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SUSTAINABILITY IN CHEMISTRY

Green of Physical Chemistry


Application of the principles of green
chemistry in CATALYSIS
12 Principles of green chemistry
Pollution Prevention
2. Atom Economy
3. Less Hazardous Chemical Synthesis
4. Designing Safer Chemicals
5. Safer Solvents and Auxiliaries
6. Design for Energy Efficiency
7. Use of Renewable Feed stocks
8. Reduce Derivatives
9. Catalysis
10. Design for Degradation
11. Real-time analysis for Pollution Prevention
12. Inherently Safer Chemistry for Accident Prevention
Principle of Green Chemistry
Industrial Process Using Solid Acid Catalyst

Introduction

Catalyst: waste minimisation


Main goals: produce product with 100% yield and 100% selectivity
Careful choice and design of catalysts manufacture chemicals with zero
waste
Anastas et al.: catalysis has manifested its role as fundamental tool in pollution
prevention.
Green chemistry: design of chemical products and processes that reduce or eliminate
the use and generation
of hazardous substances Solid Acid Catalyst
Reactions: alkylation, etherification, oligomerisations, esterification, isomerization,
cracking, dehydration, hydration, and disproportionation.
Catalysts: zeolites, oxides, ion-exchange resins, phosphates, clays, complex oxides,
heteropolyacids, and sulfated zirconia.
Industrial Process Using Solid Acid Catalyst

Introduction
Catalysis is one of the primary tools for achieving all twelve of the principles of Green
chemistry that was designed and set by Anastas
Example: manufacture of cumene utilization of substances that posses
little or no toxicity to human health or the environment.
Traditional reaction: solid phosphoric acid or aluminium trichloride catalyse the
benzene alkylation with propene. Theese catalysts: corrosive and hazardous
wastes (no Green )
Green chemistry: Mobil-Badger cumene process using zeolite as a catalyst
environmentally inert and gives high yield of product.
Industrial Process Using Solid Acid Catalyst

Strong interest: the use of solid acid catalysts as an alternative to or as replacement


for homogeneous (liquid) acid catalysts such as HCl, HF, AlCl3, and H2SO4. These
catalysts are very effective, but they produce highly corrosive media with
chemically reactive waste streams. Purification can be both difficult and
hazardous.
The major challenge: the development of cost-effective, highly active, selective and
stable solid acid replacements. By contrast: the solid acid counterparts are easier
to handle, purification is simpler and cheaper and the general operation of a large
chemical process is safer.
Well-known industrial process today use a solid acid catalyst: synthesis of high octane
fuels, which are based almost exclusively on the use of HF (and sulfuric acid for
high octane fuels).
Clearly: the ability to use a solid that is highly active, catalytic and yet sage to handle
would represent a major breakthrough in any one of the reactions described
above.
Solid acid catalysts: zeolite, clay (micropore), MCM-41, SBA-14 (mesopore)
Bronsted and Lewis acid sites (lihat contoh Chapter 6)
Solid Acid Catalyst

Hydrocracking need the use of metal/supported system catalyst:


Ni/zeolite, NiMo/zeolite, Cr/zeolite, Pd/zeolite, or Pt/zeolite
Zeolite: green chemistry
Metal/zeolite: no green chemistry; the metal cause serious problem in environment
(toxic, non degradable, hazardous) how to solve this problem?
Greening:
Use the lowest toxicity metal: replace Ni or Cr by Co, Pd or Pt.
Regeneration of catalyst: oxidation, hydrothermally treatment
Biocatalysis: enzyme (Chapter 9).
Micelle-templated silicas as catalyst (mesoporous materials): MCM, SBA.
(Chapter 7).
Biocatalysis

Introduction
Biocatalysis:
the use of a biological system to catalyse the conversion of a single material (the
substrate) to a defined product has a long hystory in organic
chemistry, and specific biocatalytic steps have ben used in the industrial
production of both bulk and fine chemicals for many years.
Enzymes ability: to catalyse organic reactions in the moderate pH range of 4 9 at
reasonable temperatures (usually 1 - 50 C) and without extremes of pressure or
the addition of metals can provide an environmentally acceptable method of
performing many reactions that otherwise may require highly acidic or alkaline
environments, high energy input for heating or toxic metal catalysts.
Biocatalysis
> Production of Acetic acid from ethanol using a strain of Acetobacter (200 years)
Utilization of nitrile hydratase enzyme from Rhodococcus to convert acrylonitrile
into acrylamide (Fig. 9.1) replaced a chemical process involving acid catalysis and
eliminated the formation of acrylic acid as a side product.
Biocatalytic nitrile hydrolysis has been employed systematically by the Lonza group
as a method for production of subtituted nicotinic acids and nicotinamide (Fig. 9.2)
Food industry: the uses of the B-galactosidase for the conversion of lactose into
glucose and galactose (Fig. 9.4)
Big scale industrial biotransformation is currently the conversion of glucose to
fructose by the enzym glucose isomerase.
Biocatalytic process: the conversion of the fermentation product penicillin G into
6-aminopenicillanic acid by the enzyme penicillin acylasi (Fig. 9.5)

