 51
4.5. Operation conditions .................................................................. 52
Chapter 5: MODELING AND SIMULATION ........................................... 53
5.1. Computer packages ................................................................... 55
5.2. Hysys Simulations ..................................................................... 55
5.2.1. Hysys devices ...................................................................... 55
5.2.2. Fluid packages ..................................................................... 58
5.2.3. Hysys Flow sheet ................................................................. 59
5.3. Model 0: Conversion .................................................................. 60
5.4. Model I: Thermodynamic ............................................................ 61
5.4.1. Excel Simulation .................................................................. 61
5.4.2. Hysys simulation .................................................................. 63
5.4.3. Hysys simulation: MODEL I A ................................................. 65
5.4.4. Hysys simulation: MODEL I C ................................................. 67
5.4.5. Hysys simulation: MODEL I B/D.............................................. 68
5.5. Model II: Chemist kinetics........................................................... 70
5.5.1. CSTR .................................................................................. 70
5.5.2. Plug Flow reactor ................................................................. 70
5.5.3. PFR: Model II A.................................................................... 70
5.5.4. PFR: Model II B.................................................................... 82
5.6. Model III: Adsorption kinetics ...................................................... 88
Chapter 6: CONCLUSIONS................................................................... 89
6.1. Proposal of possible methods....................................................... 89
6.2. Conclusions .............................................................................. 90
Chapter 7: BIBLIOGRAFIA .................................................................. 91
7.1. Referències bibliogràfiques.......................................................... 91
7.2. Bibliografía de Consulta .............................................................. 94
Annexes a la memòria
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RESUM
El Simulation of the Reverse Water Gas Shift (RWGS) in a microreactor
forma part d’una investigació major. El nostre treball es centra en una de les
parts més importants d’aquesta investigació sobre el potencial de la tecnologia
de microreactors en la generació de gasolina distribuïda. Concretament en la
creació i desenvolupament d’una simulació de la reacció RWGS. Cal afegir que la
investigació vol demostrar que la distribució de la producció d’hidrocarburs fent
ús de microreactors, és una opció factible en un futur no molt llunyà.
RESUMEN
El Simulation Simulation of the Reverse Water Gas Shift (RWGS) in a
microreactor forma parte de una investigación mayor. Nuestro trabajo se
centra en una de las partes más importantes de la investigación sobre el
potencial de la tecnología de microreactores en la generación de gasolina
distribuida. Concretamente, en la creación y desarrollo de una simulación de
reacción RWGS. Cabe añadir que la investigación quiere demostrar que la
distribución de la producción de hidrocarburos haciendo uso de microreactores,
es una opción factible en un futuro no muy lejano.
ABSTRACT
The Simulation of the Reverse Water Gas Shift (RWGS) in a microreactor
is part of bigger investigation. Our work has been focused in one of the most
important parts of the investigation about the potential of microreactor
technology for distributed fuel generation. Concretely, the creation and
development of the RWGS reaction simulation model. Furthermore, the overall
investigation wants to demonstrate that the distributed production of
hydrocarbons using microreactors is a feasible option in the not too far future.
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ACKNOWLEDGMENTS
Firstly we would like to thank Prof. Toshko Zhelev and Pádraig Mac Suibhne who
were our project supervisors and who provided guidance and support throughout
the course of the project.
We would like also to thank our appreciate Dr. Moisès Graells whose assistance
was invaluable. We would like also to acknowledge the assistance of the
following people who also helped considerably during the completion of this
project: Dr. Seamus McMonagle, Jaime Rojas, Bruno Rousset and of course our
chemical engineers lab-mates.
Finally we would like to thank to all the people that make possible to come to
Ireland.
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CHAPTER 1:
INTRODUCTION
The RWGS simulation in a microreactor is part of bigger investigation, carried

out by Pádraig Mac Suibhne, Dr. Toshko Zhelev, Dr. Erzeng Xue between the
University of Limerick and Tyndall Research Institute in Ireland. The main
purpose of the research team is to explore the potential of microreactor
technology for distributed fuel generation, i.e. the application of the required
chemical reactions for fuel re-synthesis in several distributed locations at the
required scale. Furthermore, the overall investigation wants to demonstrate that
the distributed production of hydrocarbons using microreactors is a feasible
option in the not too far future.
The investigation is being focused in four different areas:
Figure 1. Project working areas
The four studies areas can be segmented in two other parts: with and without
experimental data.
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Simulation of the Reverse water gas shift (RWGS) microreactor
1. Without experimental data: Reactor Design, Mass and Heat Transfer studies
and Microreactor simulation (Reverse Water gas shift reaction and Fisher-
Tropsch reaction)
2. With experimental data results: Demonstration of chemistry in micro-scale,

Economic evaluation.
The diagram below shows the overall process that starts with the raw materials
sources and finished by the final production of fuel.
Figure 2. Example of process that follow the general idea of the

investigation [53]
Our work has been focused in one of the most important parts of this process.
Concretely, the creation and development of the Reverse water gas shift reaction
simulation model. For this purpose two powerful computer packages have been
used: Microsoft Excel© and AspenHysys®.
1.1. Objectives
The objectives of Simulation of the Reverse water gas shift (RWGS)
microreactor are shown below:
 Proposal of four different models:
a) Model 0:conversion
b) Model 1: thermodynamic
c) Model 2: chemist kinetics and
d) Model 3: absorption kinetics.
 Analyse which of the four models proposed are the more suitable for the
RWGS system.
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CHAPTER 2:
INTRODUCTION
TO FISCHER-
TROPSCH
The hydrocarbon resources of the world are not evenly distributed. Substantial
proportions of known reserves are situated in remote locations far from areas of
high consumption. Transportation of liquid hydrocarbons from source to
consumer is a task for which a large and flexible infrastructure exists. However,
when natural gas deposits in remote locations are to be exploited, the
transportation task becomes a major challenge, particularly if geography,
economics, or combination of both precludes the possibility of a pipeline. [17]
2.1. Fischer-Tropsch
Fischer-Tropsch synthesis is a well-known process for conversion of syngas to
synfuel and raw materials for the chemical industry. The process is versatile in
the raw materials consumption, i.e. it can use any type of coal, natural gas or
similar types of carbon-containing feedstock as its material, and similarly the
product distribution can also be changed. The increase of mineral oil prices has
caused intense efforts to develop the Fischer-Tropsch process on a commercial
scale. [17]
2.1.1. History
The Fischer-Tropsch reaction is not new. It has been known about, and pplied in
the production of liquid fuels for decades. The details of the Fischer-Tropsch
reactions and process are still not completely understood, even though the
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reaction was discovered 90 years ago. Below a timeline of the reaction’s history
is outlined. The timeline is taken up from reference [1].
1902 P Sabatier and J. D. Senderens hydrogenated CO over Ni to produce CH4 .
1910 A. M. Mittasch, C. Bosch, and F. Haber developed promoted Fe catalysts
for the synthesis of NH3.
1912-1913 The Kaiser-Wilhelm Association for the advancement of knowledge
established its third institute in Mulheim, dedicated to coal research, the Kaiser-
Wilhelm-Institud fur Kohleforsheung (KWIK). Franz Fischer, Professor of
Electrochemistry at the Technical University, Berlin, was appointed Director of
the new institute.
1913 Badische Anilin und Soda Fabrik received (BASF) received patents on the
preparation of hydrocarbons and oxygenates by the hydrogenation of CO at high
pressure, usually on oxide catalysts.
1920 Brennstoff-Chemie was started by Fischer. KWIK also had been publishing
Abhandlung zur Kenntnis der Kohle since 1917.
1922-1923 Fischer and Hans Tropsch obtained Synthol, mostly oxygenates,
from H2 + CO on alkalized Fe and other catalysts.
1923 Basf and I. G. Farben (IG) obtained patents on Zn-based, Fe-free catalysts
for methanol synthesis.
1925 Fischer and Tropsch announced the synthesis of higher hydrocarbons at
atmospheric pressure; Co and Ni seemed to be promising catalysts. A reason for
working at 1 atm was that BASF had patents covering higher pressure; this
notion may have delayed the development of useful Fe catalysts for decade.
1926-1930 Studies were made on the new process in England, Japan, and the
United States. Workers at the United States. Workers at the U. S. Bureau of
Mines incorporated ethylene in the synthesis on Co catalysts.
1928 Tropsch left KWIK to become director of a coal research institute in
Prague. In 1931, he went to Chicago to work at Universal Oil Products and to be
Adjunct Professor at the Armour Institute and later at the University of Chivago.
1928-1930 P. K. Frohlich and W. K. Lewis studied the synthesis of higher
alcohols on alkalized ZnO-Cr2O3 and other catalysts.
1931-1932 Fischer and K. Meyers developed Ni-ThO2-kieselguhr and Co-ThO2-
kieselguhr, which were relatively sophisticated catalysts designed for the
primitive reactors of that time. Initial studies were on Ni because of the short
supply of Co; however, the Ni catalysts did not operate properly in large
reactors. The yields of CH4 were too large. Pilot plant work was started at KWIK
in 1930.
1933-1939 Pilot-plant tests and further development of Co catalysts were made
by Ruhrchemie AG.
1935 Tropsch returned to Germany critically ill; he died on 8 October.
1935-1945 The FTS was operated commercially in Germany using Co catalysts.
1936 Fischer and Helmut Pichler found that Co catalysts also operated
satisfactorily in the middle pressure range, 5-20 atm.
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1936 The first commercial catalytic cracking unit, developed by Eugene Houdry,
was installed.
1937 Fischer and Pichler discovered that synthesis on Fe was greatly improved
by operating at 5-20 atm. At about the same same time, Herbert Kolbel at
Rheinpreussen also performed medium-pressure tests of Fe catalysts. Alkalized
Fe in this pressure range became a possible replacement for Co in the German
commercial plants.
1938 fischer and Pichler produced high-melting-point waxes in high-pressure
synthesis on Ru.
1939-1944 German industry joined in the development of an Fe catalyst to
replace Co in the existing plants. Improved reactors were also studied, incluiding
fixed-bed reactors with recycle, hot gas recycle, oil recycle, and slurry reactors.
1939-1944 Fischer and Pichler developed the Isosynthesis, and Otto Roelen the
OXO Process.
1942-1950 Fears of an impending shortage of petroleum in the United States
caused wide interest in coal-to-oil processes. A large research and development
program was authorized for the U.S. Bureau of Mines, and the American
petroleum and related industries initiated studies of FTS, often on Fe in fluidized
or entrained reactors.
1943 Fischer retired from KWIK and moved to Munich. Karl Zielgler became the
second Director of KWIK at Mulheim.
1943-1943 Kolbel initiated and directed the comparative tests I and II held at
Schwarzheide to select an Fe catalyst to replace Co in existing reactors; KWIK
and five companies participated. Although the results were remarkably good, no
replacement catalyst was selected, -probably because of the overall disarray of
activity that attended the approach of the end of the war.
1945 World War II ended, and the operation of FTS plants in Germany stopped.
Some plants in what is now East Germany (GDR) were confiscated by the Soviet
Union.
1947 Fischer died in Munich on 1 December.
14
1948 P.H. Emmett used molecules tagged with C to study the mechanism of
the FTS.
1948 The Kaiser-Wilhelm Gesellschaft becomes the Max-Planck Gesellschaft, and
the institute at Mulheim became a Max-Planck Institute.
1949 Kolbel and F. Engelhardt discovered that H2O and CO react on FTS
catalysts to yield typical FTS products.
1950 A fluidized-fixed bed process developed by Hydrocarbon Research,
Trenton, New Jersey was installed in Brownsville, Texas. This plant, called
Carthage Hydrocol, Inc., used reformed natural gas. Severe operating difficulties
required designing a new reactor, which was installed in 1953. The new reactor
operated properly, but the plant was promptly shut down, sold, and dismantled.
By the time the plant was operating correctly, the price of natural gas had more
than doubled. Merely selling the gas was more profitable than converting it to
gasoline and chemicals. At the same time, in South Africa, the SASOL FTS plant
using coal was constructed and opened in 1955. Lurgi gas generators and
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Rectisol gas-cleaning units were employed. Two types of FTS reactors, both with
and internal diameter of ~2 in., and entrained-solids reactor by M.W. Kellogg in
New jersey. After a year or more of start-up problems, these units have operated
successfully up to the present.
1953 R. B. Anderson and J. F. Shultz found that Fe nitrides are unique, durable
catalysts for the FTS that produce large yields of alcohols. Anderson developed
equations that predict the isomer and carbon-number distributions of FTS
products. Kolbel and P. Ackermann successfully operated a large slurry reactor in
a 10-ton-per-day demonstration plant.
1954 The abundance of petroleum in the world and its availability at very low
prices caused the decrease or termination of most of the programs of research
and development on coal-to-oil processes.
1957 G. Natta and co-workers studied the methanol and higher alcohol
syntheses.
1959 Pichler resumed work on FTS on Ru, which led to the polymethylene
synthesis.
1961 H. H. Storch died; he was the architect of the useful scientific and
engineering research programs on coal-to-oil processes at the U.S. Bureau of
mines in Pittsburgh and Bruceton, Pennsylvania.
1966 Imperial Chemical Industries (ICI) developed a moderate pressure
methanol synthesis employing copper-zinc oxide catalysts in a gas-recycle
reactor.
1969 Domestic production of petroleum in the United States became fell below
demand; the United States became an importer of oil.
1973 The oil embargo by the Organization of Petroleum Exporting Countries
(OPEC), followed by a fourfold increase in the price of petroleum, accelerated
research on coal-to-oil processes in the United States and many other countries.
With the demise of the U.S. Bureau of Mines, federally sponsored coal-to-oil
research became part of the Energy Research and Development Administration
(ERDA) and subsequently the Department of Energy.
1974 H. Pichler died in Karlsruhe on 13 October.
1975 In South Africa, the decision was made to build SASOL II, scheduled for
operation in 1980, and in 1979, plans were made for SASOL III, to begin
operation in 1982. The new plants are similar to the initial plant, except that
fixed-bed FTS reactors were not included in the new installations.
1976 Mobil announced a process for converting methanol to an aromatic
gasoline and C2 to C4 olefins on the shape-selective catalyst ZSM5. This process
may be serious competitor for FTS.
1981 In the New Zealand a methanol plant operating on natural gas plus the
mobile process was planned, scheduled for completion in 1985.
1982 The worldwide recession sharply decreased demand for petroleum. OPEC
was unable to control the production and price of oil among its members. The
relatively low cost and abundance of petroleum has discouraged new coal-to-oil
ventures. [1]
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2007 New technologies of CO2 capture become F-T technology in a interesting

source of energy.
2009 Chemists working for the U.S. Navy investigated Fischer-Tropsch for
generating fuels, obtaining hydrogen by electrolysis of seawater. When combined
with the dissolved carbon dioxide using a cobalt-based catalyst, this study
produced mostly methane gas. However, when using an iron-based catalyst, it
was possible to reduce the methane produced to 30 per cent with the rest being
predominantly short-chain hydrocarbons. Further refining of the hydrocarbons
produced applying solid acid catalysts, such as zeolites, can potentially lead to
the production of kerosene-based jet fuel.
The abundance of wanted CO2 makes seawater an attractive alternative fuel
source for scientists at the US.
The Fischer-Tropsch maybe, in a non far future, will be the answer for our
problems with the CO2, and a new resource of energy better than the oil. The
objective of the all research groups is trying to improve the output of this
reaction using new outcomes technologies.
2.1.2. Process
In the Fischer–Tropsch process or Fischer–Tropsch Synthesis, hydrocarbons
(CmHn) are synthesized from carbon monoxide (CO) and hydrogen (H2) (in other
words, syngas). The Fischer–Tropsch process is an established technology and
already applied on a large scale. [17]
The process a key component of gas to liquids technology (GTL) which produces
a petroleum substitute, typically from coal, natural gas, or biomass for use as
synthetic lubrication oil and as synthetic fuel. The F-T process has received
intermittent attention as a source of low-sulphur diesel fuel and to address the
supply or cost of petroleum-derived hydrocarbons.
The number of chemical reactions involved in the manufacture of syngas is very
large. The most important of these (limited to methane because it is the major
constituent of natural gas), given the objective of producing carbon monoxide
and hydrogen from methane, are reforming and partial oxidation, resulting in
hydrogen-to-carbon-monoxide ratios of 3 and 2, respectively. If a reforming
source of carbon dioxide is available reforming with carbon dioxide provides a
hydrogen-to-carbon-monoxide ratio of 1. The figures for higher hydrocarbons in
natural gas are correspondingly lower. The final hydrogen to carbon monoxide
ratio is influenced further by the carbon monoxide shift reaction.
Reforming (strongly endothermic):
(1)
(2)
Combustion (strongly exothermic):
(3)
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(4)
Shift conversion:
(5)
The reforming reactions (1) (2) are strongly endothermic and must be supported
by the strongly exothermic reactions of partial oxidation (3) and the complete
combustion (4). [17]
The Reverse Water Gas Shift reaction (RWGS) has to increase the quantity of CO
in front of the quantity of CO2. The spontaneous direction of the reaction is CO
to CO2 (WGS):
(6)
Consequently, we need to use some catalysts to force the reverse direction

