Saka, Et Al. (2) Without Using Any Catalyst. An Experiment Has Been Carried Out in The Batch-Type
Saka, Et Al. (2) Without Using Any Catalyst. An Experiment Has Been Carried Out in The Batch-Type
Saka, Et Al. (2) Without Using Any Catalyst. An Experiment Has Been Carried Out in The Batch-Type
New process for catalyst-free biodiesel production using subcritical acetic acid and
supercritical methanol is investigated by Shiro Saka, et al. [1]. The production of glycerol as a
by-product is unavoidable in the current conventional biodiesel manufacturing processes. Since
biodiesel production is expected to increase in the near future, effective utilization of glycerol
will become an issue of interest. In this study, therefore, a process consisting of subcritical acetic
acid treatment to convert rapeseed oil to fatty acids and triacetin followed by conversion of the
obtained fatty acids to their fatty acid methyl esters in supercritical methanol treatment was
investigated. The obtained results clearly revealed that this two-step reaction could proceed
effectively at a high reaction rate, and that fatty acid methyl esters and triacetin could be obtained
under milder reaction condition than the one-step process utilizing supercritical methyl acetate
and supercritical methanol.
Rapeseed oil
Effect of CO2/N2 addition to supercritical methanol on reactivities and fuel qualities in
biodiesel production is studied by Hiroaki Imahara, et al. [4]. Addition of the third component
to supercritical methanol has been studied in the literature for biodiesel production in order to
reduce reaction temperature without deteriorating the reaction rate. However, effect of pressure
had often been neglected in the discussion. In this paper, therefore, effect of pressure was
examined with hexane, carbon dioxide (CO2) and nitrogen (N2) as one of the third components,
using batch-type and flow-type reactors. As a result, it was found that an addition of the third
component did not contribute to better product yield at constant reaction pressure. Furthermore,
the reaction rate was found to be determined by pressure and concentration of the reactants
involved in transesterification, not by the function of so-called co-solvent. Additionally, N2
addition was found to contribute to improvement in oxidation stability and reduction of the total
glycerol content, thus offering high-quality biodiesel production.
Two step reactions with alkali and acid catalyst (used canola oil)
The feasibility of using recycled canola oil as raw material to produce ASTM standard
biodiesel is evaluated by Xiaohu Fan, et al. [8]. Two-step reaction, acid-catalyzed esterification
followed by alkali-catalyzed transesterification, was performed. The high level of free fatty acids
( FFA) in the recycled canola oil was reduced to less than 1% by acid-catalyzed esterification
with 40/1 molar ratio of methanol to FFA in the presence of 5% (v/v, based on FFA) sulfuric
acid. Further alkali-catalyzed transesterification was carried out at 6/1 molar ratio of methanol to
oil and 1% (wt%, based on oil weight) potassium hydroxide. The characterizations of produced
biodiesel showed that it met the ASTM D 6751 with respect to the kinematic viscosity at 40 ºC,
acid number, flash point, water and sediment, cold soak filtration test, oxidation stability, free
and total glycerin etc. At the same time, the properties of by-product crude glycerol, such as flash
point, moisture by Karl Fisher, ash, glycerol content, were also characterized, which can
facilitate further glycerol purification and expand its applications, thus enhancing the overall
profitability of the biodiesel production process.
Biodiesel production through the use of different sources and characterization of oils and
their esters as the substitute of diesel: A review was done by singh, et al. [11]. Several methods
available for producing Biodiesel, transesterification of natural oils and fats are currently the
method of choice. The purpose of the process is to lower the viscosity of the oil or fat.
Researchers focused mainly the edible oils to produce the Biodiesel because of easily availability
and familiarity. Very few researchers concentrated on Non edible oil for the same purpose.
