DECEMBER 28, 2015

ARTICLE REVIEW
HETEROGENEOUS CATALYST FINAL EXAM

AFAN HAMZAH
2315201011
PASCASARJANA TEKNIK KIMIA INSTITUT TEKNOLOGI SEPULUH NOPEMBER
 Article Review of SOLID HETEROGENEOUS CATALYSTS FOR PRODUCTION OF
BIODIESEL FROM TRANS-ESTERIFICATION OF TRIGLYCERIDES
WITH METHANOL: A REVIEW
Afan Hamzah (2315201011)

Shruti G. Chopade*, K. S. Kulkarni, A. D. Kulkarni and Niraj S. Topare attempted to review some
research about solid heterogeneous catalysts for production of biodiesel from trans-esterification of
triglycerides with methanol. In last decade, the development of biodiesel research grew intensively,
some did biodiesel resources research, some did its process research. The new process technologies
developed during the last years made it possible to produce biodiesel from recycled frying oils
comparable in quality to that of virgin vegetable oil biodiesel with an added attractive advantage of
being lower in price. Increasing number of researches focusing on the use of solid heterogeneous
catalysts for the production of biodiesel provides evidence that these catalysts continue to evolve as
viable alternatives. From some reason that mentioned above, the writers tried to collect, review and
compare some journal about various types of heterogeneous solid acids and bases in the production
of biodiesel from trans-esterification of triglycerides.

In the first section (introduction) the writers explain about biodiesel as renewable energy
which can be substitute of fossil oil. It explained the superiority of diesel oil compared to diesel oil.
More than that, it also explained how to produce biodiesel by the trans-esterification of the vegetable
oil or animal fat feedstock. There are several methods for carrying out this trans-esterification reaction
including the common batch process, supercritical processes, ultrasonic methods, and even
microwave methods. Chemically, transesterified biodiesel comprises a mix of mono-alkyl esters of
long chain fatty acids.

The next session of this journal explained about Trans-esterification reaction. the most
common way to produce biodiesel is by trans-esterification of triglycerides of refined/edible types of
oils using alcohol, in presence of an acid or a basic catalyst. The alcohol used for trans-esterification is
usually methanol. Producing biodiesel is a bulk process; the general scheme of the trans-esterification
reaction is presented in Fig. 1, where R is a mixture of various fatty acid chains

After that, it provided information about biodiesel production from vegetable oils such as
Cotton seed, soybean, ground nut, palm, and sunflower. The fuel properties of them was compared
with diesel itself and block diagram of biodiesel production process can be seen in fig 2.

As a focus of this journal, the next section discussing about Heterogeneous Catalyst. The
heterogeneous catalyst was compared with homogeneous catalyst in some parameter. There was
reaction rate, Processing methodology, presence of water and fatty acid, catalyst reuse, and cost.
From that comparison, the writers concluded that heterogeneous catalyst was more preferable to use
in producing of biodiesel. Solid acid catalyst is used as heterogeneous catalyst in producing biodiesel.
It has Solid acid catalysts have the potential to replace strong liquid acids to eliminate the corrosion
problems and consequent environmental hazards posed by the liquid acids. However, the efforts at
exploiting solid acid catalysts for trans-esterification are limited due to the pessimistic expectations
on the possibility of low reaction rates and adverse side reaction. As a result, the factors governing
the reactivity of solid catalysts have not been fully understood. For example, simple correlations
between acid strength and activity of the catalyst have not been clearly formulated. Second, due to
diffusion restrictions the catalyst must have a porous system with interconnecting pores, so that the
entire surface of the solid is available for promoting the trans-esterification reaction. Even though, it
is possible to generate these features in the solids, it is not yet routinely possible to obtain uniform
pore architecture with absolute control over the size or radius or geometry of the pores as well as the
stability of the solid in the system. Zeolites, due to their uniform pore structure, appear to have
definite advantages for this application. In order to be favourable, the surface should be made
hydrophobic in order to promote preferential adsorption of oily hydrophobic species on the catalyst
surface and to avoid deactivation of catalytic sites by strong adsorption of polar by products like
glycerol or water. Other than zeolites, there was some other catalyst which used for producing
biodiesel including tungsten oxides, sulphonated zirconia (SZ), sulphonated saccharides, Nafion1
resins, and organosulphonic functionalized mesoporous silicas. the use of these catalysts to obtain
high conversion of triglycerides to biodiesel necessitates much higher reaction temperatures than
base catalysts because of their lower activity for transesterification. Furthermore, Alkaline metal salt
on porous support is necessary to increase catalyst ability. This jounal also provide the effect
comparison from some support to the ability of catalyst.