(RWGS).
(7)
The RWGS is an endothermic reaction and the name of the product that is
obtained is Syngas.
The Fischer–Tropsch Synthesis was originally operated in packed-bed reactors.
These reactors have several drawbacks that can be overcome by a slurry reactor.
Figure 3. Diagram of a Slurry Bubble Column Reactor [18]
In these slurry reactors, the synthesis gas is bubbled through a suspension of

catalysts particles in an inert liquid. The heat of reaction is removed by
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circulation the slurry through external or internal heat exchangers. The slurry
reactor can be operated at higher temperatures and at low H2 to CO ratios
without any problems due to efficient heat transfer and uniform temperatures.
The application of very small catalysts particles caused no occurrence of intra-
particle heat and mass transfer resistances.
Figure 4: Diagram with the three main steps in the F-T.
Process conditions
The Fischer–Tropsch process is a very complicated process that requires a well-
defined choice of reactors, catalysts, and operating conditions to synthesize the
desired products. Even then, a mixture of compounds is obtained.
Generally, the Fischer–Tropsch process is operated in the temperature range of
150–300 °C (302–572 °F). Higher temperatures lead to faster reactions and
higher conversion rates but also tend to favour methane production. As a result,
the temperature is usually maintained at the low to middle part of the range.
Increasing the pressure leads to higher conversion rates and also favours
formation of long-chained alkenes both of which are desirable. Typical pressures
range from one to several tens of atmospheres. Even higher pressures would be
favourable, but the benefits may not justify the additional costs of high-pressure
equipment.
Product distribution
The subsequent chain growth in the Fischer–Tropsch process is comparable with
a polymerization process, resulting in a distribution of chain length of the
products. In general, the product range includes the light hydrocarbons methane
(CH4), ethane (C2H6), propane (C3H8) and butane (C4H10); naphtha (C5H12 to
C12H26); kerosene diesel fuel (C13H28 to C22H46); low-molecular-weight wax
(C23H48 to C32H66); and high-molecular-weight wax (>C33H68). Linear alpha-olefins
are also produced, but the distribution of the products depends on the catalyst
and the process operation conditions (temperature, pressure and residence
time).[17]
The theoretical length chain product distribution of hydrocarbons in the Fischer–
Tropsch process can be described by means of Anderson-Schulz-Flory equation,
which can be expressed as:
(8)
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Where, Wn is the weight fraction of chains with n carbon atoms. “α” is the chain
growth probability or the probability that a molecule will continue reacting to
form a longer chain. In general, α is largely determined by the catalyst and the
specific process conditions.
Examination of the above equation reveals that methane will always be the
largest single product; however by increasing α close to one, the total amount of
methane formed can be minimized compared to the sum of all of the various
long-chained products.
Increasing the value of α, the formation of long-chained hydrocarbons increased,
too. Therefore, for production of liquid transportation fuels it may be necessary
to crack some of the Fischer-Tropsch products.
In order to avoid this, some researchers have proposed using zeolites or other
catalyst substrates with fixed sized pores that can restrict the formation of
hydrocarbons longer than some characteristic size (usually n<10). This way they
can drive the reaction so as to minimize methane formation without producing
lots of long-chained hydrocarbons. Such efforts have met with only limited
success.
Future of synfuel
Synfuels produced by Fischer-Tropsch process are nowadays more expensive
than natural-oil-based hydrocarbons fuels. However, under certain conditions
and in the next century, the process economics may become favourable. The
process deserves special attention where:
1. Coal reserves are significant and available at a cheaper rate.
2. Natural gases are abundant.
In the long run, production of hydrocarbon synthesis based on coal will exceed
that of oil. [17]
2.2. Raw Materials

The Reverse water was shift (RWGS) reaction involves two main reactants:
Carbon Dioxide (CO2) and Hydrogen (H2). Below, it is explain how both of them
are obtained.
2.2.1. Sources of Carbon Dioxide

Liquefaction of Carbon Dioxide
As generation of CO2 is inherent in the combustion of fossil fuels, efficient
capture of CO2 from industrial operations is regarded as an important strategy
which can achieve significant reduction in atmospheric CO2 levels.
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Figure 5. Purified, captured CO2 from combustion power plants.
Generally speaking, there are three basic CO2 capture:
 Pre-combustion capture
It involves the reaction of fuel with oxygen or air and in some cases steam to
produce a gas mainly composed of carbon monoxide and hydrogen, which is
known as synthesis gas (syngas) or fuel gas. In a gasification reactor, the
amount of oxygen available inside the gassifier is carefully controlled so that only
a portion of the fuel burns completely. This ‘‘partial oxidation’’ process provides
the heat necessary to chemically decompose the fuel and produce syngas.
The carbon monoxide formed is reacted with steaming a catalytic reactor, called
a shift converter, to give CO2 and more hydrogen. CO2 is then separated, usually
by a physical or chemical absorption process, resulting in a hydrogen-rich fuel.
which can be used in many applications, such as furnaces, gas turbines, engines
and fuel cells. This route needs long-term development in a number of enabling
technical areas including gasification, syngas cleaning, gas separation, hydrogen
turbine and fuel cells to achieve targeted efficiency towards a hydrogen
economy.
Figure 6. Post Combustion Capture Diagram [11]
 Oxy-fuel combustion
The Oxy-fuel combustion, nearly pure oxygen is used for combustion instead of
ambient air, thereby eliminating nitrogen is caused. If fuel is burnt in pure
oxygen, the flame temperature is excessively high, but CO2 and/or H2O-rich flue
gas can be recycled to the combustor to lower the flame temperature. Oxygen is
usually produced by low temperature air separation, and novel techniques to
supply oxygen to the fuel, such as membranes (e.g. oxygen permeable ceramic
membranes) have been utilized. The major disadvantages of oxy-fuel combustion
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are the high capital cost and large electric power requirement inherent in
conventional cryogenic air separation units required to produce oxygen.
Figure 7. Oxy-fuel Combustion Diagram [11]
 Post combustion capture.
The principle of post combustion capture is to remove CO2 from flue gas after
combustion. Instead of being discharged directly to the atmosphere, flue gas is
passed through equipment which separates/captures most of the CO2 Adopting
the post combustion capture route avoids the potentially long development times
required to develop cost-effective coal-derived syngas separation technologies,
hydrogen turbine technology, and fuel-cell technology etc. It can also provide a
means of CO2 capture in the near term for new and existing stationary fossil fuel-
fired power plants. This paper addresses post combustion CO2 capture
technologies with a focus on carbon fibre composite adsorbents.
Figure 8. Pre Combustion Capture. [11]
Capture of Carbon Dioxide Directly from Ambient Air

The continued use of fossil fuels could be made more acceptable, if carbon
dioxide capture from atmosphere proves to be a practical solution. It is
technically feasible to capture carbon dioxide directly from the air. The
technology has been used for decades to remove carbon dioxide from the air
inside submarines or spacecraft. Technologies for removing carbon dioxide from
ambient air have been used in the past to create carbon dioxide-free air prior to
air liquefaction.
It has recently shown that it is possible to develop very low cost processes for
the capture of carbon dioxide from the air, which could make carbon
management by direct CO2 capture feasible.
The direct capture of CO2 from air (or ‘air capture’) is in many ways analogous to
collecting energy from the wind. Windmills reduce CO2 accumulation in air by
avoiding emissions. Air capture devices extract CO2 from the air and thus also
reduce the CO2 load of the atmosphere. By removing all the CO2 from a cubic
meter of air it is proved that contacting the air for CO2 is far cheaper than
contacting the air for wind energy, The cost of the air capture process is not
contacting the air, but in the cost of managing the sorbent cycle.
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Figure 9. CO2 air adsorption [53]
Air capture is a form of capture and it is the capture of last resort. If capture at
the point of emission is not possible or excessively expensive, air capture at any
other place in the world offers a real alternative. The price of air capture would
put an upper limit on the price of managing carbon. If all else fails, air capture is
always a viable capture option and thus it can be applied to all types of
emissions.
Once the price of air capture becomes affordable, the cost of dealing with all CO2
emissions becomes manageable. Presumably the price of air capture will
gradually drop if more is done. In any event, air capture which provides a
method of last resort can be used to mop up after cars, air planes, or any other
emitters with a difficult local capture situation. Generally speaking, the lower the
cost of air capture, the larger its potential market in sequestration. If it comes
close to the cost of retrofitting, then it could be develop into a viable alternative
to retrofitting. Otherwise it may be limited to special applications where no other
options are available. Air capture is particularly well suited to recapture the
carbon dioxide realised from the transportation sector.
Air capture has been categorised as a form of geo-engineering in the public press
and by a number of authors. However, air capture in its simple initial application
should not be considered geo-engineering. It is about balancing out specific
emissions rather than engineering the composition of the atmosphere. The
purpose of air capture is to prevent the accumulation of excess carbon in the
environment. The only unusual feature of the approach is that one can take the
CO2 back, even after it has been released into the atmosphere.
Any emission to the atmosphere will stay in the air for a very long time. Hence, it
is not possible to close the carbon cycle in the presence of air emissions of CO2,
unless one deploys air capture technologies. [10]
Geological Storage of CO2
Geological storage of carbon dioxide captured from large stationary industrial
sources comprises injecting it into porous rocks deep in the Earth’s crust so as to
isolate this gas from the atmosphere. The whole industrial process chain involves
CO2 capture, transport and storage, commonly referred to as Carbon Capture
and Storage (CCS). [11]
- 18 -
Rocks are classified by geologists into three basic categories: sedimentary

igneous and metamorphic. Sedimentary rocks are formed from sediments that
accumulate and are buried. Sediments may be sourced by erosion from other
rocks, through bio-geochemical deposition or combination of process. All rocks
have open pores within them which can be filled with gas, water or oil.
Sedimentary rocks are, therefore, the most promising hosts for storing CO2.
Thick accumulations occur where the Earth’s crust has subsided to form
sedimentary basins.
For a successful CO2 storage permeability is the most crucial reservoir
characteristic. A rock which has very low permeability cannot easily be injected
with CO2.
Injection of gases, including CO2, into the sub-surface is routine in the oil and
gas industry, where these techniques are used to enhance oil and gas hydrogen
are already stored underground in many parts of the world. Large-scale storage
of CO2 globally still poses many technical and social challenges. There are largely
due to the scale and permanence required for CO2 storage to be an effective and
safe technology and uncertainties about the performance of saline aquifers,
which are the most ubiquitous and volumetrically the largest geological units in
CO2 might be storage. The fact that large underground accumulations of CO2
occur in nature bears testament to the fact that CO2 can be safely stored
underground, in the right geological conditions, for millions of years. [10]
Public Awareness of CO2 Storage
Public awareness of CO2 capture and storage is emerging, but is still at a
relatively low level compared to other carbon-management technologies. Recent
studies show that public awareness and attitudes to CO2 storage vary, depending
on age, culture, regional geography, nationality, education and gender.
As a general rule, people are more positive after technical information on
Carbon Capture and Storage is explained and understood, compared to when
they first hear about the concept. Scientists and engineers have an important
role to play in communicating impartial and give accurate information about the
CO2 storage. Strongest public engagement occurs at the local level when
communities perceive that they are exposed to unacceptable risk from a
particular CO2storage project, or see no local benefit great enough to outweigh
their risk aversion, of which safety concerns are most prominent. [10]
2.2.2. Sources of Hydrogen

Hydrogen is mainly used in petroleum refining, ammonia production and metal
refining such as nickel, tungsten, molybdenum, copper, zinc, uranium and lead.
[14] Hydrogen can be produced from variety of sources. Figure ## shows the
variety of hydrogen production pathways and highlight the methods that are
supported by the electric utilities. [13] The hydrogen production is dominated by
reforming of natural gas and gasification of coal and petroleum coke, as well as
gasification and reforming of heavy oil.[14] The importance of these pathways
for making fuel is that they can be produced domestically without relying on
foreign sources. [13]
- 19 -
Figure 10. Hydrogen production path ways. [12]
Although, water electrolysis to produce hydrogen (and oxygen) has been known
and it has the advantage of producing extremely pure hydrogen. Its applications
are often limited to small scale and unique situations where access to large scale
hydrogen production plants is not possible or economical, such as marine,
rockets, spacecrafts, electronic industry and food industry as well as medical
applications.
Water Electrolysis
Electrolysis was discovered in 1800 by William Nicholson and Sir Anthony Carlisle
shortly after Alessandro Volta invented the electric battery. The electrolyser
industry grew substantially during the 1920s and 1930s. Electrolysers are still
used in places where low electricity prices are available or that have high
hydrogen purity requirements. [12]
Water electrolysis can work beautifully well at small scales and, by using
renewable electricity, it can also be considered more sustainable. In a conceptual
distributed energy production, conversion, storage and use system for remote
communities, water electrolysis may play an important role in this system as it
produces hydrogen using renewable energy as a fuel gas for heating applications
and as an energy storage mechanism. When abundant renewable energy is
available, excessive energy may be stored in the form of hydrogen by water
electrolysis. The stored hydrogen can then be used in fuel cells to generate
electricity or used as a fuel gas.
Remote areas with abundant solar or wind electricity resources can take
advantage of the water electrolysis to produce hydrogen to meet their energy
need for households such as lighting and heating, powering telecommunication
stations and small-scale light manufacturing industry applications. Hydrogen
produced by renewable energy has a great advantage, mobility, which is
essential to the energy supply in remote areas away from the main electricity
grid.
Small-scale water electrolysers can avoid the need for a large fleet of cryogenic,
liquid hydrogen tankers or a massive hydrogen pipeline system. The existing
- 20 -
electrical power grid could be used as the backbone of the hydrogen

infrastructure system, contributing to the load levelling by changing operational
current density in accordance with the change in electricity demand.
Electrolysis fundamentals
A basic water electrolysis unit consists of an anode, a cathode, power supply,
and an electrolyte, as illustrated in Figure ##. A direct current (DC) is applied to
maintain the electricity balance and electrons flow from the negative terminal of
the DC source to the cathode at which the electrons are consumed by hydrogen
ions (protons) to form hydrogen. In keeping the electrical charge (and valence)
in balance, hydroxide ions (anions) transfer through the electrolyte solution to
anode, at which the hydroxide ions give away electrons and these electrons
return to the positive terminal of the DC source.
Figure 11. A schematic illustration of a basic water electrolysis system

[14]
Potassium hydroxide is most commonly used in water electrolysis, avoiding the

huge corrosion loss caused by acid electrolytes. Nickel is a popular electrode
material due to its high activity and availability as well as low cost. During the
process of water electrolysis, hydrogen ions move towards cathode, and
hydroxide ions, move towards the anode. By the use of a diaphragm, gas
receivers can collect hydrogen and oxygen, which form on and depart from the
cathode and the anode, respectively. [14]
The half reactions occurring on the cathode and anode, respectively, can be
written as:
Cathode: 2H+ + 2e → H2 (9)
Anode: 2OH- → ½O2 + H20 + 2e (10)
The overall chemical reaction of the water electrolysis can be written as:
H2O → H2 + ½O2 (11)
- 21 -
Water quality requirements differ across electrolysers. Some units include water
purification inside their hydrogen generation unit, while others require an
external deionizer or reverse osmosis unit before water is fed to the cell stacks.
For systems that do not include a water purifier, one is added in the process
flow. A water storage tank may be included to ensure that the process has
adequate water in storage in case the water system is interrupted. Each system
has a hydrogen generation unit that integrates the electrolysis stack, gas
purification and dryer, and heat removal.
Figure 12. Hydrogen generation Unit [13]
Electrolyte circulation is also included in the hydrogen generation unit in alkaline

systems. The integrated system is usually enclosed in a container or is installed
as a complete package. Oxygen and purified hydrogen are produced from the
hydrogen generation unit. If desired, a compressor and hydrogen storage can be
added to the system.
Hydrogen storage and compression are included in the process diagram below
and as can be appreciated the hydrogen produced it is fed directly into a pipeline
or truck.
Figure 13. Hydrogen process flow diagram [13]
- 22 -
Steam reforming
Steam reforming is a well-established technology, which uses natural gas as
feedstock. This process takes place at temperatures between 750 and 1000ºC.
[16]
The conventional steam methane reforming system for hydrogen production is
composed of a steam reformer, a shift converter, and a hydrogen purifier based
on the pressure swing adsorption. A mixture of natural gas and steam is
introduced into a catalyst bed (usually nickel, supported by alumina) [16] in the
steam reformer, where the steam reforming reaction proceeds on catalyst based
at high temperatures. Then the reformed gas is supplied to a shift converter,
where carbon monoxide is converted into carbon dioxide to produce more
hydrogen by the shift reaction. Then the reformed gas is passed to pressure
adsorption to separate hydrogen. By this simultaneous generation and separation
of hydrogen, the membrane reformer system can be much more compact and
can provide higher efficiency than the conventional ones. [15]
Figure 14. Principle of membrane reformer [15]
The general formulas of Steam Reforming Reaction to obtain hydrogen are

generally expressed by the following equations:
Reforming Reaction: (12)
Shift Reaction: (13)
Reforming-shift reaction: (14)
For hydrocarbons that consisit of C, H and I, general reaction formulas are

expressed by the following equation:[15]
(15)
- 23 -
The advantage of steam reforming technology is that its output has the highest
concentration compared to other technologies based on fossil fuel. However, it
does not offer fast start-up and dynamic response.
Partial oxidation, (is typically used to process heavy oil fractions; the exothermic
reaction in this case does not require the presence of a catalyst)on the other
hand, produce only low concentrations of hydrogen combined with a fast start-up
and dynamic response. [16]
A suggestion for a future work will be the combination of both technologies using
the advantages of each of them. In fact, this combination, named auto-thermal
reforming, it is not new and because some research groups are working on it.
Hydrogen storage
Hydrogen storage represents one of the difficult issues associated with operation
of the fuel cell system. This is because hydrogen is characterized by low energy
density and high specific energy. There are a number of technologies currently
used for storage, such as liquefaction or compression. Other storage methods
based on carbon nanofibers, metal hydrides, or glass microspheres are currently
under investigation.
Hydrogen liquefaction can be done through several techniques. For small scale
systems, the Stirling process is considered an important solution. An alternative
to the Stirling refrigerator is the magneto caloric refrigeration process, based on
the isentropic demagnetization of a ferromagnetic material near its Curie point
temperature. For large scale applications, the Claude process represents a viable
economic solution.
Different types of pressure cylinders or tanks are currently used for storing
compressed hydrogen with a typical maximum pressure up to 30MPa. Cylinders
are made of lightweight composite materials, which reduce the overall weigh of
the storage. Other technologies, such as hydrogen storage in solid forms, are
being research, and recent results have been reported using carbon (nano-tubes,
active carbon), metal hybrids and glass microspheres. [16]
Carbon storage is a very attractive technology, which provides the overall system
with high energy density, reliability and safety. This technology is based on a
gas-on-solids adsorption of hydrogen, and it is being developed for small
applications, in which safety and weight of the device are characteristic. [17]
Metal hybrids are another interesting option currently explored for hydrogen
storage, where hydrogen react chemically with a metal.
2.2.3. Production of Syngas

