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Msc in Catalysis

Catalyst Design Project



Edidiong Asuquo, Charlotte Corcoran and Jessica Segnan
The Dehydrogenation of Isopropanol
to form Hydrogen gas
Abstract
The design of a catalyst for the dehydrogenation of
isopropanol to generate hydrogen was studied. The
dehydrogenation is favoured thermodynamically at a
temperature range of 465-473k and by evaporation of the
products. A tri-metallic catalyst composed of Cu-Pt-Re
was proposed on a silica support in a CSTR reactor .The
heat source for the endothermic reaction is through a
microwave heater. A Pd-membrane separator is used to
separate the hydrogen. Two distillation columns are used
to separate the acetone/isopropanol/water mixture. The
isopropanol-water mixture is also recycled as feed,
therefore making the reaction environmentally viable.
Introduction
The advancement in industrialisation has placed man in an energy
driving economy. Thereby putting a heavy demand on processes that
will maximize energy production, whilst reducing the cost. This
trend has been the wheel in the energy transition.

One of the most likely sources of renewable energy is hydrogen.
Hydrogen as an energy vector was discussed in the energy
alternative plan in the 1970s. The hydrogen economy has been
proposed as a viable option as a solution to the impending energy
problem that may arise from fossil reserve decline and
environmental implications of fossil energy sources.

One of the immediate uses of hydrogen in the energy applications is
in the development of fuel cells. Fuel cells are used to convert
hydrogen to electricity. However, hydrogen basically is an energy
carrier and not a fuel

The major thermal advantage of hydrogen, over both gasoline and
natural gas, is its specific energy, which is almost 3 times the
combustion energy of the other 2 fuels

Hydrogen can be produced by the dehydrogenation of alcohols.
Isopropanol is a secondary alcohol and its dehydrogenation
products are hydrogen and acetone. However, the design of an
efficient catalyst to optimise the production of hydrogen from
isopropanol has been a limiting factor in the process of
commercialising hydrogen production using this route.

The aim of this present study is to develop an efficient catalyst
and process system for the dehydrogenation of isopropanol to
optimise hydrogen production

Hydrogen Production Techniques
3 main routes:



steam reforming of hydrocarbons (natural gas)
Steam reforming of natural gas is a well-understood
process that is being used in existing commercial plants.
Methane in natural gas reacts with water (steam) to
produce carbon monoxide and hydrogen using a nickel
catalyst on a ceramic support.

CH
4
+ H
2
O CO + 3H
2
H=+251 KJmol
-1



The carbon monoxide is put through a water-gas shift
reaction, where it combines with water to produce
hydrogen and carbon monoxide.

CO + H
2
O CO
2
+ H
2
H=-42 KJmol
-1



electrolysis of water by electricity
The system uses an electrolyser powered by electricity.
The required electricity may come from conventional
power plants such as coal or nuclear, but can also use
renewable energy resources such as wind, solar thermal,
photovoltaic and hydropower.


biomass gasification
Biomass gasification can be considered as a form of
pyrolysis, which takes place at higher temperatures and
produces a mixture of gases with hydrogen content
ranging from 6-6.5%
Hydrogen Utilization Routes


Industrially, hydrogen is used chemically as a
reducing agent in the mineral industry, as a
hydrogenation agent in the petroleum industry
and as a bonding agent in the chemical industry

Fuel cell (hydrogen to electricity) technology is
one of the most hydrogen utilising routes in the
transportation sector through fuel cell vehicles.
Fuel cells have high efficiencies and potentially
substantially lower negative externalities than
current energy systems, which has made them an
attractive future option in micro, stationary and
automotive applications.

Large-scale future applications are possible as a
fuel for power plant fuel-cell generation of
electricity, as a coolant in super conductor
technology, and as a fuel in transportation
applications such as motor vehicles with
internal-combination engines, motor vehicles
with fuel-cell electrical engines, marine vessels,
aviation jet engines and space travel.





Literature Review

Homogeneous Catalysis

Recent studies have shown that ruthenium, in the presence of easily available
amine ligands, constitutes an active catalyst for the dehydrogenation of
alcohols to generate hydrogen, under mild conditions.

