Introduction

Design and synthesis of nanomaterials for catalytic applications

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1. INTRODUCTION:
The worldwide emphasis to reduce dependence on crude oil has given a fillip to
research on renewable feedstocks for energy and materials. Biomass which is cheaply
available can be valorized for making value added products and transportation fuels
which in future can replace crude oil and gas. Biomass, mainly lignocellulose, is very
difficult to activate for further process steps. Solid catalysts are in principle very suitable
for processing biomass(Schuth et al., 2009).

Biomass has a large content of glucose in it
which can be further fermented to obtain series of products like lactic acid, succinic acid,
glutamic acid and so on. Succinic acid in particular can be valorized to -butyrolactone
(GBL) by using various catalytic routes and strategies, for instance, mono and bimetallic
supported catalysts in solvent less conditions or supercritical carbon dioxide. The work is
centered around this theme and the relevant background information is given in what
follows.
Succinic acid, a dicarboxylic acid, usually occurs in nature in the form of its
esters. It is a versatile product which is able to undergo many transformations. The
market potential for products based on succinic acid is estimated to be around 270,000
tons/year which includes 1, 4 butanediol, tetrahydrofuran, -butyrolactone (GBL), N-
methylpyrolidone (NMP) and so on. Thus the increasing demand on biorefinery
processes to produce fine chemicals from low cost renewable carbon resource can be
fulfilled by C
4
and C
5
carbon sources like succinic acid that helps to overcome increasing
limitations of petroleum based chemicals (Corma et al., 2007).
1.1 Nature and properties of succinic acid:
Succinic acid, an intermediate in Krebs acid cycle is one of simplest organic
diacids. It occurs as colourless crystals which are monoclinic and have an acid taste.
(Bergmeier and Arason, 2002). It is a dicarboxylic acid which has two dissociation
constants, capable of losing two protons. The pKa of first carbonyl group is 4.21 and that
of second is 5.64. The second group being less acidic; it takes extra energy to overcome
the second negative charge being so close to the first negative charge. Any substituent
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Design and synthesis of nanomaterials for catalytic applications
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that stabilizes a negative charge is going to enhance the dissociation process and results
in stronger acid. Thus electronegative elements can enhance the acid strength through
inductive effects. The closer the substituent to the anion the more pronounced the effect.

Figure 1.1: Nature of succinic acid molecule
Succinic acid is known to be a building block material. The basic chemistry of
succinic acid is similar to the petrochemically derived maleic acid and maleic anhydride
(Corma et al., 2007).The major technical difficulties encountered in the development of
succinic acid as a building block include the development of very low cost fermentation
routes. The only real technical consideration here is the development of heterogeneous
catalysts that would not be affected by impurities in fermentation.
Scheme 1.1 presents the various derivatives of succinic acid which are
commercially important.
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Design and synthesis of nanomaterials for catalytic applications
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O
O
N
H
O
O
O
N
OH
O H
NH
2
N H
2
1,4-diaminaobutane
O
O
N H
2
NH
2
Succinic Acid
1,4-butanediol
NC
CN
succinonitrile
O
OH
O
O H
-butyrolactone
Tetrahydrofuran
Pyrrolidin-2-one
1-ethenylpyrrolidin-2-one
Butanediamide

Scheme 1.1: Commercially important derivatives of succinic acid.
1.2 Heterogeneous catalysts:
Heterogeneous catalyst is a composite material characterized by; active species
physical or chemical promoters and supports, shape, size, pore volume and surface area.
(Vaccari et al., 2003). In order to increase the efficacy and economics, active sites are
supported on a suitable support which may be microporous or mesoporous. Good
supports combine relatively high dispersion with a high degree of thermal stability of the
catalytic component.
1.3 Nanocatalysts:
Heterogeneous catalysis engineering involves length scales ranging from atomic
to the catalyst particle or pellet size. The activity and selectivity of catalyst depends on
the atomic structure of its so called active sites. The geometry of these sites determines
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Design and synthesis of nanomaterials for catalytic applications
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how some species are bound and converted on the surface of the catalyst. The structures
of the active sites govern the conversion rates towards different products and the
probability for the products to detach from the active site. The active sites are of atomic
dimensions or rather a few nanometers in size (Ozkan, 2008). A vast network of
extremely narrow pores inside the catalyst particle is desirable to achieve a high surface
area per unit volume.
1.4 Supercritical Fluids:
Fluids at a temperature and pressure near their critical points are called as
supercritical fluids (Savage, 2000). There are many potential advantages for carrying out
chemical reactions under supercritical conditions like providing higher concentration of
reactant gases compared to the conventional gas-liquid systems, eliminating mass transfer
limitations which might exist in multiphase reacting systems, providing easier product
separation and providing higher diffusivities than liquids and better heat transfer than in
gases.
All different kinds of fluids have their respective critical temperature and
pressure. Most commonly considered fluids are supercritical water and supercritical
carbon dioxide. Supercritical water is highly corrosive in comparison to supercritical
carbon dioxide and can be considered to be most relevant and green fluid because of low
critical temperature, non-inflammability and low toxicity. The supercritical carbon
dioxide has dual properties (properties of both gas and liquid) which provide ideal
conditions for extracting compounds with a high degree of recovery in short time period.
Carbon dioxide is in supercritical state when both temperature and pressure equal or
exceed the critical point of 31
o
C and 73 atm. (Beckman, 2004).
As stated earlier the current research is based on valorization of succinic acid to
-butyrolactone and a strategy was planned accordingly.


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Design and synthesis of nanomaterials for catalytic applications
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1.5 Organization of thesis:
The thesis is covered in eight chapters.
Chapter 1 gives a brief information about biomass derived products,
heterogeneous catalysis and supercritical fluids.
Chapter 2 covers literature survey about the topic. It gives details about prior art
on the topic with regards to catalyst and support preparation, different routes to obtain the
desired product and use of different catalysts and supports to carry out hydrogenation of
succinic acid.
Chapter 3 gives details about hydrogenolysis i.e. hydrogenation and dehydration
reactions.
Chapter 4 deals with support and catalyst preparation and characterization of the
catalysts.
Chapter 5 covers hydrogenation of succinic acid and analysis of the progress of
reaction. It covers the effect of different solvents and bimetallic catalysts. Also the effect
of supports prepared by calcination and by supercritical carbon dioxide on the reaction
progress is studied.
Chapter 6 describes the kinetic model for the reaction with respect to the effects
of different parameters on the progress of reaction.
Chapter 7 discusses the results and conclusions of the work done.
Chapter 8 finally highlights the accomplishments of the present research work and
an insight on the future work.