Syngas is a mixture of carbon monoxide (CO) and Hydrogen (H2) that is
manufactured by steam-reforming natural gas. We shall emphasize natural gas
(CH4) here although heavier feedstock’s can be processed (naphtha) with similar
technologies and conditions. (9) A certain amount of carbon dioxide (CO2) is also
almost always produced.
This gas is an extremely important precursor for the synthesis of methanol,
hydrogen, ammonia and other products. In particular, methane can be converted
to syngas and gasoline are produced form this mixture (CO+H2). Using this
technology, gasoline is currently produced at Sasol, South Africa, and Malaysia.
- 24 -
Syngas produced using existing methods account for about 60% of the total
conversion cost of natural gas to gasoline. Thus, natural gas is an excellent
choice for an abundant alternative energy sources.
Syngas catalytic process

The feedstock is first desulfurized by passing it through active carbon, which may
be preceded by caustic and water washes. The desulfurized material is then
mixed with steam and passed over a nickel-based catalyst. Effluent gases are
cooled by the addition of steam or condensate to high temperature, at which
point carbon monoxide reacts with steam in the presence of iron oxide in a shift
converter to produce carbon dioxide and hydrogen. The carbon dioxide is
removed by amine washing and the remaining hydrogen is usually a high-purity
material.
Syngas noncatalytic process
Another syngas generation process is a continuous, noncatalytic process that
produces carbon monoxide and hydrogen by partial oxidation of gaseous or liquid
hydrocarbons. A controlled mixture of preheated feedstock and oxygen is fed to
the top of the reactor, where carbon dioxide and steam are the primary products.
A secondary reaction between the feedstock and the gases forms carbon
monoxide and hydrogen.
2.3. RWGS Reaction

The RWGS reaction has been known to chemistry since the 1800’s.
The reaction is slightly endothermic and although much research has been
carried out on the forward water gas shift the RWGS has only relatively recently
begun to attract serious attention. The objective of the RWGS is move the
direction of the reaction to the produce CO and H2O.
Figure 15. RWGS industrial process [53]
- 25 -
2.3.1. Reaction
Proposed mechanisms for the RWGS reaction
There are two general mechanisms proposed to explain how the RWGS proceeds.
1. The surface redox mechanism
2. The formate decomposition mechanism.
Some discrepancy exists on the dominant mechanism controlling the RWGS

reaction.
The redox mechanism is proposed to proceed as follows:
 CO2 Oxidised Cu0 to generate CO,
 H2 reduced Cu(I) to Cu0 and forms H2O,
 CO can be produced alone over Cu powder or Cu/Zn Catalyst,
 H2 plays a role of reducing agent for the reduction of Cu2O. [2]
Evidence supporting the surface redox mechanism comes primarily from kinetic
data for the reaction being predicted by models based upon the surface redox
mechanism. [2-6]
The formation decomposition mechanism is proposed to proceed as follows;
 An intermediate compound is formed from H2 and CO2 involving the

catalyst in use.
 The decomposition of this intermediate compound releases CO.
The strongest evidence for the formate decomposition mechanism comes from
studies conducted involving a TAP (Temporal analysis of products) technique [2].
This experimental technique allows the identification of intermediate compounds
formed.
Whichever mechanism is dominantly responsible during the RWGS reaction over
specific catalysts it is important to remember that the reaction still proceeds in
each case. The identification of a suitable catalyst for the RWGS (in terms of
stability, CO selectivity and conversion rates) is of more practical importance to
our project.
Methods of driving Reaction
Three realistic methods for continuing the reaction have been proposed by Tom
Meyer and Robert Zubrin [2]
They suggested that one or a combination of three approaches could allow the
reaction to proceed.
 Overload the reactor with CO2 to force the complete consumption of H2,
and then recycle the excess CO2 in the exhaust stream back into the
reactor.
 Overload the reactor with H2 to force the complete consumption of the

CO2, and then recycle the excess H2 in the exhaust stream back into the
reactor.
- 26 -
 Operate a system that removes water vapour from the reactor, thereby
driving the reaction to the right. Such a system could either be a desiccant
bed or condensing apparatus.
The choice of the most appropriated method will strongly depend upon its
efficiency and effectiveness.
2.3.2. RWGS Reaction in Microreactors

The application of the RWGS within microreactors/microchannels is also
considered. One of the most influential factors regulating the performance of this
reaction is the choice of catalyst. Several previous studies have looked at
evaluating the range of possible catalysts as well identifying the correct
mechanism of the reaction.
The performance of the RWGS within micro reactors will certainly not be without
obstacles. Some of the potential problems which may arise are also considered,
e.g. Catalyst deposition, catalyst poisoning.
The expected advantages that micro reactors will bring to the RWGS reaction are
also outlined and the future potential of the RWGS is briefly discussed. The
performing of the RWGS within micro reactors could prove to be highly
successful should the results of some previous studies be reproduced in terms of
CO selectivity and conversion rates.
There are not many examples of a micro reactor intentionally designed with the
RWGS reaction in mind. The general properties and advantages which
microreactors possess seem very promising for the RWGS reaction. i.e. the
improved heat and mass transfer characteristics. The RWGS has been
successfully carried out at micro second residence times [3]. This ability of the
reaction to proceed at very short residence times is essential when considering
performing the reaction within a microreactor.
2.3.3. Catalyst Selection

The catalyst is the tool that makes possible to move the reaction to the reverse
direction. Nowadays, it exists many studies to talk about different combinations
of catalysts, with different results, in relation with the conditions of the
experiment. Below we will explain some of them:
Publications on the Reverse Water Gas Shift Reaction
In recent years several studies have evaluated the performance of certain
catalysts at carrying out the RWGS. In general the RWGS proceeds fast over
several catalysts, metallic and oxides. [2] These studies have evaluated a range
of potential catalysts for the RWGS reaction, from conventional Cu/ZnO
substances [2] to more unusual Pt/CeO [2] catalysts. The Group VIII transition
metals are good candidates as catalysts for the RWGS reaction and typical RWGS
catalysts contain copper and/or zinc dispersed on an oxide support.
Unfortunately, the forward reaction is also catalyzed by these reactions to a high
degree, and operating conditions dictate carbon dioxide conversion and product
selectivity.
There are several factors which together would determine to effectiveness of a
particular catalyst. Not only the conversion rates and selectivity towards a
- 27 -
desired product (i.e. CO & H2O), but also the stability of the catalyst substance
over time is an important factor.
There are specific studies which have analysed this aspect of catalyst
performance. It is important that the eventual deactivation or poisoning of the
catalyst over time should be minimised and not be ignored.
Gines et al. carried out a kinetic study of the RWGS reaction in 1996[7]. The
reaction kinetics was reproduced accurately with a model based on the surface
redox mechanism. They concluded that the rate controlling step in the reaction
was the CO2 adsorption or the CO2 dissociation and H2O formation. Their tests
were carried out in an internal plug flow reactor over CuO/ZnO/Al2O3 catalysts.
They concluded that the reaction kinetics depended strongly upon the reactant
composition, i.e. CO2/H2 partial pressures. The temperature required for this
catalyst, 500K, is well within the operational range of our silicon micro-reactors.
The reaction was carried out at atmospheric pressure. A maximum CO2
conversion of 6% was achieved which diminished to 0 after 100mins of
operation.
Ching Shien Chen et al. (2000) studied the mechanism of the RWGS reaction
over a Cu/Al2O3 catalyst [2]. It was concluded that hydrogen acts as a
significant promoter to the formation of CO. The formate dissociation mechanism
was suggested to explain the reaction behaviour. It was also concluded that the
surface redox mechanism cannot explain the experimental results obtained. The
required temperature for the reaction varies, from 400-600K, depending on the
catalyst treatment employed.
In 2001 Ching-Shun Chen again published a study on the performance of the
RWGS reaction, this time over a Cu/SiO2 catalyst with and without a “potassium
promoter”. [2]It was found that the potassium catalyst generated new active
sites for the reaction and the formate dissociation mechanism was again used to
explain the behaviour observed. The reaction was undertaken at temperatures
between 500 and 600oC.
In 2003 Oh Shin Joo investigated the stability of ZnAl2O4 catalyst during the
RWGS reaction. [2] It was claimed that a CO selectivity of 100% was achieved at
pressures of 5atm. The Zn/Al2O3 Catalyst was the most stable even at high
temperatures. It was also found that an Iron oxide catalyst (Fe2O3/Cr2O3) was
easily reduced to Iron. The temperature range was between 400 and 700oC. The
pressure used was 5Atm. A CO2 conversion of between 20 and 60% was
achieved.
Also in 2003 a study by Guichang Wang et al. used an energy analysis to look at
the kinetic properties of the RWGS reaction. [2] The surface redox mechanism
was the reaction mechanism in their study. The catalysts analysed were Cu and
Au. It was found that the Au catalyst would be easily poisoned by sulphur. A rate
controlling step in the reaction was pinpointed as the dissociation of adsorbed
CO2. They also concluded that the catalyst structure was more influential for the
RWGS than the WGS.
A Goguet et al. carried out experiments focused on the deactivation of a Pt/CeO2
Catalyst during the RWGS in 2004. [2]
It was found that carbon deposits form on the catalyst rapidly when exposed to
carbon monoxide. These carbon deposits deactivate the catalyst and could prove
- 28 -
to be a major obstacle. The reaction was carried out at 300oC and a 20% CO2
conversion was achieved.
In 2005 Gary Jacobs claimed that the formate decomposition mechanism could
be the only route through which the RWGS proceeds. A steady state isotope
switching study of the RWGS was conducted. [2] The experiments were
performed over Pt/Ceria catalyst and stated that “direct evidence to support the
surface redox mechanism is lacking and the mechanism is inferred based upon
kinetic studies”
Once again in 2005 A. Goguet produced a study on the RWGS over Pt/CeO2
catalyst. [3]It was discovered again that Hydrogen increased the CO yield and
that the reaction mechanism was the formate dissociation mechanism. The
Experiments were performed using a technique called Temporal Analysis of
Products (TAP). This method allowed the identification of intermediate
compounds when formed. The temperature of the reaction was 300oC.
In 2007 Wang Luhui et al. performed the RWGS over a Co precipitated Ni-CeO2
catalyst. [3] Catalysts with varying Ni contents were prepared. The results
showed that the 2% Ni- CeO2 catalyst performed the best in terms of CO
selectivity, stability and activity. The usefulness of Cu based catalysts was also
mentioned, it was pointed out that although Cu and Pt/CeO2 catalysts are both
effective during the RWGS, Pt/CeO2 performed better at lower temperatures.
The temperature range was 400-750oC and at atmospheric pressure. The
maximum CO yield was 45% at 750ºC.
A Study conducted by D.P. VanderWiel et al., focused on the development of the
RWGS for use in space, experimented with Ruthenium based catalysts within
micro-reactors and achieved positive results. [8]A conversion of about 30% and
selectivity of 70-95% was achieved although at 540oC.
In 2007 another micro reactor based RWGS study was conducted by Jianli Hu et
al. Their findings were comparable with those of Vander Wiel in terms of
conversion and selectivity. They both made use of a Ruthenium catalyst. Jianli
Hu et al performed a condensation step between two RWGS reactors and found
that this dramatically increased the CO yield. A temperature of 700-800oC and
10 Bar pressure was applied. The maximum CO2 conversion was 43% with 97%
CO selectivity.
Table 1. Studies on RWGS
Author & Catalyst Mechanism Main Findings

Study Employed
Gines et al. Kinetic Study CuO/ZnO/Al2O Surface Redox CO2 adsorption is rate
of RWGS. (1996) 3 controlling step.
Ching Shien Chen et al. Cu/Al2O3 Formate H2 Encourages the
mechanism of the dissociation Reaction.
RWGS(2000) mechanism
Ching-Shun Chen, Effect Cu/SiO2 / K2O Formate Potassium produces
of Potassium Catalyst. dissociation new active sites for the
(2001) mechanism reaction.
Oh Shin Joo investigated ZnAl2O4 CO selectivity of 100%
the stability of ZnAl2O4 Fe2O3/Cr2O3 was achieved
- 29 -
catalyst. (2003)
Guichang Wang et al. Cu and Au surface redox Catalyst structure was
looked at the kinetic mechanism more influential for the
properties of the RWGS RWGS than the WGS. A
rate controlling step was
reaction. (2003)
pinpointed as the
dissociation of adsorbed
CO2
A. Goguet et al. Pt/CeO2 Formate carbon deposits on the

experiments focused on dissociation catalyst rapidly when
the deactivation of a mechanism exposed to carbon
Pt/CeO2 (2004) monoxide
Gary Jacobs(2005) Pt/Ceria Formate Formate Decomposition
decomposition Mechanism is in action.
mechanism
A. Goguet produced a Pt/CeO2 Formate Hydrogen increased the
study on the RWGS dissociation CO yield
(2005) mechanism
Wang Luhui et al (2007) Co 2% Ni- CeO2 catalyst

precipitated performed the best in
Ni-CeO2 with terms of CO selectivity,
varying Ni stability and activity
contents
D.P. VanderWiel et al., the Ruthenium based
(2002) development catalysts
of the RWGS
for use in
space
To sum up, for choosing the best catalyst is necessary to find the accurate
information in the literature, because for knowing the performance of the
catalyst an experiment data has to be done..
2.3.4. Reaction Kinetics

The kinetics and reaction mechanism of the RWGS/WGS system are typically
conducted over a heterogeneous catalyst system, most popularly co-precipitated
Cu/ZnO/Al2O3, which is reduced from CuO/ZnO/Al2O3. However, the kinetic
model will be determined by the experimental and operation conditions.
There are general agreement that copper provides the active site from catalysis,
the mechanism of the reaction over Cu-based catalyst is still not certain.
Although few papers have been published on the mechanism of the RWGS
reaction, the information is coincident in that the reaction proceeds through the
same surface redox mechanism used to describe the kinetics of the forward WGS
reaction, the metallic copper being the active sites. [19] This is a regenerative
mechanism whereby copper is successively oxidised and reduced by CO2 and H2
according to the following simplified scheme:
(16)
- 30 -
(17)
On the basis of previous literature, the present kinetics of the RWGS reaction will
be discussed in terms of the surface redox mechanism. Such a mechanism may
be represented by the following elementary steps:
(18)
(19)
(20)
(21)
(22)
Where L represents the vacant active sites. [19]

Summarizing and emphasizing again that the kinetic model will be determined by
the experimental and operation conditions. Thus, it will not be able to decide
which of the proposed kinetic models will the overall reaction follow.
- 31 -
CHAPTER 3:
INTRODUCTION
TO
MICROREACTORS
The aim of this chapter is to define the field referred to as micro reaction
technology, to analyze principal advantages, to comment on these benefits,
reviewing current achievements, to document the state of the art of industrial
implementation, and finally to outline future developments.
3.1. Definition
3.1.1. Microsystems termed microreactor
In accordance with the term “microsystem”, which is widely accepted,
microreactors usually are defined as miniaturized reaction systems fabricated by
using, at least partially, methods of microtechnology and precision engineering.
The characteristic dimensions of the internal structures of microreactors like fluid
channels typically range from the micrometer to the sub-millimetre range. Some
people prefer the terms nanoreactors or minireactors for devices with
characteristic dimensions at the lower or the upper boundary of this dimensional
range.
3.1.2. Structural hierarchy of microreactors

The construction of microdevices generally is performed in a hierarchic manner,
i.e. comprising an assembly of units composed of subunits and so forth. This
holds particularly for microreactors which are based on an architecture
characterized by multiplying unit cells, the so-called concept of numbering-up
- 32 -
[21,22]. In the following it is aimed to commonly define different units which

most often are assembled in microreactors.
Definitions with regard to structural hierarch

The smallest units of miniaturized continuous flow system are microstructures, in
the vast majority of cases referring to channel structures. Usually, parallel
channels are combinated to an array surrounded by inlet and outlet flow channel
configuration.
A combination of an element, connecting fluid lines and supporting base
material, is termed unit. For instance, a mixing platelet with and inter digital
structure and feed lines is a micro mixing unit. In order to increase throughput,
units may form a stack, e.g. a stack of catalytic platelets in a chamber of gas
phase microreactor. Alternatively, identical devices can be arranged in parallel in
a plane, e.g. a micro mixer array consisting of thousands of unit cells.
Figure 16. Hierarchical assembly of microreactors, as evidenced for

micro mixer components[39]
Neither units nor stacks can be operated alone; hence, they are not real
microreactors, since they need housings or, at least, top and bottom plates for
fluid connection to external periphery. A device refers to a unit embedded either
in housing or between two end caps. The build-up of complex systems can be
performed by integration of several units within one common housing. A system
can also be based on a connection of devices, in this case referred to as
components.
Any parallel or serial interconnection of components, systems or mixed
combinations may be termed set-up or plant, dependent on the type of
- 33 -
application, being lab- or industrial scale oriented, respectively. These set-ups or

plants consist of either only microdevices or-systems, or, more likely, may
contain microreactors next to conventional larger equipment.
3.1.3. Functional Classification of Microreactors

