Ain Shams Engineering Journal 10 (2019) 821–839

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Ain Shams Engineering Journal

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Review of diesel production from renewable resources: Catalysis,

process kinetics and technologies
Ashraf Amin
Chemical Engineering & Pilot Plant Department. National Research Centre, El Bohouth St., Dokki, Egypt

a r t i c l e i n f o a b s t r a c t

Article history: The biomass is a renewable source of energy. Diesel can be synthesized from biomass using different pro-
Received 31 January 2018 duction methods. Diesel from bio-resources is divided to FAME and renewable biodiesel. FAME biodiesel
Revised 13 January 2019 is produced from the transesterification of vegetable oils and fats. Renewable diesel is produced by
Accepted 6 August 2019
hydro-deoxygenation of vegetable and waste oils and fats. While FAME biodiesel can be mixed with
Available online 22 August 2019
petro-diesel. Renewable diesel is a diesel like bio-substitute which can be used instead of petro-diesel.
Throughout this article, catalysts used for producing FAME and renewable biodiesel are presented. The
Keywords:
different technologies and production methods employed for FAME and renewable biodiesel synthesizing
Biodiesel
Renewable diesel
are discussed. Finally, the reaction mechanisms and kinetics of FAME and renewable biodiesel formation
Catalyst reactions are shown.
Kinetics Ó 2019 The Author. Published by Elsevier B.V. on behalf of Faculty of Engineering, Ain Shams University.
Biomass This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-
nd/4.0/).

1. Introduction An efficient biomass conversion technology is crucial to suc-

Recently, renewable energy sources are considered around the
world due to concerns related to global energy supply reliability
and security leading to a worldwide interest in investigating new
technologies for biomass utilization as a renewable energy source.
As a CO2 neutral and a renewable energy source, biomass has
attracted the research community for decades. The global climate
change has increased the interest of research community in devel-
oping environmental and economical methods for agricultural
waste management. In addition, the depletion of fossil energy
resources necessitates the developing of new energy sources from
renewable energy resources [1–3]. The biomass is a globally avail-
able material, which is used successfully for producing bio-oil.
Developing effective techniques to use and convert biomass will
generate revenues and reduce the disposal problem. Biomass orig-
inates from different sources; including forestry, agricultural crop
residues, and food processing. In literature, the primary processes
to convert and utilize biomass are: hydrolysis, pyrolysis, gasifica-
tion, and hydrogenation [4–6].
E-mail address: ashmukhtar@yahoo.com
Peer review under responsibility of Ain Shams University.
Production and hosting by Elsevier
cessfully build a strong bio-economy. The catalyst plays an impor-
tant role in the quality and value of the final product of biomass
conversion. The conversion of biomass produces bio oil that can
be further upgraded to a variety of chemicals and fuels. Many tech-
nical problems with the final upgrading step exist; so the produc-
tion of high quality bio-chemicals and fuels is not yet economically
feasible. The key challenge is to find an effective catalyst for bio-oil
upgrading. The current upgrading catalysts are liquid catalysts.
Using these liquid catalysts leads to the formation of complex mix-
tures. These liquid catalysts are difficult to separate and result in a
low quality product. The Acidic liquid catalyst causes rapid failure
to the process vessels and the transportation vehicles. Solid cata-
lysts should be integrated into bio-oil upgrading. To improve the
economics and marketing of the bio- fuels and chemicals, there
is an emerging call for developing multifunctional solid catalysts
by employing transition metal oxides and zeolite related materials
[7–10].
There is an emerging need to replace the current liquid catalysts
with effective solid catalysts. The solid catalysts can be easily sep-
arated from the products. In addition, by combining different cat-
alytic sites, a multifunctional solid catalyst can be developed. The
multifunctional catalyst will help in process intensification and
hence reduces the energy requirements. Using solid catalyst, high
quality and value chemicals and fuels will be manufactured. The
solid catalyst is important for the industry to ensure better market-
ing of the produced chemicals; and therefore, to invest in biomass
utilization [11–13]. Several compounds can be produced when

