Research Proposal

Title

Development of Green Catalytic Processes for the Production of

Clean Fuels, Biochemical and Advance materials using Metals

Ejim Ikechukwu Fabian

Email: iykeejim@gmail.com

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1.0 Introduction

1.1 Background of study

The role of Chemistry in almost every aspect of our modern society cannot be overemphasized. It
has created a society where its numerous products make invaluable contributions to the quality
of lives of our people. However, these products contain chemicals that have given rise to global
problems, which cause damage to both humans and the environment (Kaneda et al. 2010).
Green chemistry is a chemical philosophy that motives the design of products and processes that
reduce or eliminate the use and generation of hazardous substances (Anastas et al. 2001). One of
the keys to the success of this approach lies in the development of Green Catalysts which are
eco-friendly, can be regenerated hence reused multiple times and thus minimise waste production
during process. A good example of this green catalyst is heterogeneous catalyst which has
attracted much attention due to its potentials for realizing the concept of green chemistry. These
heterogeneous catalysts processes can be addressed by a well-designed, developed and
implemented catalytic route for the required reactions as they have clear role in pollution
prevention.
1.2 Heterogeneous Catalysis Using Solid Catalysts
a. Solid Acids Catalyses - Solid acid catalysts are widely utilized in a large variety of industrial
processes such as alkylation, isomerization, esterification, etherification, hydration,
dehydration and condensation, cracking, aromatization, oligomerization, hydrocracking, and
disproportionation (Kaneda and Mizugaki, 2010). The catalysts which can be used for these
processes include zeolites, metal oxides, heteropolyacids, clays, ion-exchange resins, carbon,
is
and other less characterized catalysts (Busca, 2007; Armor, 1991). It is also important to note
that amongst these catalysts, ZSM-5 and high-silica pentasil zeolites are the most frequently
utilized zeolite catalysts for industrial processes.
b. Solid Bases Catalyses - A variety of solid base catalysts are available, ranging from simple
metals, metal oxides, and hydroxides that are infused on supports such as alumina, silica, and
ion-exchanged zeolite, having organic base functionality tied to the surface. Many basic
transformations such as the Aldol reaction, the Knoevenagel reaction, and Michael additions
are carried out under basic conditions using aqueous or organic-soluble bases such as NaOH,

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 NaOMe, and guanidine. These organic bases are difficult to recover and thus prevent
commercialization of the process. Much effort has been focused on the development of new
solid base catalysts, which show high catalytic activity and easy accessibility (Kaneda et al.
2010).
c. Acid and Base Solid Catalyses for Sequential One-Pot Synthesis - The escalating demand for
green catalysis processes has led to the evolution of catalysts for sequential one-pot
synthesis in a single reactor for the production of the desired products (Sheldon, 2008;
Fujiwara et al.2008; Shaterian et al. 2008; Sharghi, 2008; Zeng et al.2009). This one-pot
synthesis has as its advantages: - (i) reducing the number of reaction steps as well as tedious
purification and isolation steps for synthetic intermediates and waste production and (ii)
increasing the total yield and selectivity for the desired products. The concept of site isolation
of catalytically active species proposes that different active sites can complete the individual
steps of a multistep reaction in a single pot, without their mutual destruction (Voit, 2006).
Immobilization of active species on a solid is a powerful tool for the realization of site
isolation because it is difficult for immobilized active species to access, or interferes with each
other. Immobilization of solid catalysts also allows easy recovery of the catalysts as well as
their reuse, which would be a pivotal contribution to the development of economically and
environment friendly chemical processes.

1.3 Research Problems

the
Most of organic transformations are based on acid-base catalysis findings as it has a wide range of
applications in chemical industries. The acid and base catalyzed organic transformations for the
synthesis of fine chemicals are largely carried out by chemical engineers and chemists in the
industries. Homogeneous catalysts however, have some disadvantages such as; they are required
in more than stoichiometric amount to attain maximum conversion, they are corrosive to reaction
system and a very careful handling is required. As much as these catalysts are not reusable and
recoverable from reaction mixture after reaction, they form complex molecule with product and
are highly soluble in reaction mixture resulting into hazardous waste effluent. This also leads to
the formation of hazardous inorganic acids as by-products. Solid acids and bases are found to be
alternative to the homogeneous acids and bases as they are non-corrosive, required in small

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 reusable
catalytic amount, easy to separate, reuse and ecofriendly. The selectivity can be controlled by
varying the acidic and basic strength, type of acidity/basicity and texture of catalyst, which can be
tuned by varying synthetic methods and parameters during the synthesis.