Non-edible oils can also be utilized for making Biodiesel fuel. For the production of
Biodiesel fuel, an alkali-catalysis process has been established that gives high conversion levels
of oils to methyl esters. Enzymatic processes using both extra cellular and intracellular lipases
have recently been developed. The cost of lipase production is the main hurdle to
commercialization of the lipase-catalyzed process; several attempts have been made to develop
cost-effective systems. In terms of production cost, there also are two aspects, the
transesterification process and byproduct (glycerol) recovery. A continuous transesterification
process is one choice to lower the production cost. The foundations of this process are a shorter
reaction time and greater production capacity. The recovery of high quality glycerol is another
way to lower production cost. Land may be a cost increasing factor for Biodiesel production,
because of more and more land required to live the growing population. To overcome the land
problem, the high yielding Biodiesel plants (non edible producing plants) should be grown in
marginal and waste land areas.
The potential of restaurant waste lipids as biodiesel feedstocks was examined by Mustafa
Canakci [14]. Waste cooking oils, restaurant grease and animal fats are potential feedstocks for
biodiesel. These inexpensive feedstocks represent one-third of the US total fats and oil
production, but are currently devoted mostly to industrial uses and animal feed. The
characteristics of feedstock are very important during the initial research and production stage.
Free fatty acids and moisture reduce the efficiency of transesterification in converting these
feedstocks into biodiesel. Hence, this study was conducted to determine the level of these
contaminants in feedstock samples from a rendering plant. Levels of free fatty acids varied from
0.7% to 41.8%, and moisture from 0.01% to 55.38%. These wide ranges indicate that an efficient
process for converting waste grease and animal fats must tolerate a wide range of feedstock
properties.
Three principal variables, molar ratio of methanol to oil, amount of catalyst, and reaction
temperature, affecting the yield of acid-catalyzed production of methyl ester (biodiesel) from
crude palm oil were investigated by Edward Crabbe, et al. [15]. The biodiesel was then used
as an extractant in batch and continuous acetone–butanol–ethanol fermentation, and its fuel
properties and that of the biodiesel–ABE (acetone–butanol–ethanol) product mix extracted from
the batch culture analyzed. The optimized variables, 40:1 methanol/oil (mol/mol) with 5% H2SO4
(vol/wt) reacted at 95°C for 9 h, gave a maximum ester yield of 97%. Biodiesel preferentially
extracted butanol, and enhanced its production in the batch culture from 10 to 12 g. l-1. The fuel
properties of biodiesel and the biodiesel–ABE mix were comparable to that of No.2 diesel, but
their cetane numbers and the boiling points of the 90% fractions were higher. Therefore, they
could serve as efficient No. 2 diesel substitutes. The biodiesel–ABE mixture had the highest
cetane number.
Michael [16] investigated the production of fatty acid methyl esters (FAME; biodiesel)
from soapstock (SS); a byproduct of edible oil refining that is substantially less expensive than
edible-grade refined oils. The most effective method involved the complete saponification of the
soapstock followed by acidulation using methods similar to those presently employed in
industry. This resulted in acid oil with a free fatty acid (FFA) content greater than 90%. These
fatty acids were efficiently converted to methyl esters by acid-catalyzed esterification. The fatty
acid composition of the resulting ester product reflected that of soy soapstock and was largely
similar to that of soybean oil.
An environmentally benign process for the production of biodiesel from Vegetable Oils
using heterogeneous catalyst was developed by Hak-Joo Kim, et al. [18]. Na/NaOH/ ᵞ-Al2O3
heterogeneous base catalyst was firstly adopted for the production of biodiesel. A study for
optimizing the reaction conditions such as the reaction time, the stirring speed, the use of co-
solvent, the oil to methanol ratio, and the amount of catalyst, was performed. The Na/NaOH/ ᵞ-
Al2O3 heterogeneous base catalyst showed almost the same activity under the optimized reaction
conditions compared to conventional homogeneous NaOH catalyst. The basic strength of
Na/NaOH/ ᵞ-Al2O3 catalyst was estimated and the correlation with the activity towards
transesterification was proposed.