https://doi.org/10.1016/j.asej.2019.08.001
2090-4479/Ó 2019 The Author. Published by Elsevier B.V. on behalf of Faculty of Engineering, Ain Shams University.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
822 A. Amin / Ain Shams Engineering Journal 10 (2019) 821–839
biomass is thermally treated to form the bio oil. The residence
time, temperature, catalyst, and the heating rate are the factors
affecting the chemicals produced and their percentages [14]. The
bio oil may contain wide spectrum of compounds and functional
groups: steam, CO2, organic acids (carboxylic group), esters and
alcohols (hydroxyl group), ketones, aldehydes, sugars, furans, phe-
nols, and aromatic compounds in addition to traces of inorganic
compounds. The bio oil contains considerably different chemicals
in terms of composition, functional groups, chemical reactivity
and coke formation (catalyst deactivation) [9,15].
Different reactions are required to upgrade the produced bio oil
including dehydration, deoxygenation, cracking, polymerization,
and aromatization. Different reaction scenarios are expected to
occur. To run these reactions simultaneously for different com-
pounds, a multifunctional catalyst is required allowing process
intensification. Catalytic acid sites catalyze the most powerful
ways to convert the bio oil into fine chemicals and fuels: namely,
Hydrolysis, dehydration, and hydrogenolysis. Basic catalysts play
an important role in essential processes like transesterification,
deoxygenation, and depolymerization [12]. MgO, ZnO, CeO2,
MnO2 and ZrO2 are usually employed as decarboxylation catalyst
but were not studied extensively for bio oil upgrading. The pres-
ence of zeolite and molybdenum oxide is important to catalyze
the formation of olefins and aromatic compounds to increase the
octane rating of the produced fuel. The multifunctional catalysts
integrate several types of catalytic sites to create novel catalytic
sites, which reduce the energy barrier of conversion and improve
activity and selectivity [11,12].
This article discusses the production of biodiesel and the cur-
rent production technology under research. The article focuses on
catalysts used for producing biodiesel from different feedstocks.
The kinetics of producing biodiesel will be discussed. Finally, dif-
ferent commercial units around the world will be listed.
2. Biodiesel production
Renewable fuels are currently produced from several resources
including fats, vegetable oils, and waste cooking oils. FAME (Fatty
Acid Methyl Ester) biodiesel is considered as the most common
biofuel around the world, which can be produced by transesterifi-
cation of fats and vegetable oils. Biodiesel is a promising fuel; it is
highly biodegradable and has a low toxicity. It can replace diesel
fuel in power stations and vehicles since it has similar properties
to petrodiesel. Biodiesel can be blended with petroleum diesel to
Fig. 1. Biodiesel and renewable diesel manufacturing processes [19].
decrease carbon dioxide emissions [3]. Biodiesel provides different
environmental benefits since it is a carbon neutral fuel. The typical
biodiesel production process (transesterification) transforms oil
into long-chain mono alkyl esters, or FAME biodiesel using liquid
(homogenous) catalysts.
Due to many disadvantages of FAME biodiesel associated with
liquid catalyst employed in transesterification [16], different pro-
cesses are under investigation to produce a second generation bio-
diesel (renewable diesel) or to employ solid catalysts in
transesterification [17]. Renewable diesel is a diesel with a compo-
sition similar to petroleum diesel and made of renewable
resources. Renewable diesel is produced from fats and vegetable
oils like FAME biodiesel. However, the reaction of fats and oils to
form fuel is the main difference between renewable and FAME bio-
diesel production technology [18,19], as shown in Fig. 1 [19].
Renewable diesel can be manufactured using hydro-
deoxygenation of oils and fats to produce alkanes with a chemical
composition similar to petroleum diesel.
A comparison between FAME biodiesel and renewable diesel
production and application are shown in Table 1. Table 2 shows
that renewable diesel has properties closer to petro-diesel com-
pared to FAME biodiesel [18,19]. The renewable diesel and FAME
biodiesel have dissimilar properties. FAME biodiesel and renew-
able diesel have low sulfur content and near-zero aromatic content
compared to petro-diesel. Renewable diesel has the highest cetane
number and a cloud point similar to petroleum diesel. A blend of
renewable diesel and petroleum diesel can be used in conventional
engines after adding compounds (ester- and monoacid-type lubric-
ity improver additives) to improve lubrication properties.
By comparing the renewable and FAME biodiesel, techno-
economic study showed that both processes economics is depen-
dent on unit capacity and raw material price. It was found that unit
capacity less than 100,000 tons/year will result in a negative net
present. For unit capacity more than 200,000 tons/year, renewable
diesel production by hydro-deoxygenation in a petroleum refinery
is an economically feasible process [20].
The target of next bio-fuel generation reactions is to increase
bio-fuel produced annually by utilizing biomass residuals from
industry [22]. Residual biomass consists of the crops’ residues
and non-food crops. In addition to residual biomass from industry,
industrial and municipal organic wastes such as waste cooking oil
can be further utilized to generate bio-fuels [23,24].
Different types of biomass feedstock are available which
requires the development of new processes to convert the different
 A. Amin / Ain Shams Engineering Journal 10 (2019) 821–839 823

Table 1
Comparison between FAME biodiesel and renewable diesel production and applications [18,19,21].