It was shown that the addition of trialkylamines gave much better results
compared to secondary and primary amines. Also, applied coordinating
ligands showed a significant inhibition of the reaction.
Literature Review

Heterogeneous Catalysis
Supported Metal Catalysts

Dehydrogenation of isopropanol over a family of carbon-supported Pt, Cu, and
bimetallic Cu-Pt catalysts revealed that Pt was more active than copper and all catalysts
were 100% selective to acetone when supported on a high temperature treated carbon
(possessing no acidic surface groups.) bimetallic Cu-Pt catalysts were less active than
their monometallic counterparts.

Cu-SiO
2
catalysts have also been reported, the activity of the fresh Cu/SiO
2
catalyst
initially increases with time until a maximum is reached, and then rapid deactivation
follows. The results showed that simultaneous reduction and sintering processes are
responsible for the activation-deactivation behaviour observed for a Cu/SiO
2
shell
catalyst during the dehydrogenation of isopropyl alcohol to acetone.

Cu/CNF and Cu/CeO2/CNF catalysts have been synthesized on different carbon
nanofibers (CNF) . The presence of CeO2 enhanced the reduction and dispersion of Cu,
and lead to higher turnover frequencies. However, excess CeO2 enhanced hydration
activity, and thereby, reduced the selectivity. Cu/CNF activities were similar to that
found for active carbon supported Cu catalysts


Literature Review

Heterogeneous Catalysis
Influence of Rhenium additives

It has previously been found by [33] that the introduction of the 1% Re additive
enhances the activity of the Cu (1%)/Sib catalyst in the transformation of
isopropyl alcohol into acetone. The addition of 0.25% Re favours an increase in
the dehydrogenating activity and stability of the Cu (4%)/Sib catalyst.

Rhenium, being a metal with a comparatively high melting point does not
undergo recrystallisation and therefore favours an increase in the stability of the
metal-supported catalyst
Literature Review
Heterogeneous Catalysis
Recyclable Ruthenium Catalyst
Here, a recyclable and easily synthesized heterogeneous catalyst for acceptor-free
alcohol dehydrogenation is described:
Literature Review

Heterogeneous Catalysis
Metal oxides
Heterogeneous Catalysis
Simple metal oxides
Objective of Study
This work sets out to design a dehydrogenation catalyst for the generation of hydrogen
from isopropanol.
The goal of thus study is to propose a catalytic system that will be highly active, very
selective and stable for the reaction to optimise hydrogen generation at a specified
reaction condition.

Therefore, it will be designed to achieve the following:

Reaction thermodynamics: Examination of the energetics and feasibility of the reaction
at specified conditions.
Kinetics and mechanism of the reaction.
Catalyst properties and mode of operation: The catalyst feedstock phase system that will
enhance activity, selectivity and stability of the catalyst. In addition to conversion, mass
transfer effect, deactivation and regeneration considerations.
Chemical reactor design considerations.
Process economics/environmental considerations.

Catalysis is basically a kinetic phenomenon. This
is because it does not affect the thermodynamics
of the reaction.
As a catalyst does not affect the equilibrium
constant for the overall reaction , it is therefore
necessary that an examination of the
thermodynamics of the dehydrogenation reaction
be carried out using the thermodynamic properties
of the reactants and products
Thermodynamics of the
Reaction
The energetic quantities in the
thermodynamic system of the chemical
reaction are:
Enthalpy of reaction, Hr
Entropy of reaction, Sr
Gibbs Free Energy, Gr
Equilibrium Constant, K.




The standard enthalpy and entropy of the reactant and products
are :
Reactant/Product Hf (kJ/mol) Sm (J/mol K)
Isopropanol (l) -318.2 180
Acetone (l) -248.1 200.4
Hydrogen (g) 0 130.6
Thermodynamics of the
Reaction
Standard enthalpy = Hr = Hf298(products)
Of reaction - Hf298(reactants)
= (-248.1 + 0) (318.2)
= (-248.1 + 318.2)
Hr298 = 70.1 kJ/mol

Standard entropy = Sr298 = Sm298 (products)
Of reaction - Sm298 (reactants)
= [(200.4 + 130.6) 180]
= [331 180]
Sr298 = 151 J/K mol
Standard Gibbs = Gr298 = Hr298 - T Sr298
free energy of
reaction = 70.1 kJ (298.15 x 151) J
= (70100 45020.65) J
= 25079.35 J
Gr298 = 25.079 kJ/mol