Biotransformation:
carried out under neutral conditions and without the need for elevated
temperatures; anhydrous conditions and organic solvents to avoid decomposition
of the reactive product.
Friedal-Craft Reaction

N 2 + H2 NH3

Katalis awal: AlCl3 corrosive, toxic (no green)


Greening: Ni/clay catalyst (green, safe for landfill)
Photochemistry

Photochemistry is a clean technology:


1. Reduced usage of reagents
2. Lower reaction temperature
3. Control of selectivity

1.)> Photochemical reaction is initiated by the absorption of light, rather than by heat
or the action of conventional reagents. The activation energy needed is provided
by photons, which are non-material and disappear in the process. Photons
therefore can be regarded as ideal reagents: they activate reactions without
directly generating any by-products; non-toxic, avoiding the need for recovery and
disposal of harmful waste will reduce overall processing costs.
2)> Photoreactions often can be carried out without heating the reaction mixture and
the reaction vessel, thus saving energy and reducing thermal decomposition of the
product.
(see Chapter 18, page 417)
ELECTROLYSIS
Electrochemistry present a powerful method for promoting reactions:
- Within a potential scan of approximately 6,0 V it offers a vast range of opportunity
- Powerful oxidants (e.g. ozone) and reductants (e.g. solvated electrons, alkali metal)

The benefit in the use electrochemistry for greener and more sustainable processes:
- Mild chemical conditions
- Ease of control
- High process selectivity
- Novel chemistry available
- Mild process conditions
- Safer operation
- The electron is an inexpensive reagent
Electrochemisty can make a significant contribution to sustainability by satisfying a
range of targets for green chemistry:

1. Clean synthesis by direct oxidation and reduction


2. Enhanced atom utilization
3. Replacement of stoichiometric reagents: regeneration of a wide range of redox oxidants and
reductants
4. New solvents and reaction media: solid polymers, ionic liquids, supercritical fluids, etc.
5. Water-based processes and products: predominate in electrochemistry
6. Replacements for hazardous reagents: solution-phase oxidants and reductants can be
generated in situ.
7. Intensive processing: electrochemical processes can be intensified using ultrasonics, centrifugal
fields, etc.
8. Novel separation technologies: electrochemical enhancement of ion exchange, adsorption, gas
phase separation, and water filtration.
9. Alternative feedstocks: electrochemistry in many cases allows alternative feedstocks.
10. New, saver chemcals and materials: in situ, on-demand reagent can be generated.
11. Waste minimisation/reduction: achieved by reagent regeneration and meaterial recycling.
FUEL CELL
Fuel cell technology has been developed as a means of increasing the
efficiency of electricity generation from existing petroleum and natural-
gas-based fuels.
Fuel cells are able to utilize both hydrogen and methanol, potentially from
regenerative biomass sources, as a long-term alternative to petroleum
fuels.
Fuel cells were first described in 1839 by the British scientist William
Grove, who was experimenting with the electrolysis of water and
collecting the hydrogen and oxygen generated in inverted test tubes.
He observed that after removing the battery power from the electrolysis
cell current continued to flow from the cell, making use of the collected
gases as the fuel.
FUEL CELL
The fuel cells were used to generate electricity for power and water for
consumption from hydrogen fuel in a clean, efficient and reliable way.
In these cases cost was of little concern, hence fuel cell systems for
commercial and consumer applications generally were too expensive.
The financial incentive also was low for individual companies to make the
huge investments necessary to develop a feasible commercial fuel cell
system.
GO TO SLIDE 16
LIHAT POWER POINT HASIL RISET PRODUKSI H2
SEE VIDEO OF FUEL CELL

SELESAI
Fuel cells exhibit a number of advantages over alternative techniques for the
generation of electricity from chemical fuels. These advantages can be summarised
as follows:
(1) High theoretical efficiency, especially at low
operation temperatures and low load levels.
(2) Low levels of pollutant emissions due to clean
fuels, e.g. methanol or desulfurised natural gas,
and because they operate at temperatures below
that required for NOx formation.
(3) No moving parts, hence fuel cells tend to be
quiet during operation and require less on-site
maintenance than generators with moving parts.
(4) Fuel flexibility and internal reforming is possible,
especially with the high-temperature fuel
cells.
(5) Modular construction, hence the size of the fuel
cell unit can be tailored to local energy needs.
(6) Waste heat can be used, transforming the fuel
cell into a combined heat and power unit. The
ratio of heat to electrical power can be altered by
adjusting the efficiency of the fuel cell.

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