Type FAME Biodiesel Renewable Diesel

Composition Fatty acid methyl esters (FAME) Deoxygenated fuel, similar to HC
Advantages
Petroleum oil price is fluctuation
Ultra-low Sulphur diesel comparable

Fossil fuel resources are non-renewable
Higher net energy balance than petroleum or biodiesel

Fossil supply security of supply threatened
Considerably reduced GHG emissions

Carbon neutral
Constraints
5–10% in petro-diesel using current engine without modification

Energy density is low (for FAME around 38 MJ/kg1 vs. 43 MJ/kg1
for renewable diesel)

Crops demand fertile land, energy, nutrients, energy

Food price may increase significantly
Technology
Transesterification of vegetable oils and fats Pyrolytic cracking

Whole biomass or oil

High T, no O2, catalyst (zeolites, pillared clays)
Hydrogenation

1, 5–3, 8%, activated C catalysis (Pd, Ru, Rh)

Ketonic decarboxylation-hydrogenation (plus Pt/MgO or Pt/Al2O3)

Table 2 renewable diesel processes and employing solid catalyst in trans-

Diesel-Biodiesel Fuel properties [18]. esterification process to produce a higher quality FAME biodiesel
Properties Petrodiesel Biodiesel Renewable Diesel
[19,35–37]. A detailed description of different kinds of biodiesel
including biodiesel and renewable diesel types is shown below:
Cetane# 40–55 50–65 75–90
Energy Density, MJ/kg 43 38 44
Density, g/ml 0.83–0.85 0.88 0.78 3. FAME biodiesel – transesterification process
Energy Cont., BTU/gal 129 K 118 K 123 K
Cloud point, °C 5 20 10
Oxidative stability Baseline Poor Excellent
3.1. Transesterification using mechanical stirring
Clod flow Properties Baseline Poor Excellent
Lubricity Baseline Excellent Baseline FAME (Fatty-Acid Methyl Esters) biodiesel is produced by trans-
Sulfur <10 ppm <5 ppm <10 ppm esterification with an alcohol of vegetable oils or animal fats.
NOx Emissions Baseline +10 10 to 0
Transesterification reaction is carried out in a batch reactor
between triglyceride and alcohol. Transesterification is the conver-
biomass feedstock into renewable diesel and other categories of sion of triglyceride to ester such as the alkyl monoesters to make
second generation bio-fuels. Different processes are currently up biodiesel. Transesterification process is usually conducted in
under study and to some extent applied in market including: Fis- the existence of a catalytic agent. Reactant are charged in the batch
cher–Tropsch diesel process, Green diesel process, white diesel reactor and the temperature is adjusted to the required value then
process, and hybrid diesel process. Fischer–Tropsch diesel process mechanical stirring is used to mix the reactants, and that is why
is a process to convert biomass to bio-diesel using same route to this method is known as mechanical stirring method. This method
convert synthetic gas to diesel [25]. Green diesel process is a pro- is suitable for all types of catalyst. Parameters affecting the process
cess to convert vegetable oils to diesel using catalytic hydro- yield are mixing intensity, catalyst, temperature, and alcohol and
treating of oils and fats [26]. White diesel process is a process to its ratio to oil. Biodiesel produced using mechanical stirring
convert waste cooking oil to diesel using catalytic hydro-treating method is known as FAME biodiesel [38–40]. For both homoge-
similar to green diesel process [27–29]. Hybrid diesel process is a nous and heterogeneous catalysts methods, mechanical stirring
process to convert heavy refinery streams and vegetable oils into method can be used successfully [39,41].
diesel using co- hydro-processing of vegetable oils with heavy Throughout the transesterification reaction viscosity of veg-
refinery streams [30,31]. etable oils are reduced significantly by breaking the vegetable oils
fatty acids to alcohol esters and glycerol using alcohol [42]. A cat-
alyst is used during the reaction; such catalyst might be a strong
2.1. Raw material for producing biodiesel base like potassium or sodium or hydroxide, or a strong acid, such
as sulphuric acid especially for high free fatty acid raw materials,
To produce biodiesel, a source of lipid should be used. The lipid or enzymes. Alcohol is required to react with fatty acids, ethanol
source could be animal fats, vegetable oils, waste cooking oil, is preferred due to lower level of toxicity [43]. However, the most
microalgae, or cyanobacteria [32–34]. Optimum raw material widely used alcohol is due to lower price compared to ethanol
should be provided at a reasonable price and has a composition [44,45]. Using methanol widely will results in the dominance of
that ensures the production of a good biodiesel characteristics fatty acid methyl esters (FAME) [21]. The overall transesterification
[32]. Nearly 70–90% of biodiesel production price is related to process is presented in Fig. 2:
the raw material. Currently, edible oil is used widely as the main The triglyceride molecule is broken down in three steps [39]:
source of bio-diesel. 99% of the global biodiesel produced comes
from edible oil. Rapeseed oil represents 59% of the total edible oil (1) An intermediate tetrahedral is produced
used for biodiesel production followed by soybean (around 25%), (2) Fatty acid ester and diglyceride ion and are formed from
then palm oil (10%), and finally sunflower oil (5%) [35]. unstable intermediate tetrahedral dissociation
Relying on edible oils as a major source for biodiesel is associ- (3) Finally, recovery of the catalyst by proton transfer.
ated with ethical and environmental problems. The current trend
is to produce biodiesel from waste oil, waste fats, and non-edible As a result, three fatty acid esters and a glycerol are formed.
oil resources like jatropha and castor oils. Utilizing low grade FAME biodiesel can be manufactured from different raw mate-
raw materials required development of more efficient process like rials. In U.S., soybean is used for producing FAME while rapeseed is
824 A. Amin / Ain Shams Engineering Journal 10 (2019) 821–839