In the final section, Shruti G. Chopade*, K. S. Kulkarni, A. D. Kulkarni and Niraj S. Topare
suggest that the interest in heterogeneous catalysis for biodiesel production has been growing. From
the commercial point of view, solid base catalysts are seen more effective than acid catalysts and
enzymes. However, more researches on solid base catalysis are needed to substantiate this because
the favorable results from previously reported works were at the expense of high temperatures and
high pressures. This jounal review has good explanation about the role of heterogeneous catalyst in
biodiesel production, but as it mentioned in journal review, many of those method is worked in high
temperature and pressure, so it cant be fully applicable. Therefore, this review must push other
researcher to study more efficient and low cost biodiesel technology
 Article review of Nanoparticles for Heterogeneous Catalysis: New
Mechanistic Insights

Afan Hamzah (2315201011)

Swetlana Schauermann, Niklas Nilius, Shamil Shaikhutdinov, And Hans-Joachim Freund had
done research about Nanoparticles for Heterogeneous Catalysis: New Mechanistic Insights. In many
recent years, Heterogeneous catalyst technology became really popular. The range of applications of
heterogeneous catalysis covers chemical manufacturing, energy harvesting, conversion and storage,
to environmental technology. Many researchers have used surface science methods and metal single
crystals to explore elementary processes in heterogeneous catalysis. In this account, the writers use
more realistic materials that capture part of the complexity inherent to industrial catalysts. The writers
assess the impacts on the overall catalytic performance of characteristics such as finite particle size,
particle structure, particle chemical composition, flexibility of atoms in clusters, and metal support
interactions.
In the introduction section, they slightly explain application of heterogeneous catalyst
technology, how it works and the background of their research. In that account the writers will address
some of fundamental question: How can particle size and shape be controlled by doping impurity ions
of different valence into the oxide support? How does the binding energy of reactants depend on the
particle size? What is the role of surface modifiers such as, for example, carbonaceous deposits, which
are usually formed on transitions metals under operation conditions, in catalytic conversions of
hydrocarbons? What is the role of the strong metal support interaction and what consequences does
this have for the catalytic performance under realistic reaction conditions? With these case studies,
they will illustrate some of the key aspects of heterogeneous catalysis based on metal nanoparticles.
In the next section, the writers provide their research which is answered the fundamental
question in introduction section. Firstly, Controlling the shape of supported metal nanoparticles via
doping the oxide support. The method is inserting dopant dopants into the oxide volume, which act
as intrinsic charge donors/acceptors depending on their valence state with respect to the original ions.
Binding energy adsorbates: particle size effect is the second study in this account, bond in
heterogeneous catalyst is correlated with the performance of catalyst, they addressed this problem
by the direct calorimetric measurement of adsorption enthalpies of gas phase molecules on well-
defined Pd nanoparticles supported on a Fe3O4(111)/Pt (111) film. The dependence of initial CO
adsorption heats (corresponding to adsorption of a few CO molecules per Pd nanoparticle) on particle
size shows a pronounced trend: the initial heat of adsorption decreases with decreasing particle size.
According to theoretical calculations and experimental evidence, such irregular sites exhibit only
slightly higher CO adsorption energies than Pd(111). Two alternative microscopic effects may
contribute to the observed decrease of the initial CO adsorption heat with decreasing particle size: (i)
weakening of the chemisorptive interaction and (ii) reduction of the van der Waals attraction.
The next discussion is about kinetics of surface reactions: effects of surface modifiers and
atomic flexibility of metallic nanoparticles. Real catalytic processes often require small amounts of
some additives (promoters), such as, for example, alkali metals or halogens, that ensure high catalytic
activity and selectivity. The role that these compounds play at a microscopic level remains unclear for
most of the known catalytic systems in operation. In their studies, by comparing the hydrogenation
activity of clean and C-containing Pd nanoparticles they addressed the underlying microscopic
mechanisms of C-induced changes in the catalytic performance for hydrogenation of olefins and the
proposed mechanism was confirmed both theoretically and experimentally. Such insight allowed us
to identify an exceptionally important role of carbon in hydrogenation chemistry on nanostructured
catalysts that was previously not clearly appreciated. According to our model, small amounts of carbon
modify the low-coordinated surface site of Pd nanoclusters (edges, corners), thus allowing for
effective replenishment of subsurface H in steady state and enabling with this sustained
hydrogenation. These results also highlight the crucial role of subsurface H diffusion, which is a
strongly structure-sensitive process on Pd surfaces, in hydrogenation of the olefinic bond.
Computational studies suggest that the atomic flexibility of the low-coordinated surface sites is an
important structural feature that is responsible for easy subsurface diffusion of H under operation
condition.
The final question which is answered in this account is modelling strong metal/support
interaction. The term Strong Metal-Support Interaction (SMSI) has been originally used to describe
the decreased chemisorption capacity for CO and H2 on metal particles supported on reducible oxides
after heat treatment, most notably observed for Pt supported on TiO2. In this study, they address this
issue using model systems consisting of (i) Pt nanoparticles supported on Fe3O4(111) and (ii) thin iron
oxide films on Pt (111). The above models demonstrate that ultrathin oxide films formed as modifiers
on metal particles may have a promotional effect on reactivity, particularly in oxidation reactions at
low temperatures, where pure metal catalysts may suffer from site-blocking effects and strong
chemisorption of reactants. These results may aid in a deeper understanding of the reactivity of metal
catalysts supported on reducible oxides, which exhibit Strong Metal-Support Interaction.
In final section, Swetlana Schauermann, Niklas Nilius, Shamil Shaikhutdinov, And Hans-
Joachim Freund conclude that The investigation of model catalysts based on supported nanoparticles
has proven successful for mimicking structural properties of real catalytic surfaces. And it holds a great
potential to provide fundamental insight into heterogeneous catalysis. This research must have big
impact in heterogeneous catalyst research because it provides not only sight effect but also the
microscopic effect. It will push the researcher to study or finding the more efficient and low cost
heterogeneous catalyst.