Two classes of microreactors exist, referring to applications in analysis, especially
in the field of biochemistry and biology, or chemical engineering and chemistry.
Although these fields are distinctly different in most cases, as analytical and
preparative equipment are, some microreactors cover both aspects. This holds
particularly for combinatorial chemistry and screeing microdevices which serve
as analytical tools for information gathering as well as synthetic tools providing
milligram quantities of products.
A further classification of microreactors is based on the operation mode, either
being continuous flow or batch-type. Instead, batch systems such as micro and
nano titer plates, e.g. for solid-supported chemical synthesis of drugs, will not be
reported. [23-25].
The same holds for a large number of continuous flow micro fluidic devices which
were developed for analytical purposes starting in the late 1980s. If a series of
processes such as filtration, mixing, separation and analysis is combined within
one unit, the corresponding microsystems usually were termed micro total
analysis systems (µTAS) [26-32]. Most often, these systems were applied for
biochemical and chemical analysis. Modern developments consider e.g.
polymerase chain reaction, electrophoretic separation, or proteome analysis, just
to mention a few [33-35].
3.1.4. Dividing line between Analysis and Reaction systems

Reaction systems generally differ from analysis by producing or converting
materials or substances. The latter devices are designed to gather information,
e.g. to measure the content of certain analyte in a water sample taken from a
lake. However, comparing extremely small individual systems, this difference
apparently vanishes, because miniaturization of reaction devices ultimately will
decrease the amount of converted materials to a level close to that of analytical
devices. Therefore, the productivity of such small reaction devices, which is not
sufficient anymore for synthesis purposes, can be used for process development
or for screening only.
Both applications clearly refer to measuring tasks, the former regarding the
finding of optimum process conditions, the latter of application-tailored
materials. Actually, such measuring tools gather information similar to analytical
devices. However, the purpose of using the information is distinctly different. In
analytics, information gathering is an end in itself. For instance, the detection of
ozone concentration in certain layer of the atmosphere provides important
information for ecological research. In contrast, information obtained in small
reaction systems is used to optimize a lab synthesis or a large-scale process as
well as to produce a new material with advanced properties, thus, finally is
related to production issues. Hence, there is a clear dividing line between
miniaturized analysis systems and microreactors for chemical applications. [34]
- 34 -
3.2. Fundamental Advantages of Microreactors

Before analyzing the fundamental advantages of microreactors it is worthwhile to
shortly review the benefits of miniaturized analysis systems, designed with
similar characteristic dimensions as microreactors, and nanoscale reactors of
much smaller size.
3.2.1. Fundamental Advantages of miniaturized analysis systems

A large number of applications within the last two decades clearly demonstrated
fundamental advantages for miniaturized analysis systems compared to lab-scale
equipment. The smaller devices needed less space, materials, and energy and
often had shorter response times. In particular, more information per space and
time is gained. By parallel micro fabrication and automated assembly, the costs
per device could be kept low. Decreasing the component size, in addition,
allowed the integration of a multitude of small functional elements, thereby
enhancing the system performance [27].
3.2.2. Fundamental Advantages of nano-scale reactors.

In the following, a nano-scale reactor is defined as any supramolecular assembly
which acts as a reaction unit, i.e. being a host providing a small reaction colume,
sometimes encasing only one molecule. To mention only a few, supramolecular
assemblies such as molecular tweezers, zeolites, micelles, liposomes and
Langmuir-Blodgett layers were, among other applications, utilizaed as small
“reaction vessels”. Most often, the molecular encapsulation strongly modified the
reactivity of the reactants, e.g. by electronic interaction of π systems within a
bola-type amphiphile, by adsorption and isolation in a zeolite cavity, or by
separation within micelles in order to prevent radical recombination.
Figure 17. Bola-type amphiphile forming a small nano-sized reaction

vessel by means of self-organization. The chlorination of encapsuled
phenol is thereby prohibited [27]
Hence, small vessels, cavities and clefts provided in nanoreactors allow an

interaction by means of molecular forces and modify the electronic structure of
reactants. In addition, steric interactions are possible, e.g. influencing the
- 35 -
conformation of a molecule or the free rotation of a group attached to a

molecule. All these factors, known to modify the reactivity of “free” molecules as
well, have a similar effect on “encapsulated” reactants. In this sense,
nanoreactors behave like a solvent or a weak complexing agent.
To summarize, the most remarkable feature of nanoreactors is that they are
actively changing chemistry, although the encasement certainly influences
transport properties as well.
3.2.3. Advantages of microreactors due to decrease of physical size.

The volumes of microreactors are too large in order to interact with reactants
significantly on a molecular level. Their main impact focuses on intensifying mass
and heat transport as well as improving flow patterns. Therefore, benefit
concerning chemical engineering is the main driver for microreactor
investigations, while chemistry, in terms of reaction mechanism and kinetics,
remains widely unchanged.
Decrease of linear dimensions
Decreasing the linear dimensions increases, for given difference in a physical
property, the respective gradient. This refers to properties particularly important
for processing in chemical reactors, such as temperature, concentration, density,
or pressure. Consequently, the driving forces for heat transfer, mass transport,
or diffusional flux per unit volume or unit area increase when using
microreactors.
These simple theoretical predictions were evidenced by a number of studies, e.g.
concerning heat and mass transport. The majority of today’s microreactor / heat
exchanger devices contain microchannels with typical widths of 50 µm to 500
µm; the separating wall material between reaction and heat transfer channels
can kept down to 20 to 50 µm, if necessary. As a result, heat transfer
coefficients up to 25000 W/m2K measured in microdevices exceed those of
conventional heat exchangers by at least one order of magnitude[36].
Typical fluid layer thicknesses in micro mixers can be set to a few tens of
micrometers, in micro mixers amount to milliseconds, in some cases even to
nanoseconds, which is hardly achievable using stirring equipment or other
conventional mixers.
Increase of surface-to-volume ratio
As a consequence of the decrease in fluid layer thickness, the corresponding
surface-to-volume ratio of the fluid entity is also notably increased. Specific
surfaces of microchannels amount to 10000 to 50000 m2 /m3, whereas typical
laboratory and production vessels usually do not exceed 1000 m2/m3 and
100m2/m3, respectively. Apart from benefits of heat transfer mentioned above,
this increase in specific vessel surface can be utilized, e.g., in catalytic gas phase
reactors coated with the active material on the inner walls.
Decrease of volume
Due to the reduction of the linear dimensions, the volume of microreactors is
significantly decreased compared to large-scale reactors, typically amounting to
a few microliters. This difference becomes even large when, in combination with
reactor miniaturization, a large-scale batch process is replaced by continuous
- 36 -
flow operation in microdevices. In case of a metallorganic reaction, the material

hold-up could be decreased from tank of 6000 l size to a volume of a few
millilitres within five miniaturized mixers. The smaller hold-up increases process
safety and, due to shorter residence time, improves selectivity.
3.2.4. Advantages of microreactors due to increase of number of units.

A characteristic feature of micro structured fluidic devices is the multiple
repetitions of basic units either fed separately in screening devices or operated in
parallel, using a common feed line, for production purposes.
Fast and cost-saving screening of Materials and processes
Recently, the application of combinatorial strategies has been more and more
extended from drug development in pharmacy [23, 24] to screening of inorganic
materials, catalysts and polymers. Whilst the former processing route was
focused on the use of small batch reaction vessels, so-called micro and nano titer
plates, the latter approaches demand a diversification of reactor types. So far,
inorganic materials, and in selected cases catalysts, were tested as arrays of
spatially separated thin zones consisting of different materials. These zones
usually were coated on wafers by means of thin film deposition techniques, in
most cases using mask processes in order to locally change material properties,
e.g. generating concentration profiles.
However, this straightforward approach is limited, especially regarding catalyst
and polymer material research. The need for support porosity in the former case
and long reaction times in the latter case are two among several arguments
favouring the use of tube-like continuous flow reactors. A combined processing in
many small tubes in parallel was already realized in flow-through tube reactors.
A further decrease in hydraulic diameter leads to more and more compact
microreactor design.
First design concepts for such screening microreactors were a stack providing a
frame for insertion of disposable catalyst carrier plates and a sheet consisting of
a number of reaction plates, structurally analogous to a titer plate. Apart from
increasing the number of samples to be investigated, further benefits in
screening microreactors are the rapid and precise change of temperature,
concentration and pressure. In particular, the possibility of isothermal operation
and the high efficiency of mass transfer provide a sound information base, e.g.
allowing to measure intrinsic kinetic properties.
Although currently screening in microreactors is most often performed by parallel
processing, the continuous flow operation of microreactors enables rapid serial
synthesis as well. One possible strategy can be based on the separation of liquid
plugs containing the different samples separated by immiscible liquid in a
miniaturized channel. [23,24]
- 37 -
Figure 18. Simplified scheme illustrating scale-up versus numbering

strategies [39]
The generation of many samples, either by parallel or serial means, requires fast
analysis. The integration of synthesis and analysis in one device has a number of
advantages besides compactness. This serves to speed up analysis times, to
save sample material and to eliminate additional sample transfer, either
performed manually or by a robot.
Due to this interdependence of sample generation and testing, screening is,
among all application fields of microreactors, strongly dependent on the
development of a particle total system approach, combining all relevant
components in one device.
Production Flexibility
An increase in throughput in microreactors is achieved by a numbering-up
approach, rather than by scaling-up[21, 22]. The functional unit of a
microreactor, e.g. a mixing structure, is multiply repeat. Fluid connection
between these units can be achieved by using distribution lines and flow
equiparation zones, most likely hierarchically assembled.
Numbering-up widely guarantees that desired features of a basic unit are kept
when increasing the total system size [21, 22]. In an ideal case, measuring
devices for process development and production reactor become similar, being
composed of identical units. This was, e.g. demonstrated by comparison of
mixing quality of an array of ten mixing units with the performance of a single
unit. However, these results also showed the crucial importance of flow
distribution for the efficiency of the total reaction unit.
In addition, a larger number of units results in higher flexibility in adapting
production rate to varying demand since, at least in principle, a certain number
of systems can be switched off or further systems may be simply can, again at
least in principle, be modified to perform a variety of reactions by changing the
piping network, i.e. the plant may be adapted to the synthesis of various
substances using microreactors modules like a “LEGO” system. This flexibility
may be supported by a considerably broader range of operating conditions of a
microreactor compared with macroscopic system.
- 38 -
3.3. Process Intregration/Intensifications

3.3.1. Introduction to Distributed generation
The aim of the investigation is know if the Microreactor technology can support
and improve fuel re-synthesis and if distributed fuel generation is a feasible
option. (The simulation in this project considers the RWGS reaction and is only
the first part of this investigation).
The concept of different types of distributed generation will be explained. In a
not far future, the combination of fuel re-synthesis microreactors and other
elements of distributed generation in a no far future maybe will change our
concept of energy generation.
Distributed generation (DG) is emerging as a new paradigm to produce-on-site
highly reliable and good quality electrical power. Thus, the DG systems are
presented as a suitable form to offer highly reliable electrical power supply. The
concept is particularly interesting when different kinds of energy resources are
available, such as photovoltaic (PV) panels, fuel cells (FCs), or wind turbines.
The DG of different kinds of energy system allows for the integration of
renewable and nonconventional energy resources. Hence, the DG is becoming a
part of the strategic plans of most countries to address current challenges
associated with energy management. Today, electrical and energy engineering
have to face a new scenario in which small distributed power generators and
dispersed energy storage devices have to be integrated together into the grid.
The new electrical grid will deliver electricity from suppliers to consumers using
digital technology to control appliances at consumer’s homes to save energy,
reducing cost and increasing reliability and transparency.
The idea behind this concept is to have devices that plug into your outlet and you
would plug your appliance into this device. These devices would communicate
and report to the electric companies at what time your appliance used energy
and how much energy was used. This will in turn charge you more for the
electricity that you use during peak hours of late afternoon and early evening. In
this sense, the expected whole energy system will be more interactive,
intelligent, and distributed [9].
Nowadays, many types of Distributed energy generators exist which are
explained below.
These types of DGs must be compared to each other to help in taking the
decision with regard to which kind is more suitable to be chosen in different
situations. However, in our paper we are concerned with the technologies and
types of the new emerging DGs: micro-turbines and fuel cells. The different kinds
of distributed generation are discussed below:
- 39 -
Figure 19. Distributed generation types and technologies [39]
3.3.2. Traditional combustion generators

Microturbine (MT)
Microturbine technologies are expected to have a bright future. They are small
capacity combustion turbines, which can operate using natural gas, propane, and
fuel oil. In a simple form, they consist of a compressor, combustor, mall turbine,
and generator. Sometimes, they have only one moving shaft, and use air or oil
for lubrication.
MTs are small scale of 0.4–1m3 in volume and 20–500kW in size. Unlike the
traditional combustion turbines, MTs run at less temperature and pressure and
faster speed (100,000 rpm), which sometimes require no gearbox [41]. Some
existing commercial examples have low costs, good reliability, fast speed with air
foil bearings ratings range of 30–75kW are installed in North-eastern US and
Eastern Canada and Argentina by Honeywell Company [37] and 30–50kW for
Capstone and Allison/GE companies, respectively [42].
Another example is ABB MT: of size 100kW, which runs at maximum power with
a speed of 70,000 rpm and has one shaft with no gearbox where the turbine,
compressor, and a special designed high speed generator are on the same shaft
[41].
- 40 -
Advantages of MTs.
 They can be installed on-site especially if there are space limitations. Also
they are compact in size and light in weight with respect to traditional
combustion engines.
 They are very efficient (more than 80%) and have lower emissions (less
than 10 ppm NOx) with respect to large scale ones.
 They have well-known technology and they can start-up easily, have good
load tracking characteristics and require less maintenance due their simple
design.
 They have lower electricity costs and lower capital costs than any other DG
technology costs .
 They have a small number of moving parts with small inertia not like a
large gas turbine with large inertia.
 Modern power electronic interface between the MT and the load or grid
increases its flexibility to be controlled efficiently.
There are different types of MTs according to their operation such as gas turbines
and combustion turbines. Gas turbines are combustion turbines that produce
high temperature and pressure gas. This high-pressure gas is used to rotate
turbine shaft, which drives a compressor, an electric alternator and generator.
Gas turbines are always used above 1MW, but nowadays we can generate
electricity through small modulars with a micro-gas turbine of 200kW size [41].
The produced heat can be used as a waste heat recovery to generate steam for
compound heat and power (CHP) as shown in Fig. X, combined cycle application
and fuel cell/turbine hybrids applications. MT types are different according to
their operating cycle configurations [43]:
Simple-cycle gas turbines: Simple gas turbines can be either a single-shaft
machine (with air compressor and power turbine (PT) on the same shaft) or a
split-shaft machine. Also, they have a burner or combustor, and an electric
generator rotated by power turbine.
Figure 20. Typical micro-turbine operation [39]
- 41 -
Figure 21. Combined cycle gas turbine [39]
Recuperated gas turbines: They are similar to simple-cycle gas turbines, but
with a special heat exchanger. It uses the output exhaust thermal energy to
preheat compressed air in its pass to the burner to increase the turbine electrical
efficiency.
Combined cycle gas turbine uses the exhaust energy in a heat recovery steam
generator (HRSG) based on the concept of heat recovery, which may include a
burner to increase the steam output. Steam from the HRSG drives a steam
turbine, which generates power in addition to the main power turbine as shown
above, to increase the total electric efficiency.
3.3.3. Non-traditional generators