Fig. 2. Transesterification process [46].

used in Europe [47]. By products produced during transesterifica-
tion, are glycerine, water, and traces of alcohol, should be removed
to improve the quality of produced FAME. New release of diesel
engines which has manufacturer approval for using FAME is
started to be used in market. Currently, FAME is mostly used in a
mixture with petro-diesel in conventional engines [48]. A detailed
description of the FAME biodiesel production process is presented
in Fig. 3.
At 2010, 20 million metric tons are produced globally. FAME
biodiesel is available widely in gas stations around the world since
many countries have imposed the use of biodiesel [49]. Feed stock
price is the major factor in defining the biodiesel market price, the
feed stock may represent up 88% of the total cost for production
process [50]. The total cost of production can be reduced dramati-
cally by employing low cost feedstock options such as waste fat or
oils, which may reduce the FAME biodiesel properties [39,51].
stock with higher free fatty acids should be conducted as a
preliminary step before the transesterification reaction to convert
free fatty acids to esters. The optimum condition for acidic catalyst
transesterification is: 80–100 °C, methanol/oil ratio of 12:1, and
using 3 wt% sulfuric acid [46,53,57].
During the transesterification using liquid acidic catalyst, car-
bonyl group of ester molecule is protonated leading to carbocation.
Subsequently, alcohol performs nucleophilic attack to form a tetra-
hedral intermediate. The tetrahedral intermediate releases glycerol
to produce esters and to restore the acidic catalyst. The detailed
reaction mechanism of acidic catalyst transesterification of veg-
etable oil (using a mono-glyceride as an example) is shown in
Fig. 4. The same mechanism and analogy can be used also for
diglycerides and triglycerides transesterification using acidic liquid
catalyst [39,41]. Table 3 shows different examples of homogenous
acidic/alkaline catalysts experiments conducted in literature.

