Introduction
The fundamental reaction in organic synthesis is esterification
of carboxylic acid and alcohol which can produce high value of
material in the areas of cosmetics, plastics, food, medicines, intermediates,
etc. Furthermore, this reaction is used in the pretreatment
step for biodiesel production from low cost, lower
quality feedstocks (with high free fatty acid content) to improve the
economics of production. The cost of utilization of virgin oil (higher
quality feedstock with lower FFA content) as a raw material for
biodiesel production constitutes 70% of the total biodiesel production
cost [1]. Homogeneous acid catalysts, such as sulfuric acid,
p-toluene sulfonic acid and phosphoric acid, are conventional catalysts
for esterification [2]. However, the uses of these homogeneous
acid catalysts are limited in a practical application due to
corrosion, environmental pollution, side reactions and a more
tedious separation process, less likely catalyst recovery, sensitivity
to water and so on. Enzyme catalysts, such as lipases which remain
active even under unfavorable conditions, have been employed to
catalyze esterification [3]. Nevertheless, it should be emphasized
that use of enzymatic esterification is mainly limited by the high
cost of the lipases. Besides that, the issues of the lipase stability,
selectivity, mass transfer and other factors limited practical application
in the esterification process.
Because of environmental concerns and need for sustainable
development, heterogeneous acid catalyst for esterification have
been proposed during the past few years, including Bronsted acid €
catalysts [4e7], Lewis acid catalysts [8], and mixed Bronsted and €
Lewis acid catalysts [9e11]. There have been numerous research
efforts to develop novel solid acid catalysts in terms of activity,
selectivity, reusability, stability, and reproducibility for use in
simple and economical processes [12e14]. Endalew et al. [15] reported
that zeolites with low Si/Al ratio provide the highest catalytic
activity. However, the critical diameter of most long chain free
fatty acid molecules is greater than the pore diameters of zeolites
resulting in diffusion limitations for adsorption of reactants on
most of the acid sites. Typically, large pore acid resins, such as Nafion and Amberlyst, are more expensive than mineral acid catalysts
[16]. Sani et al. [16] summarized the ideal characteristics of a
solid acid catalyst required for biodiesel production: “(1) a hydrophobic
surface on the solid acid catalyst to promote the selectivity,
(2) an interconnected system of large pores to minimize diffusion
problems, and (3) a moderate to high concentration of strong acidic
sites to obtain appreciable reaction rates at synthesis conditions”.
Unfortunately, shortcomings of the above mentioned catalysts,
such as low specific surface area, easy deactivation, inconvenient
separation and recovery, are difficult to overcome. Thus, new
economical and eco-friendly catalysts to replace the aforementioned
catalysts are needed.
Sulfonated carbon-based catalysts have been proposed as low
cost renewable “green catalysts” able to be prepared from either
biomass or from household waste [17]. To meet this challenge,
coffee residue, a ubiquitous waste material, could be tapped into as
a potential carbon source as well as other forms of waste biomass.
Coffee is second largest commodity traded after petroleum and
commercialized worldwide as the most popular beverage in the
world [18]. According to, International Coffee Organization (ICO),
the world's coffee production is 8 million tons per year [19]. They
have also reported that 50% of the world coffee production is
delivered to the instant coffee industry, while the other 50% is used
in cafeterias, restaurants and homes to make directly beverages
from the grounded coffee. Therefore, the huge amount of coffee
residue waste from coffee industry presents an environmental
problem that has to be dealt with. For instant, it has a high
biochemical oxygen demand (BOD) caused by toxic organic compounds
such as caffeine, polyphenols and tannins [19]. In the present
study, coffee residue is shown to be a potential material to
produce activated carbon suitable for catalysts. Since it is readily
available in large quantities and easy to process without any size
reduction or pre-treatment step, it permits production of activated
carbon from waste rather than an original raw material. Bandosz
and Kante [20] reported that an activated carbon derived from
coffee residue (CAC) has enrichment surface properties such as
surface basicity and polarity as well as inducing positive charge on
the carbon atom due to the presence of nitrogen compound
(caffeine and amino acids). Synthesis of CAC via carbonization using
ZnCl2 as a chemical activation agent can obtain the desirable
properties such as high thermal stability, mesoporous structure
with high specific surface area, and a hydropho