Electrochemical devices: fuel cell (FC)
The fuel cell is a device used to generate electric power and provide thermal
energy from chemical energy through electrochemical processes. It can be
considered as a battery supplying electric energy as long as its fuels are
continued to supply. Unlike batteries, FC does not need to be charged for the
consumed materials during the electrochemical process since these materials are
continuously supplied.
FC is a well-known technology from the early 1960s when they were used in the
Modulated States Space Program and many automobile industry companies.
Later in 1997, the US Department of Energy tested gasoline fuel for FC to study
its availability for generating electric power [42]. FC capacities vary from kW to
MW for portable and stationary units, respectively. It provides clean power and
heat for several applications by using gaseous and liquid fuels [45]. FCs can use
a variety of hydrogen-rich fuels such as natural gas, gasoline, biogas or propane
[46].
Fuel Cells operate at different pressures and temperatures which varies from
atmospheric to hundreds of atmospheric pressure and from 20 to 200 ◦C,
respectively [46].
- 42 -
Figure 22. Polymer electrolyte membrane FC [39]
The figure above is a typical FC consists of two oxidant electrodes separated by

an electrolyte member. Oxygen, as an oxidant, passes through one electrode
(cathode) either at low pressure (using a blower) or at high pressure (using air
compressor). Hydrogen, as a fuel, passes through the other electrode (anode).
FC technology is based on an electrochemical process in which hydrogen and
oxygen are combined to produce electricity without combustion. The catalyst
splits the hydrogen atom into a proton and an electron. The proton passes
through the electrolyte; however, electrons create a separate current that can be
utilized before they return to the cathode, to be demodulated with the hydrogen
and oxygen in a molecule of water. The operating stages and products of this
electrochemical process, as shown in below are direct current electric power,
water, heat, and some low emitted gases (like NOx and CO2) with respect to
traditional generators and hence is considered an environmentally safe electric
power generation.
Figure 23. FC construction, operation, and products [39]
A fuel processor is used to convert the source fuel to a hydrogen-rich fuel

stream, which is needed for the electrochemical reaction. A power electronic
device (a power conditioner) has to be used to convert the output direct current
to the alternating one to be connected to the grid and control its voltage level
according to the required application [44, 45].
The hydrogen used can be obtained either by reformation of hydrocarbons or by
means of chemical and electrolysis operations from water. The most commonly
- 43 -
used method is reformation of hydrocarbons such as natural gas because it is

already commercially available as it can be transmitted by means of pipelines.
Producing hydrogen can be done chemically by using steam on heated carbon.
The output products of this process are H2 and CO2. This chemical operation
requires heating for the steam and the carbon, which is considered a waste of
energy. Another means of producing H2, and storing the energy in it, is from
electrolysis of water. This process is not economic as it uses electric energy to do
the process and cover its losses [46]. Usually the reforming process, which is
known as “steam catalytic reforming process” to get a hydrogen-rich fuel [47],
occurs at high temperature around 800 ◦C.
Advantages of FCs
FCs transform the fuel chemical energy to electric power with a 60% efficiency,
which is considered to be twice of that of the traditional generating stations.
 The absence of moving parts in FCs operation, except for air blowers (for
O2) and fuel (for H2) and/or water pumps, results in very low noise levels,
relatively higher efficiencies and emits lower air pollutants.
 No combustion is involved in the FC operation make it environmental

friendly generation with approximately negligible emissions (low CO2).
 Also, due to the output bi-product (electricity and heat as a result of high
fuel conversion efficiency) and their prices, small size FCs in the coming
recent years are expected to be implemented in commercial and
residential buildings for both purposes of lighting and heating at the same
time.
 Today, Fuel Cells consist of staking cells, which give it the flexibility to be
built to match specific power needed with less capital cost. FC power
plants are commercially available for use by electric power producers and
industrial applications.
Disadvantages of FCs
From the electrical point of view, as a result of aging the FC internal impedance
slowly increases, therefore, we need a power electronic interface to regulate the
output voltage [45].
FC types and technologies
There are different types and operating technologies of fuel cells depending on
the electrolyte used such as: proton exchange membrane or polymer electrolyte
membrane fuel cell (PEMFC), alkaline fuel cell (AFC), direct methanol fuel cell
(DMFC), phosphoric acid fuel cell (PAFC), molten carbonate fuel cell (MCFC) and
solid oxide fuel cell (SOFC). The electrochemical process is based on the
electrolyte media used, which determines the FC operating temperature.
STORAGE DEVICES
It consists of batteries, flywheels, and other devices, which are charged during
low load demand and used when required. It is usually combined with other
kinds of DG types to supply the required peak load demand. These batteries are
called “deep cycle”.
- 44 -
Unlike car batteries, “shallow cycle” which will be damaged if they have several
times of deep discharging, deep cycle batteries can be charged and discharged a
large number of times without any failure or damage. These batteries have a
charging controller for protection from overcharge and over discharge as it
disconnects the charging process when the batteries have full charge. The sizes
of these batteries determine the battery discharge period. However, flywheels
systems can charge and provide 700kW in 5 s [42].
RENEWABLE DEVICES
Green power is a new clean energy from renewable resources like; sun, wind,
and water. Its electricity price is still higher than that of power generated from
conventional oil sources. Some types of renewable resources are discussed
below:
Photovoltaic (PV)
The construction of the Photovoltaic cell is based on the unit of PV. It is a cell
that may be square or round in shape, made of doped silicon crystal. Cells are
connected to form a module or panel and modules are connected to form an
array to generate the required power.
Figure 24. Photovoltaic cell diagram [53]
The operation and ratings of a PV cell is based on the absorption of solar energy
from the sunlight, where the light photons force cell electrons to flow, and
convert it to dc electricity. Practically, each cell provides 2–4A according to its
size with an output voltage of 0.5V. Normally an array, cells connected in series,
provides 12V to charge batteries.
Restrictions: PVs consist of modular which can be connected to provide a variety
of power ranges but on the other hand there are many restrictions:
 It provides low output power.
 The cost of land where PVs installed is expensive.
 It is restricted to certain geographic and weather features [37].
- 45 -
Some applications of PV are:
 Space programs as it provides power to satellites equipments and

transmitters in space.
 Remote communications, lighting road signs, roof projects for home

lighting and heating and road lighting. Also, PV provides “load direct
application” such as solar water pumping for use or storage that operates
only while sunlight exists. PV is cost efficient especially if the nearest line
of power is far from the application’s place.
 Solar energy can be used during the peak loads to fit with load curve
peaks. For example during summer days PV is used to provide the
necessary excess power required due to air conditioning and cooling
processes and the rest of the power is supplied to the grid so there is no
need to be “dispatchable”. There are different types of PV applications
such as:
 PV–diesel hybrid power system, which uses supervisory control and data
acquisition (SCADA) for control purposes.
 Standalone PV direct-coupled system supplies the output dc power directly

to a dc load, which operates only when there is solar energy. However,
standalone PV can be combined with storage “deep cycle” batteries to
maintain supplying loads even during nights, cloudy and bad weather.
 Also, in some applications PV systems can have an inverter to operate ac

loads as well.
Wind-turbines (WT)
Wind energy is not a new form it has been used for decades. A WT consists of a
rotor, turbine blades, generator, drive or coupling device, shaft, and the nacelle
(the turbine head) that contains the gearbox and the generator drive. Modern
wind turbines can provide clean electricity as individuals or as wind farms. Wind
turbine blades usually are two or three blades each nearly 10–30m long.
Figure 25. Wind turbine sketch [53]
The wind rotates the windmill-like blades, which in turn rotate their attached
shaft. This shaft operates a pump or a generator that produces electricity.
Although, the energy characteristics of larger wind turbine farms are closer to
- 46 -
the centralized energy sources, small wind turbines (working as modules) can be
combined with PV and battery systems to serve area of 25–100kW.
The advantages of wind turbines are.
 Contribute to clean air (no pollution) unlike the traditional oil fuel that
contributes acid rain (from sulphur dioxide or nitrogen oxides) and global
warming (from carbon dioxide) to the environment.
 Contribute to global safety (non-hazardous or radioactive wastes) unlike

nuclear power.
 Future sustainable (It has no input fuel, just the wind which will not run
out by time).
 Traditional fuel costs increase with time but wind energy costs decrease
with time
- 47 -
CHAPTER 4:
EXPERIMENTAL
DESIGN
This chapter is focused on the microreactor description, i.e. microreactor sizing,

microreactor material and operation conditions. We must say that all the
microreactor physic specifications have been carried out by a mechanical
engineer using CoventorWare®. It is a micro fluidic simulation package intended
for fluid flows at the micro scale.
We would like to emphasize that this chapter is only a summary of the overall
microreactor mechanical studio. However, some of the specifications like length,
flow rate, etc, have been used in the simulation work.
We would like to announce that the designs were finalized some time ago and
are now being fabricated in Tyndal national Institute in Cork City.
4.1. Experimental set-up

The Experimental set-up wants to specify which are the devices needed for
carrying out the overall process. Furthermore, it is important to find out exactly
what equipment will need to be ordered.
 Temperature controllers
 Gas Chromatographer
 Pressure gauge
 Gases
 Steel tubing, valves and fittings
 Brooks instrumental display
- 48 -
 Connections to the microreactor capillary tubing
 Brooks pressure controller
 Brooks mass flow controller for micro flow.
Some instruments are present in the laboratory already. Once the required
instrumentations is understood and a full and detailed process schematic is
produced, an order of equipment can be made.
Figure 26. Initial experimental set-up
4.2. Microreactor main parts

The design can be divided into the following parts.
 Cell (outline of the device). Cell size is 20 by 30 mm. Three design

variations. A 5mm keep-out area around the rim of the device for handling
and inlets.
 Inlet. The inlets are 5mm long and 365 μm wide. They have a notch at
500 μm from the exit. This is to stop the capillary tube when inserting so it
doesn’t block the exit. There are four inlets, two extra for catalyst
deposition. The etch is 365 μm deep.
 Catalyst. The catalyst is 300 μm wide and 10 mm long. The etch is 6 or

60 μm deep.
 Channel. There will be three different channel configurations with varying

channel number and length. The channels are 12 μm wide. A 100 μm wide
taper is drawn at the catalyst/taper connection. The etch is 6 or 60 μm
deep.
- 49 -
4.3. Proposed of micro reactor designs.

Various micro-channel reactor designs have been assessed according to several
studies of fluid dynamics. After considering,
 The choice of channel size an length in similar studies
 The maximum pressure acceptable within the silicon reactors
 The flow rate or volume of gaseous product required for Gas

Chromatography
 The inevitable energy losses of the gas flow through the channels
 The importance of the inclusion of meanders for the thorough mixing of

the reactants
 The need to vary the residence time within the micro channels.
The conclusion is that parallel micro channels are necessary for adequate flow
determined, thus the length and diameter of the channels varied. [53]
Figure 27. Micro reactor designs [53]
Below the width of the channels are shown:
Table 2. Width of the Channels (μm) depending on number of parallel

channels [53]
Straight 2 Bends 4 Bends
- 50 -
16[um] 58 19 11
60[um] 46 15 9
160[um] 31 10 6
In any of these reactors designs, the heat transfer study is required. The parallel
arrangements gives a lower velocity of the fluid tubes, which in turn results in a
lower pressure drop, but also a lower heat transfer coefficient (which affects the
temperature of the reactant mixture). The parallel arrangement is very suitable if
a second fluid outside the tubes is used for heat transfer. [54]
Figure 28. Microchannels in parallel and in series. [53]
On the other hand, with tubes in series, a high fluid velocity is obtained inside
the tubes and a higher heat transfer coefficient results. The series arrangements
is therefore often more suitable if heat transfer is by radiation, when the high
heat transfer coefficient helps to prevent overheating of the tubes and coke
formation in the case of organic materials.
4.4. Material of construction

The micro-reactors are based on a glass and silicon sandwich. The Silicon is
patterned and covered by glass to create the channels. The silicon is patterned
by deep reactive ion etching. [53]
Silicon is normally chosen as the substrate material because of its well-
established processing techniques, excellent thermal properties, and suitability
for catalyst coating.
Figure 29. Cross-section of structure to illustrate the different layers

[53]
The rank of experiment temperatures and pressure will be restricted by the

silicon. Furthermore, it is simulated that the top of temperature and pressure is
600K (~327ºC) and 10bar (~10atm), respectively.
- 51 -
Despite this restriction, the silicon is the best material that can be used in the
fabrication of the microreactor.
4.5. Operation conditions

It was assumed, based on the microreactor specifications that the microreactor is
operating: [53]
 Temperature: from -253K (~20ºC) to 600K (~327ºC)
 Pressure: from 1bar (~1atm) to 10bar (~10atmFor every micro channel

the flow rate is 0.01ml/min.
 Flow Rate: for each micro channel the flow is 0.01 ml/min.
- 52 -
CHAPTER 5:
MODELING AND
SIMULATION
The main idea of simulation is pretending to give a prediction of the experimental

behavior. Nowadays, the simulation procedure is more used than processes
based on finding the optimum theory adjust. The principal reason is the amount
of powerful computer packages that makes the calculations easier and quicker
than a human i.e. iterations, approximations. In fact, nowadays complex
experiments can be simulated by using empirical models only.
As it is said in previous chapter, the aim of the project is modelling and
simulating the RWGS reaction in a microreactor.
The simulations will be divided in two different models:
e) Empirical which guided by practical experience rather than precepts or
theory and
f) Semi-empirical which is guided by practical experience with some precepts
or theory.
Four models have been presented for the simulation of the RWGS reaction in a
microreactor. All the options are presented in the diagram below:
- 53 -
Figure 30. RWGS proposed models diagram
- 54 -
All of them must be executed following the order established above for achieving
which one fits better with the experimental data.
The three models above are carried out using two versatile software packages:
Microsoft Excel© and Aspen Hysys®
5.1. Computer packages

Microsoft Excel 2007©
Excel was used consistently for calculations throughout the design project. On
selection of the design project topic, it was necessary to decide on the target and
use this to perform the simulation calculations. This formed the basis for our
project. As a result of a many data results meant that Excel was especially useful
when carrying out calculations for the full range of products or for repetitive
calculations. When used to its full potential, it was also useful for examining the
effect of changing one parameter on any range of design.
Aspentech Hysys 2004.1®
Hysys is a process modelling program that allows us to simulate our production
plant. A flow sheet of our plant was modelled on Hysys. By inputting a number of
key data, such as composition, flow rate and temperature or pressure, it was
able to calculate a range of properties relating to energy, mass and other
parameters. Hysys was used to obtain a number of reports showing the
composition of our process streams and other stream data. Hysys allowed us to
print a range of reports on a range of stream data. We were able to print a range
of flow sheets from Hysys, each deal with important parameters such as stream
composition or physical conditions.
Ultimately, this design project aims to match manually calculated stream data
with Hysys calculations.
5.2. Hysys Simulations

5.2.1. Hysys devices
MIXER
The mixer operation combines two or more inlet streams to produce a single
outlet stream. A complete heat and material balance is performed with the
mixer. If the properties of all the inlet streams to the mixer are known, i.e.
temperature, pressure and composition, the properties of the outlet stream is
calculates automatically since the composition, pressure, and enthalpy is known
for that stream.
The mixture pressure and temperature are usually the unknowns to be
determined. However, the mixer also determines the missing temperature for
one of the inlet streams if the outlet is completely defined. [55]
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Figure 31. Hysys Mixer unit for the H2 and CO2 mixture.
COOLER/HEATER
The cooler and heater operation is one-side heat exchanger. The inlet stream is
cooled or heated, to the required outlet conditions, and the energy stream
absorbs (or provides) the enthalpy difference between the two streams. These
operations are useful when you are interested only in how much energy is
required to cool a process stream with a utility, but you are not interested in the
conditions of the utility itself. [55]
Figure 32. Hysys cooler unit.
REACTORS
The two reactors that have been used in the Hysys simulation are shown below.
Equilibrium reactor
The equilibrium reactor is a vessel which models equilibrium reactions. The outlet
streams of the reactor are in a state of chemical and physical equilibrium. [55] In
the production world this type of reactor does not exist, because the equilibrium
state depends exclusively of the temperature, pressure and compositions of the
reactants. Furthermore, for reaching the equilibrium state any of the previous
parameters have not to experiment any variation along the time. Thus, the
volume or the characteristics of the vessel will not have quite any influence in
the equilibrium stage. [55]
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Figure 33. Hysys Equilibrium reactor.
Plug flow reactor (PFR)

The tubular-low reactor is chosen when it is desired to operate the reactor
continuously but without back-mixing of reactant and products. In the case of an
ideal tubular reactor, the reaction mixture passes through in a state of plug flow
which means that the fluid moves like a solid plug or piston. [55]
Figure 34. Basic Tubular-flow reactor
Furthermore, in the ideal reactor it is assumed that not only the local mass flow
rate but also the fluid properties: temperature, pressure and compositions are
uniform across any section normal to the fluid motion. Of course the
compositions and possibly the temperature and pressure also, change between
inlet and outlet of the reactor in the longitudinal direction.
In the laboratory, tubular reactors are very convenient for gas-phase reactions.
Measurements are usually made when the reactor is operating in a steady state,
so that the conversion at the outlet or at any intermediate point does not change
with time.
For fast reactions, a physical method of determining the conversion is preferred
to avoid disturbing the reaction. The conversion obtained at the outlet is
regulated by changing either the flow rate or the volume of the reactor. In the
case of our microreactor, changing the volume will be forbidden because it is
being built. [54]
Figure 35. Hysys Plug Flow reactor
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The volume [Annex 8] of the two reactors have to be specify for making the
microreactor simulation more closer to the one that have been ordered.
5.2.2. Fluid packages

For the Hysys simulation a fluid package needed to be chosen. Choosing a
suitable property package is one of the most important considerations for a
successful process simulation. Two of the key factors to consider are:
 Specific system under consideration (what components are involved).
 Operating conditions.
Equations of state, such as Peng Robinson model, were developed originally to

deal with hydrocarbon gas systems.[51] Although they have proven to be very
reliable in predicting properties of most hydrocarbon based fluids over a large
range of operating conditions.
These are just some general guidelines in selecting property packages. [52]
 Peng-Robinson is most enhanced in Hysys, T & P range, has special

treatment for key components, largest binary interaction database: good
standard for hydrocarbons
 PRSV: extends PR to moderately non-ideal systems and better represents

poor components and mixtures. Adds a new parameter to the equation.
Slower calculation speeds than Peng-Robinson
 Chao-Seader: hydrocarbons if T = 0-500C, P<10,000 kPa
 Antoine: OK for low pressure ideal systems
The Fluid-Package that has been chosen is Peng-Robison. Its equation of state is
one of the simplest methods for accurately calculating saturated vapor densities,
vapor pressures and the vapor–liquid equilibrium, so it is widely used in the
chemical industry and for oil, gas and petrochemical applications, the Peng-
Robinson Equation of State is generally the recommended property package.
Enhancements to this equation of state enable its accuracy for a variety of
systems over a wide range of conditions. It rigorously solves most single-phase,
two-phase, and three-phase systems with a high degree of efficiency and
reliability. [51]
The Peng-Robinson Equation of State is shown as follow:
(23)
Where:
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The Peng-Robinson equation of stated can be also expressed in polynomial form:
(24)
Where:
This model is ideal for volume-liquid-equilibrium (VLE) calculations as well as

calculating liquid densities for hydrocarbon systems. Several enhancements to
the original Peng-Robinson model were made to extend its range of applicability
and to improve its predictions for some non-ideal systems. [52]
Another reason to choose The Peng-Robinson as a fluid package is because the
rank of temperature and pressure fits with the experimental conditions.
Table 3. Peng-Robinson Limited stages
TEMPERATURE (ºC) PRESSURE (kPa)