3.1.1. Acidic catalyzed homogenous transesterification process:
The liquid acid catalysts such as sulphuric, hydrochloric, sul-
fonic and phosphoric acids are more suitable for feedstock with
high free fatty acids. The acidic liquid catalyst decreases the ratio
of the free fatty acids through esterification processes. However,
the acidic catalyst slows down the transesterification reaction
and requires higher methanol/oil ratio [53–56]. Using an acidic cat-
alyst, the reaction might take longer reaction time and should be
conducted at higher temperature, which will accelerate the corro-
sion of the equipment. In general, using acidic catalyst for feed-
3.1.2. Alkali-catalyzed homogenous transesterification processes
Alkali-catalyzed esterification is the most common method
used for transesterification by employing liquid alkaline metal
hydroxides, sodium, or potassium carbonates. Alkali-catalysts are
more active than acid catalysts [58–60]. The optimum conditions
for alkaline catalyst transesterification are: 60–65 °C, methanol/
oil ratio of 6:1, and using 1–1.5 wt% KOH or NaOH [38,61].
During the transesterification using alkaline catalyst, the first
step is a preparatory step at which alkoxide group is formed. Then,
the ion of alkoxide reacts with the carbonyl group of glyceride to

Fig. 3. FAME biodiesel process [52].

 A. Amin / Ain Shams Engineering Journal 10 (2019) 821–839 825

Fig. 4. Mechanism of acidic catalyst transesterification [41].

Table 3
Summary of homogenous catalysts experiments for FAME biodiesel production.

Feedstock Catalyst used Catalyst/oil ratio (wt%) Yield/Conversion (Y/C, %) Temp. (°C) Reaction time (h) Reference
Used Frying NaOH 1.1 Y = 88.8 60 0.33 [53]
Waste cooking KOH 1 Y = 98.2 70 1 [62]
Canola NaOH 0.5 Y = 98 25 0.33 [63]
Soybean KOH 1.5–2.2 Y = 99.4 40 0.25 [64]
Canola KOH 0.7 Y = 99 25 50 [65]
Waste cooking KOH 1 Y = 99 27–32 0.016 [66]
Waste cooking H2SO4 4 C > 90 95 95 [67]
Sunflower H2SO4 1 C = 90 65 65 [68]

compose a tetrahedral intermediate; which reacts with alcohol to
release the alkoxide ion. Finally, the tetrahedral intermediate dis-
sociates to ester and glycerol. The mechanism of alkaline catalyst
transesterification is shown (using a mono-glyceride as an exam-
ple) in the Fig. 5. The same mechanism and analogy can be used
also for diglycerides and triglycerides transesterification [39,41].
To decide the best catalyst for transesterification, humidity and
free fatty acid (FFA) content are the governing factors. The alkali
catalyst is better for transesterification of feedstock containing less
than 1% of free fatty acids. This is attributed to the neutralization of
the alkaline catalytic medium in a saponification reaction of potas-
sium and sodium by the free fatty acids. The formation of such
undesired soap works to increase the reaction time, the soap is sol-
uble in glycerin. On the other hand, acidic catalyst is highly sensi-
tive to humidity in feedstock. The corrosion induced by acidic
catalyst reduces the FAME biodiesel applicability [55,56,58,60].
3.1.3. Heterogeneous catalysts
When Liquid catalysts are used, catalyst must be removed from
FAME biodiesel to eliminate engine problems. Alkaline catalysts
cause elevated ash levels while the acidic catalyst results in corro-
sion [57]. Due to costly separation and purifications costs associ-
ated with transesterification using homogenous catalyst,
heterogeneous solid catalysts like metal oxides and zeolites are
employed for transesterification [39]. The solid catalyst can be sep-
arated easily and reused which will improve the overall process
economics. Acidic and alkaline oxide solid catalysts are used by
supporting the catalyst over a material with large surface area.
Acidic catalysts are mostly sulphonated/phosphated metal cata-
lysts [69]. Alkaline based-catalysts showed a higher activity com-
pared to acidic based-catalysts, similar to homogenous catalysts
[4,19,70]. Table 4 shows a list of vegetable oil transesterification
under different types of heterogeneous catalysis.
Many Studies concerned with transesterification using hetero-
geneous catalysts are found in literature. Calcium aluminums dou-
ble layer oxide and modified calcium-Iron-aluminums oxide were
employed for the esterification of soybean oil. Optimal yield
reached 91% using modified combined catalysts under optimal
reaction condition: 65 °C, 270 rpm stirring rate, 1 h reaction time,
and 6% weight-ratio of catalyst/oil. Lu et al. [71] revealed that
the developed catalyst is greatly insoluble in the reacting mixture
methanol/methyl esters, leading to easier separation of catalyst to
be reused.
Xie and Zhao [78] used (CaO–SnO2 composite) for the transes-
terification of soybean. Ratio of Ca/Sn and temperature of calcina-
tion showed dominant effect on the activity. 90% yield was
observed under the following optimal conditions: Ca/Sn equal to
4:1, calcination temperature of 975 K, and 7 h reaction time. The
developed catalyst showed excellent stability and durability, easy
recycling, and can be reused.
Zhou et al. [79] studied the transesterification of Jatropha curcas
L. using solid catalyst of nano-La2O3. The developed catalyst
showed excellent activity due to its high alkaline nature and high
surface area. The reported yield reached 98% under optimal condi-
tions: 180 °C, 2 h reaction time, and 10% weight-ratio of catalyst/
oil.
Solid catalyst for transesterification may arise from biomass
materials, these materials acquire a catalytic activity suitable for
FAME biodiesel transesterification [58,80]. The application of such
natural catalysts will improve the overall economics of the transes-
terification and will improve its environmental impact [81]. An
eco-friendly process for biodiesel production can also be initiated.
Employing such natural material will save the long process for cat-
826 A. Amin / Ain Shams Engineering Journal 10 (2019) 821–839