Currently, alkaline bases are used to catalyze the reaction. These catalysts require
anhydrous conditions and feedstocks with low levels of free fatty acids (FFAs). Inexpensive
feedstocks containing high levels of FFAs cannot be directly used with the base catalysts
currently employed. Strong liquid acid catalysts are less sensitive to FFAs and can
simultaneously conduct esterification and transesterification. However, they are slower and
necessitate higher reaction temperatures. Nonetheless, acid-catalyzed processes could produce
biodiesel from low-cost feedstocks, lowering production costs. Better yet, if solid acid catalysts
could replace liquid acids, the corrosion and environmental problems associated with them could
be avoided and product purification protocols reduced, significantly simplifying biodiesel
production and reducing cost. Edgar Lotero, et al. [19] research was related to biodiesel
production using acid catalysts, including solid acids.
Algae
The use of microalgae can be a suitable alternative feedstock for next generation biofuels
because certain species contain high amounts of oil, which could be extracted, processed and
refined into transportation fuels, using currently available technology; they have fast growth rate,
permit the use of non-arable land and non-potable water, use far less water and do not displace
food crops cultures; their production is not seasonal and they can be harvested daily.
Luisa Gouveia, et al. [20] experimented with Neochloris oleabundans and
Nannochloropsis sp. and these algae proved to be suitable as raw materials for biofuels
production, due to their high oil content (29.0 and 28.7% respectively). Both microalgae, when
grown under nitrogen deficient culture medium, show a great increase in oil quantity (e.g.
Neochloris oleabundans can reach 56%, results not shown). If the purpose is to produce
biodiesel from one algal species, Scenedesmus obliquus presents the most adequate fatty acid
profile, namely in terms of linolenic and polyunsaturated fatty acids. However, Neochloris
oleabundans, Nannochloropsis sp. and Dunaliella tertiolecta can also be used if associated with
other microalgae oils and/or vegetable oils.
solid base catalyst (edible soybean oil & wco)
Masato Kouzu, et al. [21] was experimented with solid base catalyst for biodiesel
production with environmental benignity, transesterification of edible soybean oil with refluxing
methanol was carried out in the presence of calcium oxide (CaO), -hydroxide (Ca(OH)2), or
-carbonate (CaCO3). At 1 h of reaction time, yield of FAME was 93% for CaO, 12% for
Ca(OH)2, and 0% for CaCO3. Under the same reacting condition, sodium hydroxide with the
homogeneous catalysis brought about the complete conversion into FAME. Also, CaO was used
for the further tests transesterifying waste cooking oil (WCO) with acid value of 5.1 mg-KOH/g.
The yield of FAME was above 99% at 2 h of reaction time, but a portion of catalyst changed into
calcium soap by reacting with free fatty acids included in WCO at initial stage of the
transesterification. Owing to the neutralizing reaction of the catalyst, concentration of calcium in
FAME increased from 187 ppm to 3065 ppm. By processing WCO at reflux of methanol in the
presence of cation-exchange resin, only the free fatty acids could be converted into FAME. The
transesterification of the processed WCO with acid value of 0.3 mg-KOH/g resulted in the
production of FAME including calcium of 565 ppm.
Pyrolysis ( Wco)
The production of biodiesel using waste triglycerides as feedstock offers economic
advantages over its production from edible oils. However, because of its high acidity and
chemical complexity, many problems arise in the production of biodiesel. To facilitate the use of
waste oils as a feedstock of biofuels, there is an alternative method to obtain pyrolytic oil by
thermal_chemical conversion. Junming Xu, et al. [23] discussed the observations on the
production of biofuels by a pyrolysis reaction from high-acid-value waste oil. It was found that
the pyrolytic products consisted of hydrocarbon compounds accompanied by undesired products,
such as carboxylic acids. These pyrolytic oils were further reacted with an alcohol to decrease
their acid value. The results showed that the acid number of the pyrolytic oil decreased
dramatically from 28.8 to 2.0 mg of KOH/g after esterification. The results of gas
chromatography_mass spectrometry (GC_MS) and Fourier transform infrared (FTIR)
spectroscopy analyses indicated that the pyrolysis of waste oil generates fuels that have chemical
compositions comparable to that of petroleum-based fuel.
WCO (KOH)
Arjun, et al. [24] was experimented with waste cooking oils and KOH catalyst to
produce biodiesel. He characterized the biodiesel by its physical and fuel properties including
density, viscosity, acid value, flash point, cloud point, pour point, cetane index, water and
sediment content, total and free glycerin content, diglycerides and monoglycerides, phosphorus
content and sulfur content according to ASTM standards.