Equilibrium = Keqm = e (- G)
Constant RT
= e (- 25079)
298.15 x 8.314
= e (-25079)
2478.81
Keqm = e (-10.11)
Keqm = 4.03 x 10
-5
Thermodynamics of the
Reaction
For the dehydrogenation reaction of isopropanol to generate
hydrogen, the following thermodynamic results were
obtained at standard conditions (298 K):
Hr298 0 reaction is endothermic
Sr298 0 net formation of gas in reaction
Gr298 0 Reverse reaction is spontaneous
Forward reaction not favourable
at standard conditions.
Keqm = 4.03 x 10-5
Thermodynamics of the
Reaction
Since the Gibbs free energy is positive at standard conditions (298 K),
then the reaction is not thermodynamically favourable at this
temperature. Therefore, heat must be applied to make it favourable.

At a temperature of 465 K the Gibbs free energy will become negative.
Hence for the reaction to be thermodynamically favourable it should
be operated at temperatures above 465 K.

Since the reaction is limited by its thermodynamics in the liquid phase,
the equilibrium can be shifted by evaporation of either one or both of
the products, thereby reducing the concentration of the products. If
both hydrogen and acetone are continuously expelled, then the
equilibrium will shift towards the formation of the products according
to Le Chateliers principle. Therefore a high temperature is needed.
Kinetics and Mechanism of
Isopropanol Dehydrogenation
The study of the kinetics and mechanism of any reaction is useful in the
selection of a suitable catalyst and appropriate reaction conditions that will
enhance the selectivity and conversion of the process towards the desired
products.

The generally accepted, simplified mechanism of solid-catalysed fluid (gas or
liquid) phase reaction is outlined below :

1. Transport of reactants from fluid phase to exterior surface of catalyst pellet.
2. Transport of reactants to active sites inside the pores.
3. Adsorption of reactant onto the surface at active sites.
4. Chemical reaction of reactants on surface of catalyst with formation of
products.
5. Desorption of products from the surface.
6. Transport of products out of the pores to the pellet surface.
7. Transport of products from the catalyst pellet surface to the bulk of the fluid.


Kinetics and Mechanism of
Isopropanol Dehydrogenation
Fig 2 Mechanisms proposed for 2-propanol
decomposition
Catalyst design for Reaction

The suitability of a catalyst for an industrial process depends mainly on the following three
properties:

Activity
Selectivity
Stability (deactivation) behaviour.

The activity is a measure of how fast one of more reactions proceeds in the presence of a
catalyst ad can be expressed using:

Reaction rate
Rate constant
Activation energy, Ea.

Catalyst/support Interaction

Since selectivity in alcohol dehydrogenation depends on the strength
and distribution of acidic or basic sites, recent efforts have been made
in order to design a catalyst with controlled acidity and a number of
mixed oxide catalysts have been designed for this purpose.

The catalyst supports can be basic, acidic or both. The acidity of the
support determines whether the dehydration or the dehydrogenation
reaction will be favoured. Basic supports favour the dehydrogenation
reaction, while acidic supports favour the dehydration reactions. Silica
(basic) and alumina (acidic) have very high surface areas compared to
the other oxides.
Catalyst Choice

The type of catalyst we propose for the dehydrogenation of
isopropanol to give hydrogen and acetone is a tri-metallic
catalyst, composed of Cu-Pt-Re. This is because of the need to
increase the overall catalytic activity, selectivity and stability of
the catalyst under reaction conditions in the reactor.

Copper was chosen because if exhibits the highest selectivity to
the dehydrogenation reaction.

Platinum has been reported to have a high activity in the
dehydrogenation of isopropanol and shows less sensitivity to
the acetone inhibition of the rate.

Rhenium exhibits the highest stability and is resistant to
thermal sintering, this helps to stabilize the copper which is
very susceptible to sintering, thereby increasing the overall
catalytic conversion.


Choice of Support

The nature of the support for the heterogeneous Cu-Pt-Re catalyst is also an important
factor. Dehydrogenation activity is decreased when active sites contain a high number of
acidic sites, due to the presence of a dehydration reaction. However, dehydrogenation
activity of a catalyst can be improved by the incorporation of amphoteric or basic metal
oxides into the catalyst.