Fig. 5. Mechanism of alkaline catalyst transesterification [41].

Table 4
Summary of heterogeneous catalysts experiments for FAME biodiesel production.

Feedstock Catalyst used Catalyst/oil ratio (wt%) Yield/ Conversion (Y/C, %) Temp. (°C) Reaction time (h) Reference
Palm Kernel CaO 6 Y = 98 60 3 [72]
Sunflower CaO 3 C = 100 252 0.1 [73]
Soybean MgO 5 Y = 60 130 7 [74]
Waste cooking K3PO4 4 Y = 97.3 60 2 [75]
Canola SO42/ZrO2 3 Y = 93.6 120 4 [76]
Waste cooking Sr(NO3)2/ZnO 5 Y = 94.7 65 4 [77]
Soybean CaFeAl 6 Y = 90 60 1 [71]
Soybean CaO–SnO2 composite 8 Y = 90 70 6 [78]
Jatropha curcas L. nano-La2O3 10 Y = 97.6 180 2 [79]

alyst preparation [82]. Limestone calcite and dolomite have shown
excellent catalytic activity during transesterification with a
reported yield of 95% and 98% respectively, which is attributed to
the formation of calcium oxide during calcination [58,83]. Fly
ash-based catalysis has also been reported [75]. Babajide et al.
[80] have reported an alternative route for the utilization of South
African coal industry fly ash as a catalyst in transesterification
reaction. A conversion of 86% can be obtained with fly ash loaded
with 5% KNO3 during transesterification of sunflower oil at 160 °C.
3.1.4. Enzyme-catalyst transesterification
Enzyme catalysts represent another solution to overcome the
challenges associated with separation and purification processes
for FAME biodiesel to separate liquid catalysts. Lipase is usually
used as a catalyst FAME biodiesel transesterification, however
lipase is quite expensive [84,85]. The economics of such process
is not promising due to the lipase high cost and technical chal-
lenges related to immobilization and recovery of lipase [86–88].
Nelson et al. [89] reported a conversion of 95% using lipozyme as
 A. Amin / Ain Shams Engineering Journal 10 (2019) 821–839
a catalyst for FAME biodiesel transesterification. Methanol was
used as an alcoholic reactant under the following transesterifica-
tion conditions: Enzyme concentration of 12.5–25%, reaction time
of 4–8 h, and a reaction temperature of 45 °C.
3.2. New technologies for transesterification process
3.2.1. Ultrasonic irradiation method
Ultrasonic irradiation method is employed as a technique for
conducting transesterification to overcome the mass transfer limi-
tation between the two immiscible reactants, oil and methanol
[90]. The sound waves with appropriate frequency are transmitted
to the reacting mixture forming cavitation bubbles, which may dis-
rupt the phase boundary between oil and methanol creating a
well-mixed emulsion. Quicker transesterification reaction is estab-
lished as a result of good mixing and can be conducted using less
methanol, less catalyst, and at lower temperatures. 24–40 kHz fre-
quency is usually employed for producing biodiesel [39,91,92].
3.2.2. Supercritical alcohol method
This method depends on conducting the transesterification
reaction at temperature and pressure higher than the critical tem-
perature and pressure leading to a one phase mixture. One phase
formation results in better mass transfer, leading to a faster reac-
tion. Supercritical methanol method is usually conducted at 80
atm and a temperature between 300 and 400 °C [39]. Despite the
high pressure and temperature, the supercritical method does
not require a catalyst which saves separation cost and catalyst
price and reduces reaction time to around 3 min. This process is
suitable for a wide variety of feedstock and characterized by pro-
ducing high quality glycerol [39,93,94]. Temperature is the most
effective factor in supercritical transesterification. A lower temper-
ature range can be used (250 °C), if a catalyst such as CH3ONa (non-
homogenous solid catalyst) is employed in the transesterification
process [93,95].
3.3. Development of new utilization and reforming techniques for
Glycerol