>-271 <100000
5.2.3. Hysys Flow sheet

The general structure of the two Hysys simulations follows the same approach.
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Figure 36. General Hysys simulation plan
Two streams (H2 and CO2) come inside the mixer unit which provides the
accurate conditions.
Table 4. Mixing unit Operation conditions
INPUTS OUT PUTS

CO2 H2 CO2 + H2
FLOW RATE mL/min 0,5 0,5 1
TEMPERATURE ºC 25 25 25
PRESSURE atm 10 10 10
After that, the blend needs to be heated in a heat exchanger. The heat
exchanger has been included in the simulation because, as far as we known, one
of them will be used in the future work.
Table 5. Heat exchanger operation conditions
INPUTS OUT PUTS

CO2 + H2 CO2 + H2
FLOW RATE mL/min 1 1
TEMPERATURE ºC 25 300
PRESSURE atm 10 ~ 10
After the heat exchanger process, the blend is transferred to the RWGS reaction.
The reactor inputs will be the same as the heat exchanger outputs. We want to
emphasize that the input reactor temperature can be change despite the Table 5
above marks 300ºC.
5.3. Model 0: Conversion

Conversion is the simplest model proposed in this project. However, it must be
taken into consideration because the specified conversion of a base reactant
might be required.
The main point of this model is that the conversion reminds constant along the
time; as a result, the equilibrium constant reminds constant, too. Thus, the
unknown compositions can be calculated at any time when the conversion is
known.
No Microsoft Excel© worksheet is required for the Aspen Hysys® simulation
because the conversion will be automatically calculated at the end of the
microreactor by a chromatograph.
On the Aspen Hysys® the conversion calculation may be performed on an
equilibrium reactor specifying in the equilibrium reaction tab the Keq Fixed
option. The Aspen Hysys® file simulation is: RWGS_MODEL_I.hch
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We would like to point out that another way to introduce the conversion is
possible: conversion can be defined as a function of reaction temperature.
However, it is assumed that the conversion will remind constant along time.
5.4. Model I: Thermodynamic

Thermodynamic model is the first simulation of the RWGS reaction in the
microreactor.
An equilibrium conversion is assumed and then equilibrium constant (Keq) is
calculated based on inputted results. The value of Keq can be related to the
reaction temperature or not.
The model is divided in the following part:
 Microsoft Excel© Worksheets : RWGS_MODEL_I
 Aspen Hysys®
a. RWGS_MODEL_I.HSC
5.4.1. Excel Simulation

The Excel simulation calculates the Equilibrium constant and the conversion for
each temperature. Furthermore, a plot is performed calculating the equilibrium
constants values.
Figure 37. Microsoft Excel © Sheet
The entire Excel follows the same coloration structure:
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 Values displayed in blue are user supplied.
 Black values represent calculated values or information that is provided by

calculations
First of all, it is established a rank of temperatures (150-400 ºC) separated by 10

ºC. These values can be changed if it is required.
For each temperature, an initial concentration of the main reactants will be
introduced. It is assumed, that either the initial concentrations or partial pressure
(CO2 and H2) are equals.
Table 6. General Excel-cell data
STAGE State i
Temperature (ºC) Ti
Temperature (K) Ti+273
1/T(K) 1/Ti(K)
[CO2] initial 0,5
[H2] initial 0,5
[CO2] final 0,37157032
[H2] final 0,38355005
[CO] final 0,12842968
[H20] final 0,11644995
Keq 0,10494015
ln(Keq) -2,25436512
X 0.24487963
The table above shows the general structure of the Excel. A part from the initial
concentrations, the experimental results is introduced. Using the next
expression:
(25)
The equilibrium constant (Keq) and its logarithm is calculated. Afterwards, a

graphic is performed between the ln (Keq) versus the inverse of the
temperature.
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Figure 38. Graphic ln (Keq) Vs 1/T (K) with the linear tendency
A linear trend line is added using the experimental data, which accuracy depends
exclusively on the experimental results, i.e. the higher value of the R-squared
value, the better is adjust.
The purpose of the trend line is to find the constant at any temperature by
interpolating in the line.
Table 7. Conversion for a desired temperature
ºC K 1/T
T study 255 528 0,00189394
liniar tendency: y = ax + b
a= -1243,916479
b= 0,734187009
ln(Keq) -1,621715413
Keq 0,197559512
conversion
X1 X2
-0,400052212 0,153853877
Once the equilibrium constant is found at the study temperature, two options can
be chosen:
1. Finding the conversion or equilibrium with the Microsoft Excel © Worksheets
2. Go to the AspenHysys®:
a) RWGS_MODEL_I.HSC and find the parameters desired.
5.4.2. Hysys simulation
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The two Hysys simulations follow the same structure: Mixer, Heater and
Equilibrium Reactor.
It must be noted that both simulations have to be configured with the
instructions given in [Annex 7]
Figure 39. Hysys Equilibrium simulation sheet
The Hysys simulation is divided in the following parts which are basis in reaction
selection.
a) MODEL I A Keq is fixed and is thus independent of temperature. You may
specify either Keq or Ln(Keq) on the Keq tab.
b) MODEL I C The Keq is determined from the default HYSYS pure
component Gibbs Free Energy (G) database and correlation.
c) MODEL I B/D Keq is related to temperature (Keq Vs. T Table) or is
related to the next equation a+bT.
Depending on which option was selected in the Keq source group, the Keq tab
will be display the appropriate information.
Figure 40. Hysys Equilibrium reaction tab
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Figure 41. Hysys Equilibrium Keq source tab
5.4.3. Hysys simulation: MODEL I A

The simulation A starts with the configuration of the temperature in the input
and outputs in the reactor, e. g. 200°C
Figure 42. RWGS_MODEL_I_A temperature configurations
Following, the reaction base is configured by selection the Fixed Keq tip as it is
shown below.
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Figure 43. RWGS_MODEL_I_A Keq configurations
If the temperature is 200ºC the equilibrium constant is 0, 14487875 which is

picked on the Microsoft Excel© worksheet.
Figure 44. Microsoft Excel© and Aspen Hysys ® Keq at 200ºC
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When the Keq and the temperature are configured we must check if the final
compositions follow the experimental values disposed in the Excel Worksheet.
Figure 45. Aspen Hysys ® compositions at 200ºC
When everything is ready and the compositions are adjusted to the experimental
data, the only parameter that cannot be changed in Aspen Hysys ® is the
temperature.
Furthermore, a CASE STUDY [Annex 6] is the best tool for knowing the
experiment behaviour.
5.4.4. Hysys simulation: MODEL I C

The C Hysys simulation is a black box calculation.
Like the previous simulation (A), simulation C starts with the configuration of the
temperature in the input and outputs in the reactor, e. g. 200°C.
Following, the reaction base is configured by selection the Gibbs Free Energy tip
as it is shown below.
Figure 46. RWGS_MODEL_I Keq configurations
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The equilibrium constant is determined from the default HYSYS pure component
Gibbs Free Energy (G) database and correlation.
The correlation and database values are valid/accurate for a temperature (T)
range of 25ºC to 426,85ºC.
If a wider range of G-T correlation is required, we can clone the library
component and input the components Gibbs Free Energy correlation to
temperatures beyond the default temperature limit.
Figure 47. RWGS_MODEL_I Gibbs Free Energy vs Keq
5.4.5. Hysys simulation: MODEL I B/D

The simulation B/D will provide us a closer approximation with the real
experimental results.
Like the previous simulation (A), simulation B/D starts with the configuration of
the temperature in the input and outputs in the reactor, e. g. 200°C.
Following, the reaction base is configured by selection the Keq vs T table tip as it
is shown below. In this model we have two options but in RWGS_MODEL_I.hch
only works Keq versus T Table.
Figure 48. RWGS_MODEL_I Keq configurations
We will introduce for each temperature the Keq that corresponds. Each pair is
provided in the Microsoft Excel© worksheet. We must say that the temperature
steps (in the figure below is every 50 degrees) this may be altered as desired.
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Figure 49. Microsoft Excel© and Aspen Hysys ® Keq at 200ºC
When the Keq and the temperature are configured we must check if the final
compositions follow the experimental values disposed in the Excel Worksheet.
Figure 50. Aspen Hysys ® compositions at 200ºC
When everything is well defined and the composition is adjusted to the

experimental data, the only parameter that cannot be changed in Aspen Hysys ®
is the temperature.
Furthermore, CASE STUDY [Annex 6] is the best tool for knowing the experiment
behaviour.
- 69 -
5.5. Model II: Chemist kinetics

The Chemist Kinetics models are proposed because the RWGS is a catalytic
reaction and the reaction proceeding might be controlled by the kinetics, i.e. no
adsorption or desorption from the catalyst have any effect on the reaction.
Two chemist kinetic models have been studied:
a) CSTR: Continuous-Stirred Tank Reactor
b) PFR: Plug Flow Reactor
5.5.1. CSTR
Continuous-Stirred Tank Reactor is a vessel in which a blend is agitated.
In the previous chapter, the microreactor characteristics have been explained.
The conclusion has been that parallel microchannels might be used for obtaining
a high performance. Thus, the CSTR simulation will not be the appropriate way
to simulate the RWGS reaction. The microreactor will follow a Tubular reactor
structure which generally consists of a bank of cylindrical pipes, tubes or
microchannels.
It is decided to reject the CSTR model because the microreactor design
specifications do not follow the CSTR ones.
5.5.2. Plug Flow reactor

We proposed two Chemist Kinetics models where the main difference between
them is the reaction structure.
The first model follows a simple reaction as:
(26)
And the second model will follow the structure:
(27)
For each of them, the same things will be determined, i.e. Arrhenius equation
parameters, constant rates, etc. Some of these parameters are determined using
two Microsoft Excel© books:
a) RWGS_MODEL_II_A
b) RWGS_MODEL_II_B
Afterwards, an Aspen Hysys® simulation program will be used:
RWGS_MODEL_II
The reactions above have two directions: forward and reverse. It is assumed that
the forward reaction is the RWGS and the reverse reaction is the WGS.
5.5.3. PFR: Model II A

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The first model introduced a chemistry equation [Annex 1] to calculate the final
concentration of the reactants and products at the end of the reactor. The two
expressions below will be the starting point for the manual calculations of the
kinetic equation parameters.
(28)
(29)
In this case, the Microsoft Excel© software becomes a helper tool for the future
Hysys simulation. The Excel book called: RWGS_MODEL_II_A is composed by
three sheets:
a) K_values
b) Arrehenius and
c) K_equilibrim.
First sheet: K_values

The objective of the first sheet is finding the two rate constants (kRWGS, kWGS)
from the Arrhenius Equation. Experimental data and theory results, achieved by
the two equations above, will configure the Microsoft Excel© model. Afterwards,
using the Excel tool called SOLVER [Annex 5] the adjustment of the two rate
constants will be done.
- 71 -
Figure 51. K_values sheet in Microsoft Excel© in Model II a
The procedure starts by introducing two random values of the rate constant.
Afterwards the initial concentrations of A and B have to be insert in the
respective cells at t=0. The rank of concentrations will depend on the
microreactor flow rate, however the initial concentration of B will be zero because
it is assumed that at the t=0 will not be any conversion. Automatically, the final
concentrations of A and B will be calculated.
Once this is done, the experimental results have to be introduced in the
Experimental columns.
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Table 8. Model values for a kRWR=1 and kWGS=0,5
Model Experimental
t Ca o Cb o Ca f Cb f t Ca o Cb o Ca f Cb f
0 1 0 1 0 0 1 0 1 0
0,1 1 0 0,907139 0,092861 0,1 1 0 0,95 0,17

0,2 1 0 0,827212 0,172788 0,2 1 0 0,9 0,35
0,3 1 0 0,758419 0,241581 0,3 1 0 0,88 0,39
0,4 1 0 0,699208 0,300792 0,4 1 0 0,85 0,44
0,5 1 0 0,648244 0,351756 0,5 1 0 0,83 0,52
0,6 1 0 0,604380 0,395620 0,6 1 0 0,8 0,53
0,7 1 0 0,566625 0,433375 0,7 1 0 0,77 0,54
0,8 1 0 0,534129 0,465871 0,8 1 0 0,76 0,57
0,9 1 0 0,506160 0,493840 0,9 1 0 0,75 0,56
1 1 0 0,482087 0,517913 1 1 0 0,74 0,56
1,1 1 0 0,461367 0,538633 1,1 1 0 0,73 0,58
1,2 1 0 0,443533 0,556467 1,2 1 0 0,69 0,58
1,3 1 0 0,428183 0,571817 1,3 1 0 0,65 0,58
1,4 1 0 0,414971 0,585029 1,4 1 0 0,62 0,59
1,5 1 0 0,403599 0,596401 1,5 1 0 0,6 0,59
1,6 1 0 0,393812 0,606188 1,6 1 0 0,57 0,59
1,7 1 0 0,385388 0,614612 1,7 1 0 0,56 0,6
1,8 1 0 0,378137 0,621863 1,8 1 0 0,52 0,6
1,9 1 0 0,371896 0,628104 1,9 1 0 0,5 0,6
Simultaneously, the model calculates the square errors between the model
values and experimental data. Furthermore, the summation of the square error
(SSE) and the square regression parameter are also calculated for each of the
cases (Ca, Cb).
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Table 9. Square errors, SSE and quadratic
MODEL VS EXPERIMENTAL
Ca Cb
0,000000 0,000000
0,001837 0,005950
0,005298 0,031404
0,014782 0,022028
0,022738 0,019379
0,033035 0,028306
0,038267 0,018058
0,041361 0,011369
0,051017 0,010843
0,059458 0,004377
0,066519 0,001771
0,072164 0,001711
0,060746 0,000814
0,049203 0,000231
0,042037 0,000025
0,038573 0,000007
0,031042 0,000056
0,030489 0,000214
0,020125 0,000478
0,016411 0,000790
SSE 0,695104 0,157811
R2 0,887200 0,877558
SOLVER, the Microsoft Excel© tool, must be used for minimizing the SSE values.
However, SOLVER does not let us optimize two independent cells. This means
that an objective function has to be established. [Annex 5] The following
objective function (Z) is the one that have been assumed:
(30)
The SOLVER will minimize the objective function by changing the two rate
constants (kRWGS, kWGS) cells.
Figure 52. Solver sketch
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For the example above, where the initials kRWGS and kWGS are 0,5 and 1,
respectively; after the SOLVER application the new rate constants are kRWGS =
0,95 and kWGS = 1,04.
With these two new values, the experimental values are closer to the model
curve. There are two ways to visualize the approach: graphically or
mathematically.
 Graphically: comparing the two plots and observe the behaviour of the
model in front of the experiment results.
Figure 53. From left to right: kRWGS = 0,5 and kWGS = 1; kRWGS = 0,95
and kWGS = 1,04.
 Mathematically: comparing the SSE or the square regression parameter.
- 75 -
Table 10. Mathematic comparison
kRWGS = 0,5 and kWGS = 1 kRWGS = 0,95 and kWGS = 1,04

Ca Cb Ca Cb
SSE 0,695104 0,157811 SSE 0,330821 0,316619
R2 0,887200 0,877558 R2 0,829866 0,929007
Once the optimization has been done it is time to move to the next Excel flap.
Second Sheet: A of Arrhenius

With the rate constants founded in K_values sheet in excel, to find the pre-
exponential factor for the Arrhenius equation [Annex 2].
The two values from the Energy activation (Ea) are possible:
1. Find their value in the relevant literature or
2. Obtain it by doing some laboratory experiments.
Figure 54. Microsoft EXCEL© A of Arrhenius sheet
Finally, with the A parameter all the chemical parameters are completed. In fact
we have now two options to carry on with the simulation.
1. Microsoft Excel ©: the parameters will be introduced in the third sheet

K_equilibrium; thus, we can compare the experimental Keq constants
between model Keq constant.
2. Aspen Hysys®: the parameters (Ea and A) will be introduced in the Hysys
simulation.
OPTION 1. Microsoft Excel©

All the parameters are introduced in the third sheet K_equilibrium. The
objective of the Excel simulation is the comparison of the experimental Keq
constant against model Keq constant.
- 76 -
Figure 55. Microsoft EXCEL© K_equilibrium sheet
To achieve the best adjustment of the overall rate constant, it is possible to

modify the β parameter; initially they do not have any value.
The β value is a parameter which has not a real chemical meaning, it is only a
parameter that gives a better adjust to the simulation.
Figure 56. Beta (β) parameters
Below two plots are shown where the effects of changing the β parameters can
be appreciated.
- 77 -
Figure 57. Left to right: βRWGS=βWGS=0; βRWGS= 0,4 and βWGS=0,01
With an accurate adjust from the Keq it is possible to predict the conversion of
the products. [Annex 4]
OPTION 2. Aspen Hysys®