MgO is very basic. It needs high temperatures to give dehydrogenation. At 200-300C
propene is the major product.

Al
2
O
3
is very acidic and gives propene/Di-isopropyl Ether(DIE).

SiO
2
is amphoteric. Has very low propene formation due to very weak basic sites, so there is
no ether formation

Ce
3+
, Mg
2+
, Al
3+
- mixed oxides form the condensation product (MIBK) with copper.

TiO
2
- ZrO
2
mixed oxides catalyse di-isopropyl ether formation.

Activated carbon has the tendency to lead to the formation of carbonaceous species on the
surface of the catalyst.

Silica has been shown to contain weak basic sites, which means it is capable of catalysing the
dehydrogenation reaction. The catalytic reaction is also sensitive to the number of active
sites on the catalyst. So a high surface area of silica is necessary.




Catalyst Preparation

Reactor Design
Chemical reactors are the most important part of a chemical process plant. In most cases,
improvement in reaction rates and selectivities to desired products can be attained by
changes to the reactor design.
The reactor must be designed in such a way that it produces the desired products,
hydrogen and acetone, in a safe, reliable and economic way.
The choice of reactor depends on the nature of the reactants, products and reaction
conditions. The factors which influence these are given below:

Catalyst form (pellet, extruders, monolithic)
Reactor volume
Level of agitation between catalyst and reactant
Heat transfer and control
Temperature of reaction
Pressure of reaction

The choice of reactor had to take into account the thermodynamics and selectivity of the
reaction. A batch reactor would not be favourable in this case as the products would
remain inside the reactor and cause inhibition of the catalyst and subsequent side
reactions such as self-condensation of the acetone to give MIBK. Therefore the
selectivity would be low.
Reactor Design
For this project we chose a continuous stir tank reactor. This is a reactor in which there
is continuous agitation of the catalyst bed. The products are also continuously removed
and so it favours formation of the desired products.

The reaction conditions for our reactor are as follows:
Temperature- 465-473K
Pressure- 20 bar N
2

Solvent- Water

The choice of water as a solvent was made due to the fact that the side reaction of
isopropanol dehydrogenation to give propene and isopropyl ether gives water as a co-
product. In order to inhibit the presence of unwanted side reactions, water was use as a
solvent.

The reactor is kept in continuous operation and the continuous removal of the products,
acetone and hydrogen, favours equilibrium. The heat source is from a microwave
heater, as it provides many advantages to conventional heating routes therefore it has
the ability to provide heat throughout the catalyst bed.

A schematic representation of the reactor process:

Process Economics
Using either, palladium, ruthenium, rhodium or platinum catalysts supported on carbon
or amberlyst, isopropanol can be obtained from a renewable feedstock. This will greatly
enhance the economics and viability of this route for production of hydrogen. This will
also ensure that the production capacity of isopropanol is increased to meet the new and
old uses of the feedstock.

Furthermore, to improve the economics of the isopropanol route for hydrogen
production, the use of the by-product of the process is also very commercially attractive.
Acetone is obtained as the by-product of the process. Acetone is manufactured primarily
as a co-product of phenol production via cumene peroxidation.

Methyl isobutyl ketone (MIBK) is used as a solvent for paint and protective coatings, an
extracting agent for production of antibiotics and commercial lubricating oils.

The most important factor in the economics of this isopropanol conversion process is the
generation of hydrogen. Its production capacity must increase and be made more
sustainable if it can be obtained from renewable resources.
Conclusion
Concerns about the depletion of fossil fuel energy sources and the pollution
caused by continuous energy demands make hydrogen an attractive alternative
energy source.

Hydrogen is currently being derived from non-renewable natural gas and
petroleum however the dehydrogenation of alcohols is an alternative and
renewable source of hydrogen.

The dehydrogenation of isopropanol to give acetone and hydrogen is one route
that offers the possibility of hydrogen production for various uses.

A tri-metallic catalyst composed of Cu-Pt-Re supported on silica has been
designed in this project in order to maximise hydrogen and acetone production
in an economic and environmentally friendly way.

The thermodynamics of the process indicate a temperature above 465K must
be used and that the reaction is favourable when the gaseous products are
removed thus driving the reaction to favour product formation.

A continuous stirred flow tank reactor (CSTR) has been proposed for the
reaction.

Thank you!

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