1.4 Aims and Objectives of the Study

1. Selection of starting materials (Selection of renewable feedstocks)

2. To design, synthesize and manufacture solid acid and base catalysts by loading.
3. To determine the effects of synthesis parameter on the catalyst structure and activity.
4. To determine the immobilization of solid acids and bases.
5. To evaluate the result of the immobilization of solid acids and bases on selected reactions.
6. To characterize the prepared catalysts for the type of acidity and basicity by carrying out
catalytic activity tests.
7. To study the catalytic applications of different solid acid and base catalyzed organic
compounds in clean fuel, biochemical and advance material production (transeterification,
and alkylation respectively).
8. Regeneration and reuse of the catalyst after complete production of clean fuel,
biochemical and advance materials and the development of no waste synthetic processes
for other industrial application.
9. To study the adsorption properties of the prepared materials for waste removal.
10. Catalytic activity of the prepared catalysts will be compared with the other existing solid
catalysts.

1.5 Significance of Study

This research will focus on the design and development of a novel catalytic system consisting of
immobilized solid acids and bases used in the synthesis.

The protocol presented herein offers salient advantages and features: (1) Synthesis of catalysts; (2)
producing a catalyst that will be very effective under mild conditions; (3) ensuring it requires no
organic solvent; (4) the catalyst will be moisture stable, low toxic, easily handling, and readily
available reagent; (4) simple workup procedure; (6) the utility of this method will be proved from

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the synthesized products used as energy for consumption and industrially important
intermediates. This organic solvent-free process proposed here could show much potential
application in industry due to its simplicity, easy product separation from reaction medium,
catalyst recycling and cleaner alternative pathways.

2.0 Materials and Methods

2.1 Proposed Research Work

This research proposal focuses on the use of solid acids and/or bases in the synthesis of highly
selective and efficient clean fuel, biochemical and advanced materials. Furthermore, supported
catalysts with catalytic amounts of metals attached to easily recyclable solid materials suitable for
fixed bed operations, possess promising alternative in heterogenized catalysis.
1. Novel heterogeneous catalysts will be synthesized by immobilizing solid catalysts on solid
support because they display excellent stability (chemical and thermal), good accessibility and
porosity. The effect of synthetic parameters on the catalyst structure and activity will be studied
in detail. The immobilization of solid acids/bases will be done and the results of the above
catalysts will be evaluated for production.
2. The prepared catalysts will be characterized by Chemisorption Methods, FT-IR spectroscopy,
UV-Visible spectroscopy, X-Ray Diffraction patterns, TGA, SEM, solid NMR, X-Ray Photoelectron
spectroscopy, EXAFS, Analytical Electron Microscopy (Transmission electron (TEM), Scanning
Electron (SEM), Scanning Transmission Electron (STEM), Modeling Active Site and
Temperature-programmed Reduction, X-Ray adsorption-desorption spectroscopy.
3. The catalytic performance will be determined for catalyzing reactions such as:
(i) Transesterification of oil with methanol
(ii) Condensation
(iii) Alkylation of Phenol
(iv) Oxidation of alkenes, alcohol.
(v) Hydrogenation of alkenes, alkynes and unsaturated aldehydes.
4. Optimization of reaction conditions will be done to get high yield of desired products
5. Regeneration and reuse of the catalysts in the next reaction cycles will also be performed.

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2.2 Conclusion
Some novel and highly efficient heterogeneous catalysts will be prepared by infusion into the

production of biomaterials and support materials for the application of industrially important reaction

to replace conventional homogeneous catalysts. The synthesis parameters and reaction parameters

will be optimized to develop more efficient and economic catalytic process. The structural, textural

and morphological properties of catalyst will be evaluated by FT-IR, XRD, TGA, SEM, solid NMR, XRF,

EXAFS, TEM, AFM, N2 adsorption-desorption and H2-TPR studies

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