As it is appreciated the RWGS microreactor is now a Plug Flow Reactor which
means that only certain reaction sets are allowed, i.e. Kinetic, Heterogeneous
Catalytic and Simple reaction. Kinetic is the one that has been chosen.
To define a Kinetic Reaction, it is necessary to specify the forward Arrhenius
Parameters, the stoichiometry coefficients for each component and the forward
reaction orders.
The second option allows us to introduce the Microsoft Excel© parameters Ea
(energy activation) and A (pre-exponential factor) in the Aspen Hysys®
software. This option is the best because, as it is mentioned previously, Aspen
Hysys® is simulator software which may provide us a higher accuracy.
It must be noted that the mixer and the heater must configured following the
instructions given in [Annex 7]
- 78 -
Figure 58. Hysys Kinetic model I simulation sheet
On the Parameters tab, you may specify the forward and reverse parameters for
the Arrhenius equations, previously calculated it in the RWGS_MODEL_II_A.xls
Figure 59. Aspen Hysys® previous kinetic parameters tabs window for
a kinetic Reaction in the Plug flow reactor
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Figure 60. Aspen Hysys® Kinetic parameters tabs for a kinetic

Reaction in the Plug flow reactor
Once the reaction has been introduced in the Plug Flow Reactor set many aspects
have to be considered.
 If the OUTPUT_1 stream conditions (temperature and compositions) are

not the ones that the user wants, some of the reactor conditions must be
changed.
Figure 61. Aspen Hysys® OUTPUT_1 stream conditions
- 80 -
Figure 62. Aspen Hysys® OUTPUT_1 stream compositions
 If the OUTPUT_1 stream compositions are not the ones that give an
accurate adjustment from the experiment, the beta (β) parameter must be
changed.
Figure 63. Aspen Hysys® Kinetic parameters tabs for a kinetic

Reaction in the Plug flow reactor with different beta values
Once all the aspects have been done, the compositions of the inputs and output
from the reactor must be checked again.
- 81 -
Figure 64. Aspen Hysys® Kinetic composition in the Input and output
from the Plug flow Reactor
When the reactor has been shaped, it is time to check if there is no problem by
changing different operation conditions like: temperature, pressure, etc.
Furthermore, while we change these parameters, new output conditions are
obtained. The best way to collect the new results is using the Aspen Hysys®
CASESTUDY. [Annex 6]
5.5.4. PFR: Model II B

The second model introduced a mathematic approximation, EULER, [Annex 3] to
calculate the final concentrations of the reactants and products at the end of the
reactor.
Once again, the Microsoft Excel© software becomes a helper tool for the future
Hysys simulation. The Excel book called: RWGS_MODEL_II_B is composed by
three sheets:
a) K_values
b) Arrehenius and
c) K_equilibrim.
The final concentrations are calculated using an algorithm that is introduced in
Microsoft Visual Basic as a macro.
Figure 65. Microsoft Visual Basic EULER function
- 82 -
First sheet: K_values

The objective of the first sheet, as it was in the RWGS_MODEL_II_B is finding the
two rate constants (kRWGS, kWGS). Experimental data and theory results, achieved
by C_EULER function above, will configure the Microsoft Excel© model.
Afterwards, using the Excel tool called SOLVER the adjustment of the two rate
constants will be done.
Figure 66. K_values sheet in Microsoft Excel© in Model II B
The procedure starts by introducing two random values of the rate constant and
the number of steps that C_EULER have to do for making the adjust. Afterwards
the initial concentrations of H2 and CO2 are inserted insert in the respective cells
at t=0. The rank of concentrations will depend on the microreactor flow rate,
however the initial concentrations of CO and H2O will be zero because it is
assumed that at the t=0 will not be any outputs. Automatically, the final
concentrations from all the reactants and products are calculated using the
C_EULER function.
- 83 -
Table 11. Initial Model values for a kRWGS=1 and kWGS=0,5
Initial Model
to H2 CO2 CO H2O t H2 CO2 CO H2O Steps
0 0,7 0,8 0 0 0,00 0,7000 0,8000 0,0000 0,0000 100
0 0,5 0,8 0 0 0,10 0,6730 0,7730 0,0270 0,0270 100
0 0,5 0,8 0 0 0,20 0,6481 0,7481 0,0519 0,0519 100
0 0,5 0,8 0 0 0,30 0,6250 0,7250 0,0750 0,0750 100
0 0,5 0,8 0 0 0,40 0,6037 0,7037 0,0963 0,0963 100
0 0,5 0,8 0 0 0,50 0,5842 0,6842 0,1158 0,1158 100
0 0,5 0,8 0 0 0,60 0,5662 0,6662 0,1338 0,1338 100
0 0,5 0,8 0 0 0,70 0,5498 0,6498 0,1502 0,1502 100
0 0,5 0,8 0 0 0,80 0,5348 0,6348 0,1652 0,1652 100
0 0,5 0,8 0 0 0,90 0,5211 0,6211 0,1789 0,1789 100
0 0,5 0,8 0 0 1,00 0,5086 0,6086 0,1914 0,1914 100
0 0,5 0,8 0 0 1,10 0,4972 0,5972 0,2028 0,2028 100
0 0,5 0,8 0 0 1,20 0,4869 0,5869 0,2131 0,2131 100
0 0,5 0,8 0 0 1,30 0,4775 0,5775 0,2225 0,2225 100
0 0,5 0,8 0 0 1,40 0,4690 0,5690 0,2310 0,2310 100
0 0,5 0,8 0 0 1,50 0,4612 0,5612 0,2388 0,2388 100
0 0,5 0,8 0 0 1,60 0,4543 0,5543 0,2457 0,2457 100
0 0,5 0,8 0 0 1,70 0,4479 0,5479 0,2521 0,2521 100
0 0,5 0,8 0 0 1,80 0,4422 0,5422 0,2578 0,2578 100
0 0,5 0,8 0 0 1,90 0,4370 0,5370 0,2630 0,2630 100
Once this is done, the experimental results have to be introduced in the

Experimental columns.
- 84 -
Table 12. Initial Model values for a kRWGS=1 and kWGS=0,5
Experimental
t H2 CO2 CO H2O
0,00 0,7440 0,8029 0,0000 0,0000
0,10 0,6510 0,8086 0,0251 0,0261
0,20 0,6888 0,7918 0,0526 0,0539
0,30 0,5794 0,7710 0,0789 0,0742
0,40 0,6487 0,6796 0,1007 0,0924
0,50 0,5834 0,6886 0,1148 0,1154
0,60 0,5987 0,6541 0,1357 0,1399
0,70 0,5705 0,6421 0,1453 0,1418
0,80 0,5586 0,6171 0,1578 0,1649
0,90 0,5601 0,6248 0,1793 0,1881
1,00 0,5198 0,5861 0,1878 0,1997
1,10 0,4613 0,6385 0,1898 0,1994
1,20 0,4704 0,5956 0,2138 0,2116
1,30 0,4422 0,5656 0,2336 0,2289
1,40 0,4588 0,5335 0,2431 0,2449
1,50 0,4855 0,5272 0,2566 0,2400
1,60 0,4687 0,5490 0,2592 0,2374
1,70 0,4230 0,5619 0,2561 0,2358
1,80 0,4749 0,5334 0,2694 0,2568
1,90 0,4140 0,5098 0,2554 0,2571
Simultaneously, the model calculates the square errors between the model
values and experimental data. Furthermore, the summation of the square error
(SSE) and the square regression parameter are also calculated for each of the
components (CO2, H2, CO, H2O)
- 85 -
Table 13. Square errors, SSE and quadratic
MODEL VS EXPERIMENTAL
H2 CO2 CO H2O
0,0019 0,0000 0,0000 0,0000
0,0005 0,0013 0,0000 0,0000
0,0017 0,0019 0,0000 0,0000
0,0021 0,0021 0,0000 0,0000
0,0020 0,0006 0,0000 0,0000
0,0000 0,0000 0,0000 0,0000
0,0011 0,0001 0,0000 0,0000
0,0004 0,0001 0,0000 0,0001
0,0006 0,0003 0,0001 0,0000
0,0015 0,0000 0,0000 0,0001
0,0001 0,0005 0,0000 0,0001
0,0013 0,0017 0,0002 0,0000
0,0003 0,0001 0,0000 0,0000
0,0012 0,0001 0,0001 0,0000
0,0001 0,0013 0,0001 0,0002
0,0006 0,0012 0,0003 0,0000
0,0002 0,0000 0,0002 0,0001
0,0006 0,0002 0,0000 0,0003
0,0011 0,0001 0,0001 0,0000
0,0005 0,0007 0,0001 0,0000
SSE 0,0178 0,0123 0,0013 0,0009
R2 0,9031 0,9470 0,9919 0,9929
SOLVER, the Microsoft Excel© tool, must be used for minimizing the SSE values.
However, SOLVER does not let us optimize two independent cells, what means
that an objective function has to be established, as it is done in the kinetic model
II. The same objective function (Z) has been assumed.
(30)
The SOLVER will minimize the objective function by changing the two rate
constants (kRWGS, kWGS) cells.
Figure 49. SOLVER sketch
- 86 -
For the example above, where the initials kRWGS and kWGS are 0,5 and 1,
respectively; after the SOLVER application the new rate constants are kRWGS =
0,68 and kWGS = 0,48.
With these two new values, the experimental values are closer to the model
curve. There are two ways to visualize the approach: graphically or
mathematically.
 Graphically: comparing the two plots and observe the behaviour of the
model in front of the experiment results.
Figure 67. Up and down: kRWGS = 0,5 and kWGS = 1; kRWGS = 0,68 and
kWGS = 0,48.
 Mathematically: comparing the SSE or the square regression parameter.
Table 14. Mathematic comparison
kRWGS = 0,5 and kWGS = 1 kRWGS = 0,68 and kWGS = 0,48

H2 CO2 CO H2O H2 CO2 CO H2O
SSE 0,0178 0,0123 0,0013 0,0009 0,0173 0,0116 0,0011 0,0014 0,0173
R2 0,9031 0,9470 0,9919 0,9929 0,9034 0,9452 0,9924 0,9902 0,9034
- 87 -
Second sheet: A of Arrhenius

With the rate constants founded in K_values the pre-exponential factor from the
Arrhenius equation.
The two values from the Energy activation (Ea) are possible to find their value in
the literature. However, we suggest calculating it by doing some laboratory
experiments
Figure 68. Microsoft EXCEL© A of Arrhenius sheet
Finally, with the A parameter all the chemical parameters are completed. In fact,
we have now two options to carry on with the simulation.
1. Microsoft excel ©: the parameters will be introduced in the third sheet

K_equilibrium; thus, we can compare the experimental Keq constants
between model Keq constant.
2. Aspen Hysys®: the parameters (Ea and A) will be introduced in the Hysys
simulation
Both options and procedures are exactly the same as the once explain in the
Model II A.
5.6. Model III: Adsorption kinetics

Adsorption kinetics is being mentioned just in case the RWGS system does not
follow the three other models, i.e. conversion, thermodynamic or chemist
kinetics.
As it is mention in the RWGS reaction kinetics, the RWGS system is carried out
using a heterogenic catalyst (CuO/ZnO/Al2O3) where the general agreement is
that copper provides the active site from catalysis i.e . adsorption/desorption
mechanism is probable to be the reaction limited stage. However, the
mechanism of the reaction over Cu-based catalyst is still not certain.
To conclude we want to state that the Adsorption kinetics model has been
avoided because the in the Aspen Hysys® software is not allowed to introduce
the heterogeneous catalyst parameters.
- 88 -
CHAPTER 6:
CONCLUSIONS
6.1. Proposal of possible methods

The key of the simulation is that we can improve the experiment without
investing more money or loosing time. The simulation software lets us to:
 Play with the software tools and propose different operating conditions,
like changing temperature, pressure, etc.
 Obtain new results with the operation conditions modifications without

doing the experiment.
 Use more devices in the overall process, e.g. introduction of a recirculation

in the RGWS process, as it shows below:
Figure 69. RWGS recirculation process
- 89 -
6.2. Conclusions
The project achieves the objectives established in the beginning of the report:
 A simulation of the RWGS in a microreactor has been performed.
 The RWGS reaction in a microreactor is being simulated by using two

versatile software packages, i.e. Microsoft Excel© and Aspen Hysys®.
 The Microsoft Excel© worksheets are performed for giving an adjustment

of the unknown parameters from the Aspen Hysys® simulations.
 The invention of the Microsoft Excel© experimental results (given in blue)

is been done because it is the only way to verify if the manual calculations
are correct.
 Model 0: Conversion follows the same structure us Model I case A ( Keq

fixed)
 Model 0: Conversion has been avoided because of the conversion along

the microreactor is constant.
 Model 1: Thermodynamic has been decided to be one of most reliable

adjust for the RWGS system. Concretely, the cases B and D, where the
Equilibrium constant varies with the temperature. ( Keq Vs Tª)
 Model 2: Chemist kinetics case CSTR has been avoided because of the
rector design specifications, i.e. the microreactor is not a continuous
stirred tank reactor, it is a continuous plug flow.
 Model 2: Chemist kinetics case PFR is proposed to be the model which will
give a better fitting with the ordered microreactor.
 Model 3: Adsorption kinetics is being mentioned just in case the RWGS

system does not follow the three other models, i.e. conversion,
thermodynamic or chemist kinetics.
 Model 3: Adsorption kinetics model has been avoided because the in the
Aspen Hysys® software is not allowed to introduce the heterogeneous
catalyst parameters.
- 90 -
CHAPTER 7:
BIBLIOGRAFIA
7.1. Referències bibliogràfiques

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[7] Gery Jacobs Applied Catalysis A: General 284 (2005) 31–38
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for hydrogen production and applications. ELSEVIER publications, september 2009.
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Production by Nuclear-Heated Steam Reforming of Fossil Fuels. ELSEVIER, Great Britain, 2005.
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technologies. CRC Press Editions, New York:2008.
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Bubble column reactor, Chem. Eng. Comm., 190: 445 – 474, 2003
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Angentina. ELSEVIER, October 1996.
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Chemistry, Wiley-VCH, Weinheim, (1999)
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µTAS96 – Special Issue of Analytical Methods & Instrumentation AMI, pp. 3-8, Basel, (1996).
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Technology; IMRET 1 pp. 278-288, SpringerVerlag, Berlin, (1997).
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microfabricated capillary array electrophoresis chip, Proc. Natl. #acad. #sci. USA 91, (1994)
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Microsystems for analysis in flowig solutions, in Proceedings of the “Micro Total Analysis
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Analysis Systems, µTAS96 – Special Issue of Analytical Methods & Instrumentation AMI, pp.
28-30, Basel, (1996).
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International Conference on Microreaction Technology; Topical Conference Preprints, pp. 241-
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111, 17 (1999) 2630-2647.
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of microstructure reactors, micro heat exchangers and micromixers for industrial applications in
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Preprints, pp. 88-95, AICHE, New Orleans, USA, (1998).
[37] J.L. Del Monaco, The role of distributed generation in the critical electric power infrastructure,
in: Proceedings of the Power Engineering Society Winter Meeting IEEE, vol. 1, 2001, 144–145.
[38] Microsoft EXCEL© 2007. Help Manual. Edited by Microsoft 2007
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Chemistry. Wiley-Vch first edition 2001
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Surf. Sci. Catal., Vol. 109, 401-416 (1997).
[41] M. Suter, Active filter for a microturbine, in: Proceedings of the Telecommunications Energy
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[42] B. Lasseter, Microgrids [distributed power generation], in: Proceedings of the Power
Engineering Society Winter Meeting IEEE, vol. 1, 2001, pp. 146–149.
[43] Willam, E. Liss, Natural gas power systems for the distributed generation market, in:
Proceedings of the Power-Gen International’99 Conference, New Orleans, LA, 1999.
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conversion for the 21st century, in: Proceedings of the IEEE, vol. 89, issue 12, December 2001,
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[45] M. Farooque, H.C. Maru, Fuel cells—the clean and efficient power generators, in: Proceedings
of the IEEE, vol. 89, issue 12, 2001, pp. 1819–1829.
[46] Wm.L. Hughes, Comments on the hydrogen fuel cell as a competitive energy source, in:
Proceedings of the Power Engineering Society Summer Meeting IEEE, vol. 1, 2001, 726–730.
[47] S. Rahman, Fuel gm as a distributed generation technology, in: Proceedings of the Power
Engineering Society Summer Meeting IEEE, vol. 1, 2001, pp. 551–552.
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[49] Chen, C.-S., Cheng, W.-H., Lin, S.-S., Mechanism of CO formation in reverse water-gas shift
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Fundam., 15, 59-64, 1976.
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[53] MacSuibhne, Pádraig. Reports about the Micro-reactor design. Microsoft word© and Microsoft
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7.2. Bibliografía de Consulta

Wang Luhui, Zhang Shaoxing, and Liu Yuan “Reverse water gas shift reaction over Co-precipitated
Ni-CeO2 catalysts” Journal of rare earths, 26 (2008) 66-70. Sciencedirect.com
Robert Bernard Anderson “The Fischer-Tropsch synthesis” Academic Press (Harcourt Brace
Jovanovich, Publishers)
Howard F. Rase “Chemical reactor design for process plants” Vol. II Case Studies & Design Data.
Wiley-Interscience Publication. 1977.
B.H. Davis and M.L. Ocelli “Fischer-Tropsch synthesis, catalysts and catalysis” Studies in Surface
Science and Catalysis. Vol. 163. Elsevier first edition 2007.
Klaus S. Lackner (Director of the Lenfest Center for Sustainable energy),
www.earthinstitute.columbia.edu
A.P. Steynberg, M. E. Dry; “Fischer-Tropsch Technology“ Studies in Surface Science and Catalysis
Elsevier Vol. 152; Elsevier first edition 2004.
Wolfgang Ehrfeld, Volker Hessel, Holger Lowe; “Microreactors” New Technology for Modern
Chemistry. Wiley-Vch first edition 2001.
Sujit Srinivasa, Amit Dhingrab, Hong Imb, Erdogan Gulari. A scalable silicon microreactor for
preferential CO oxidation: performance comparison with a tubular packed-bed microreactor.
Elsevier June 2004.
- 94 -
ANNEX 1. EQUILIBRIUM REACTIONS OR OPPOSED REACTIONS