The optimal production of second-generation biodiesel using waste cooking oil and algae
oil was simulated by Mariano Martin, et al. [29]. They consider five different technologies for
the transesterification of the oil (homogeneous acid- or alkali-catalyzed, heterogeneous basic-
catalyzed, enzymatic, and supercritical uncatalyzed). They formulate the problem as a mixed-
integer nonlinear programming (MINLP) problem where the models for each of the reactors are
based on surface response methodology to capture the effects of the variables on the yield. The
aim is to perform simultaneous optimization and heat integration for the production of biodiesel
from each of the different oil sources in terms of the technology to use and the operating
conditions to apply. Furthermore, a process network is designed to minimize the freshwater
consumption. The optimal conditions in the reactors differ from those traditionally used because
the separation tasks are taken into account in this work. For algae oil, the optimal process
employs alkali as the catalyst and has a production cost of 0.42$/gal, an energy consumption of
1.94 MJ/gal, and a freshwater consumption of 0.60 galwater/galethanol. For cooking oil, the
optimal process is the one with the heterogeneous catalyst and has a production cost and energy
and water consumption of $0.66/gal, 1.94 MJ/gal, and 0.33 galwater/galethanol, respectively.
Sharif Hossain, et al. [31] used common species Oedogonium and Spirogyra to compare
the amount of biodiesel production. Algal oil and biodiesel (ester) production was higher in
Oedogonium than Spirogyra sp. However, biomass (after oil extraction) was higher in Spirogyra
than Oedogonium sp. Sediments (glycerine, water and pigments) was higher in Spirogyra than
Oedogonium sp. There was no difference of pH between Spirogyra and Oedogonium sp. The
results indicate that biodiesel can be produced from both species and Oedogonium is better
source than Spirogyra sp.
The objective is to convert waste sunflower oil used for domestic purposes such as
cooking oil into biodiesel using an alkali catalysed transesterification process.
Thirumarimurugan, et al. [32] reports experimental data on the production of fatty acid methyl
esters from sunflower oil using sodium hydroxide as alkaline catalyst. The variables affecting the
yield and characteristics of the biodiesel produced from these vegetable oils were studied.
Deshpande, et al. [33] planned to produce methyl ester fuels based on non edible oils
like castor oil by using different catalysts like NaOH and H2SO4. The effect of various
parameters like temp, residence time, and catalyst concentration investigated on yield of
biodiesel and physical properties like Viscosity, Specific gravity, Acid value.
Transesterification of waste fryer grease (WFG) containing 5–6 wt.% free fatty acid
(FFA) was carried out with methanol, ethanol, and mixtures of methanol/ethanol maintaining the
oil to alcohol molar ratio of 1:6, and initially with KOH as a catalyst was investigated by
Titipong Issariyakul, et al.[34]. Mixtures of methanol and ethanol were used for
transesterification in order to use the better solvent property of ethanol and rapid equilibrium
using methanol. Formation of soap by reaction of FFA present in WFG with KOH instigated
difficulty in the separation of glycerol from biodiesel ester. To untangle this problem, two-stage
(acid and alkali catalyzed) method was used for biodiesel synthesis. More than 90% ester was
obtained when two-stage method was used compared to ∼50% ester in single stage alkaline
catalyst. In the case of mixed alcohol, a relatively smaller amount of ethyl esters was formed
along with methyl esters. Acid value, viscosity, and cetane number of all the esters prepared from
WFG were within the range of the ASTM standard. Esters obtained from WFG showed good
performance as a lubricity additive.
Biodiesel processing and quality are closely related. The processes used to refine the
feedstock and convert it to biodiesel determine whether the fuel will meet the applicable
specifications. Jon Van Gerpen [35] described the processing and production of biodiesel and
how this determines fuel quality. The emphasis will be on processing as it is conducted in the
United States, where most biodiesel is produced by reacting soybean oil or used cooking oils
with methanol and the standard for fuel quality will be ASTM D 6751-02.