A pair of forward and reverse reactions may define an equilibrium process. For
example A and B react into X and Y and vice versa (s, t, u and v are the
stoichiometry coefficients):
(27)
The reaction rate expression for the above reactions (assuming they each are
elementary) can be expressed as:
(31)
Where: k1 is the rate coefficient for the reaction which consumes A and B; k2 is
the rate coefficient for the backwards reaction, which consumes X and Y and
produces A and B.
(32)
(33)
The constants k1 and k2 are related to the equilibrium coefficient for the reaction
(K) by the following relationship (set r=0 in balance):
Figure 70. Concentration of A (A0 = 0.25 mole/l) and B versus time

reaching equilibrium kf = 2 min-1 and kr = 1 min-1
- 95 -
Simple Example
In a simple equilibrium between two species:
(26)
Where the reactions starts with an initial concentration of A, [A]0, with an initial
concentration of 0 for B at time t=0. Then the constant K at equilibrium is
expressed as:
(34)
Where [A]e and [B]e are the concentrations of A and B at equilibrium,

respectively.
The concentration of A at time t, [A]t, is related to the concentration of B at time
t, [B]t, by the equilibrium reaction equation:
(35)
Note the term [B]0 is not present because in this simple example, the initial
concentration of B is 0.
This applies even when time t is at infinity, i.e. equilibrium has been reached:
(36)
Then it follows, by the definition of K, that
(37)
and therefore,
(38)
These equations allow us to uncouple the system of differential equations, and

allow us to solve for the concentration of A alone.
The reaction equation, given previously as:
(39)
- 96 -
The derivative is negative because this is the rate of the reaction going from A to
B, and therefore the concentration of A is decreasing. To simplify annotation, let
x be [A]t, the concentration of A at time t. Let xe be the concentration of A at
equilibrium. Then:
(40)
(41)
(42)
(43)
Since:
(44)
The reaction rate becomes:
(45)
Which results in:
(46)
A plot of the negative natural logarithm of the concentration of A in time minus

the concentration at equilibrium versus time t gives a straight line with slope kf +
kb. By measurement of Ae and Be the values of K and the two reaction rate
constants will be known.
Generalization of Simple Example

If the concentration at the time t = 0 is different then above, the simplifications
above are invalid, and a system of differential equations must be solved.
However, this system can also be solved exactly to yield the following
generalized expressions:
(28)
- 97 -
(29)
- 98 -
ANNEX 2. ARRHENIUS EQUATION

The Arrhenius equation gives the dependence of the rate constant k of chemical
reactions on the temperature T.
At higher temperatures, the probability that two molecules will collide is higher.
This higher collision rate results in a higher kinetic energy, which has an effect
on the activation energy of the reaction. The activation energy is the amount of
energy required to ensure that a reaction happens.
This calculator calculates the effect of temperature on reaction rates using the
Arrhenius equation
(47)
Where k is the rate coefficient, A is a constant, Ea is the activation energy, R is

the universal gas constant, and T is the temperature (in Kelvin)·R has the value
of 8.314 x 10-3 kJ mol-1K-1
In our case we will use the Arrhenius equation to obtain the A parameter, Hence
the equation will be the following:
(48)
- 99 -
ANNEX 3. EULER APROXIMATION

Leonhard Euler was a pioneering Swiss mathematician and physic. He made
important discoveries in fields as diverse as infinitesimal calculus, graph theory
and algebra.
The EXCEL worksheet RWGS_kinetics_MODEL_II applies for a function C_Euler
which objective is to precede a final product concentration, generated by addition
of an infinitesimal fraction to the initial value.
(49)
The approximated function is the rate of the reaction:
(50)
The infinitesimal fraction is the difference between two consecutive times divided
by the number of steps. The step number is introduced by the user when
C_Euler is applied.
The Microsoft Visual Basic algorithm is shown below:
Public Function C_Euler(Cao, Cbo, Cco, Cdo,

kf, kb, na, nb, nc nd, t1, t2, steps) As Variant
dt = (t2 - t1) / steps
Ca = Cao
Cb = Cbo
Cc = Cco
Cd = Cdo
For i = 1 To steps
r = -kf * Ca ^ na * Cb ^ nb _
+ kb * Cc ^ nc * Cd ^ nd
{r = -dCa/dt= -dCb/dt= dCc/dt= dCd/dt}
dCa = r * dt
dCb = r * dt
dCc = -r * dt
dCd = -r * dt
Ca = Ca + dCa
Cb = Cb + dCb
Cc = Cc + dCc
Cd = Cd + dCd
Next i
C_Euler = Array(Ca, Cb, Cc, Cd)
End Function
Figure 71. Microsoft Visual Basic C_Euler algorithm.
- 100 -
ANNEX 4. CONVERSION CALCULATION

General approximation
In first instance it is considered the following conversion reaction:
(51)
Where a,b,c and d are the respective stoichiometric coefficients of the reactants
(A and B) and products ( C and D ).
In general, the reaction components obey the folloing reaction stoichiometry:
(52)
(53)
(54)
(55)
Where:
N = the final composition of moles of components
No = the inicial moles of components
Xa = the conversion of the base components A.
The reaction conversion is calculated as the percentage if the base component
that was consumed in the reaction.
RWGS conversion
The conversion or rate from the RWGS reaction is calculated by the following
equation.
(56)
Where:
X = conversion
nCO = Moles of CO
nH2O = Moles of H2O
nCO2 = Moles of CO2
- 101 -
nH2O = Moles of H2O
- 102 -
ANNEX 5. SOLVER TOOL

SOLVER is part of a suit of commands sometimes called what-if analysis tools.
With SOLVE, you can find an optimal value for a formula in one cell (target cell)
on a worksheet. SOLVER works with a group of cells that are related, either
directly or indirectly, to the formula in the target cell.
Solver adjusts the values in the changing cells you specify (adjustable cells) to
produce the result you specify from the target cell formula. You can apply
constraints to restrict the values SOLVER can use in the model, and the
constraints can refer to other cells that affect the target cell formula. [38]
Figure 72. Solver Parameters windows
 Target: SOLVER will be used for minimizing the SSE values.
 Target cell: cell filled in yellow in the worksheets.
Table 15. Target Cells.
SOLVER MIN
Objective functions
Sume SSE
 Adjustable cells: kRWGS and kWGS
Table 16. Adjustable Cells
k (WGS) = 0,95 k(RWGS) = 1,04
 Constrains: kRWGS , kWGS > 0
 Objective function (Z) is been assumed to be: Z = SSE (Ca) + SSE (Cb)
by doing some studies.
- 103 -
OBJECTIVE FUNCTION STUDY

The objective function study has been done because it is necessary to know if all
the direct and indirect functions from the EXCEL worksheet have more than one
minimum.
The steps that have been followed for the correct Objective Function
determination are shown below:
1. Ten possible objective functions are assumed in first instance.
Table 17. Objective functions proposed
A SSE(Ca)+SSE(Cb)
B SSE(Ca)*SSE(Cb)
C SSE(0,1Ca)+SSE(0,9Cb)
D SSE(0,2Ca)+SSE(0,8Cb)
E SSE(0,3Ca)+SSE(0,7Cb)
F SSE(0,4Ca)+SSE(0,6Cb)
G SSE(0,5Ca)+SSE(0,5Cb)
H SSE(0,6Ca)+SSE(0,4Cb)
I SSE(0,7Ca)+SSE(0,3Cb)
J SSE(0,8Ca)+SSE(0,2Cb)
K SSE(0,9Ca)+SSE(0,1Cb)
2. Five different space points are studied for each of the objective functions.
Each pair of points (x, y) correspond to two pair of (kWGS, KRWGS) values. These
points will let us know if there is only one minimum in all the functions.
Table 18. Objective functions proposed
CASE 1 CASE 2 CASE 3 CASE 4 CASE 5

0,1 0,1 2 2 1 4 4 1 4 4
Figure 73. Study points chart
- 104 -
3. For each pair, the SOLVER tool is applied and kWGS, KRWGS values are obtained.
Despite the study points, the same results are obtained for each objective
function proposed.
Table 19. SOLVER objective functions results
CASE 1 CASE 2 CASE 3 CASE 4 CASE 5
0,1 0,1 2 2 1 0,1 0,1 2 2 1

A SSE(Ca)+SSE(Cb) 3,18 3,85 3,19 3,85 3,18 3,85 3,18 3,85 3,18 3,85
B SSE(Ca)*SSE(Cb) 3,84 4,44 3,84 4,44 3,81 4,41 3,84 4,44 3,84 4,44
C SSE(0,1Ca)+SSE(0,9Cb) 4,18 4,74 4,18 4,74 4,18 4,74 4,18 4,74 4,18 4,74
D SSE(0,2Ca)+SSE(0,8Cb) 3,89 4,48 3,89 4,48 3,89 4,48 3,89 4,48 3,89 4,48
E SSE(0,3Ca)+SSE(0,7Cb) 3,63 4,25 3,63 4,25 3,63 4,25 3,63 4,25 3,63 4,25
F SSE(0,4Ca)+SSE(0,6Cb) 3,39 4,04 3,39 4,04 3,39 4,04 3,39 4,04 3,39 4,04
G SSE(0,5Ca)+SSE(0,5Cb) 3,18 3,85 3,18 3,85 3,18 3,85 3,18 3,85 3,18 3,85
H SSE(0,6Ca)+SSE(0,4Cb) 3 3,68 3 3,68 3 3,68 3 3,68 3 3,68
I SSE(0,7Ca)+SSE(0,3Cb) 2,82 3,53 2,82 3,53 2,82 3,53 2,82 3,53 2,82 3,53
J SSE(0,8Ca)+SSE(0,2Cb) 2,67 3,39 2,66 3,39 2,66 3,39 2,67 3,39 2,66 3,39
K SSE(0,9Ca)+SSE(0,1Cb) 2,52 3,26 2,52 3,26 2,52 3,25 2,52 3,26 2,52 3,26
Figure 74. SOLVER objective functions results
- 105 -
The results above show that there is only one convergent point:
2,25 < kRWGS <4.18 3,25 < kWGS <4,74
The minimum point, for any objective functions proposed, is:
kRGWS = 3,3 kWGS=3,95
To conclude we must say that it does not matter which objective function is
chosen because always we are going to obtain the same values. The objective
function chose is:
Z = SSE(Ca) + SSE(Cb) (30)
- 106 -
ANNEX 6. HYSYS CASE STUDIES

CASESTUDY is a tool in Aspen Hysis ® which objective is performing studies by
changing parameters and conditions from the main simulation process.
The explanation of CASE STUDY is shown below.
When the reactor gets configured, it must be checked if the overall process
works for different operation conditions, i.e. tempeture, pressure, compositions,
flow rates, etc.
Figure 75. Aspen Hysys® tool menu
For example in the following example we will play with the INPUT stream
temperature and the OUTPUT stream of CO composition.
Figure 76. Aspen Hysys® CASE STUDY window
- 107 -
In the Case study is possible to define the range of variables which can be
dependents or independents, and the step size for our range.
Figure 77. Aspen Hysys® CASE STUDY window where the T(ºC)
is the independent variable.
After all the specifications are processed, we run the CASE STUDY, and the
results are displayed in two different ways: graphically or table.
Figure 78. Aspen Hysys® CASE STUDY graphical results
- 108 -
Figure 79. Aspen Hysys® CASE STUDY results table
Finally, we must check if the results in table or plot are adjusted to the
experimental data results.
- 109 -
ANNEX 7. HYSYS SPECIFICATIONS

The two Aspen Hysys ® are composed by the same components before the
reactor a mixer and a heat exchanger (Heater).
Figure 80. Aspen Hysys® Model I simulation
Figure 81. Aspen Hysys® Kinetics model I and II simulation
The steps of their start up are explained below:
1. The properties of all our raw materials have to be checked just in case there
is any specification wrong; i.e. boiling point, density, viscosity, etc.
Figure 82. Aspen Hysys® H2 properties
- 110 -
2. Temperature, composition and the rest of the operation conditions have to be

introduced in the two firsts streams: H2 and CO2
Figure 83. Aspen Hysys® raw materials streams
Figure 84. Aspen Hysys® H2 conditions
Figure 85. Aspen Hysys® H2 compositions
- 111 -
3. The Heater configuration is one of the most important parts from all the
simulation process, because the input reactor temperature condition depends
on the heater specifications.
Figure 86. Aspen Hysys® heater part
On the heater window, it is possible configure many thinks to achieve the desired
temperature.
d) Delta P and Duty adjust.
Figure 87. Aspen Hysys® heater tab
e) Or the direct introduction of the desired temperature in the INPUT stream.

Consequently, DUTY becomes a degree of freedom.
- 112 -
Figure 88. Aspen Hysys® INPUT stream worksheet.
When all the streams and the heater have been specified, we can proceed to the
microreactor specifications.
The components of this part of the simulation are available to change if the
experiment requires.
- 113 -
ANNEX 8. REACTOR VOLUME SPECIFICATIONS

The reactor Volumes (Equilibrium and Plug Flow) have to be described for given
to the simulation more real. Aspen Hysys® gives you the option to add geometry
constrains.
It is assumed that the reactor will adopt the horizontal cylinder form which
specifications are: diameter and height. The vessel volume is calculated as:
(57)
Where:
Vreactor= volume of the reactor
Vboot = volume of the boot
Height, Diameter = values taken from the respective fields.
In both Hysys simulations it is assumed:
 Microreactor volume: 8,5 mL
 Microreactor diameter: 3,40 μm
However, for the Plug Flow reactor other parameters need to be defined, like the
number of tubes, wall thickness and void fraction.
 Number of tubes: 1
 Wall thickness: 0,005m
 Void fraction: 1
Figure 89. Aspen Hysys® Equilibrium Reactor volume specifications
- 114 -
Figure 90. Aspen Hysys® Plug Flow Reactor volume specifications
- 115 -

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REPORT INDEX

Report index .............................................................................................1

3.3. Process Intregration/Intensifications............................................. 39

The RWGS simulation in a microreactor is part of bigger investigation, carried

Figure 1. Project working areas

2. With experimental data results: Demonstration of chemistry in micro-scale,

Figure 2. Example of process that follow the general idea of the

 Proposal of four different models:

2007 New technologies of CO2 capture become F-T technology in a interesting

Combustion (strongly exothermic):

Consequently, we need to use some catalysts to force the reverse direction

Figure 3. Diagram of a Slurry Bubble Column Reactor [18]

In these slurry reactors, the synthesis gas is bubbled through a suspension of

Figure 4: Diagram with the three main steps in the F-T.

1. Coal reserves are significant and available at a cheaper rate.

2. Natural gases are abundant.

2.2. Raw Materials

2.2.1. Sources of Carbon Dioxide

Figure 5. Purified, captured CO2 from combustion power plants.

Generally speaking, there are three basic CO2 capture:

Figure 6. Post Combustion Capture Diagram [11]

Figure 7. Oxy-fuel Combustion Diagram [11]

 Post combustion capture.

Figure 8. Pre Combustion Capture. [11]

Capture of Carbon Dioxide Directly from Ambient Air

Figure 9. CO2 air adsorption [53]

Rocks are classified by geologists into three basic categories: sedimentary

2.2.2. Sources of Hydrogen

Figure 10. Hydrogen production path ways. [12]

electrical power grid could be used as the backbone of the hydrogen

Figure 11. A schematic illustration of a basic water electrolysis system

Potassium hydroxide is most commonly used in water electrolysis, avoiding the

Cathode: 2H+ + 2e → H2 (9)

Anode: 2OH- → ½O2 + H20 + 2e (10)

H2O → H2 + ½O2 (11)

Figure 12. Hydrogen generation Unit [13]

Electrolyte circulation is also included in the hydrogen generation unit in alkaline

Figure 13. Hydrogen process flow diagram [13]

Figure 14. Principle of membrane reformer [15]

The general formulas of Steam Reforming Reaction to obtain hydrogen are

Reforming Reaction: (12)

Shift Reaction: (13)

Reforming-shift reaction: (14)

For hydrocarbons that consisit of C, H and I, general reaction formulas are

2.2.3. Production of Syngas

Syngas catalytic process

2.3. RWGS Reaction

Figure 15. RWGS industrial process [53]

1. The surface redox mechanism

2. The formate decomposition mechanism.

Some discrepancy exists on the dominant mechanism controlling the RWGS

 CO2 Oxidised Cu0 to generate CO,

 H2 reduced Cu(I) to Cu0 and forms H2O,

 CO can be produced alone over Cu powder or Cu/Zn Catalyst,

 H2 plays a role of reducing agent for the reduction of Cu2O. [2]

 An intermediate compound is formed from H2 and CO2 involving the

 The decomposition of this intermediate compound releases CO.

 Overload the reactor with H2 to force the complete consumption of the

2.3.2. RWGS Reaction in Microreactors

2.3.3. Catalyst Selection

Table 1. Studies on RWGS

Author & Catalyst Mechanism Main Findings

A. Goguet et al. Pt/CeO2 Formate carbon deposits on the