During the production of FAME biodiesel, glycerol is produced
in large quantities. Glycerol is a raw material for different indus-
tries like pharmaceuticals, cosmetics, foods, etc. Such applications
are still not enough to utilize amount of glycerol expected to be
produced when biodiesel is manufactured on a full scale. There is
a challenge for the biodiesel industry, which is developing new
uses and demands for glycerol [39]. A new promising utilization
of glycerol is the reforming of glycerol to produce variety of chem-
icals like butanol, ethanol, formic acid, propionic acid, and H2 [96].
Different reaction pathways can be employed to produce fine
chemicals from glycerin such as dehydration, dehydrogenation,
acetylation, and esterification [97]. Another way is to focus on glyc-
erin free-pathways for producing biodiesel like renewable diesel.
4. Renewable diesel
Renewable diesel is a biodiesel fuel made of vegetable and
waste oils and animal fats through hydro-deoxygenation of the
feedstock, it is also called hydrogenated vegetable oil (HVO). The
renewable diesel represents an opportunity to utilize food industry
waste to synthesize diesel. The hydro-treated vegetable oils pro-
duction is a mature commercial technology. Factors affecting
hydro-treating process are: temperature, hydrogen/oil ratio, pres-
sure, catalyst, and space velocity [17,98,99]. The triglyceride mole-
cule is divided into three molecules by removing oxygen
throughout the reaction with hydrogen. Removing oxygen will
827
produce hydrocarbons molecules similar to diesel constituents,
as shown in Fig. 6. So, the renewable diesel can be mixed with
petro-diesel without any fears about the quality of fuel or technical
modification of the diesel engine [19,36].
Hydro-treated vegetable oils are a mixture of C15–C18 straight
chain and branched paraffins. Hydro-treated vegetable oils repre-
sent a cleaner fuel replacement for petro-diesel. Aromatics are pre-
sent in diesel in a significant ratio. Aromatics are not a favourable
option for clean combustion, hence renewable diesel is environ-
mentally friendly compared to petro-diesel. Different technologies
are available for producing renewable diesel [18,36,49]:
4.1. Green diesel process (Catalytic hydro-processing)
4.1.1. Catalytic hydro-processing of vegetable oils and fats
Green diesel can be defined as a substitute of diesel substitute
originating from renewable sources including vegetable oils and
fats. The difference between Green diesel and FAME biodiesel is
related to method of production: green biodiesel is produced via
catalytic hydro-processing of vegetable oils and fats while FAME
is produced through transesterification [100]. As commonly used
in petroleum refineries, catalytic hydro-processing is a process by
which hydrogen/carbon ratio is increased, concentration of het-
eroatom’s and metals and boiling point of refinery products are
reduced. Catalytic hydro-processing is designed to convert veg-
etable oils to high quality diesel, which can be used in existing die-
sel engines. Overall, the green diesel process contains two steps,
namely: a catalytic hydro-treatment step to produce normal paraf-
fin and a catalytic isomerization step to end up with n-and iso-
paraffin’s mixture [101].
4.1.2. Comparison between green diesel and FAME biodiesel:
The product of green diesel is composed of paraffin without
oxygen, aromatics or sulphur. The green diesel fuel has higher
heating value and cetane number in comparison to FAME biodiesel
and petro-diesel, as shown in Table 2. In addition, catalytic hydro-
processing leaves no by-products; while during transesterification,
glycerin is produced. During hydro-processing desulphurization
takes place, green diesel has low sulphur content (10 ppm wt).
Green diesel is produced commonly from rapeseed and palm oil.
However, several types of vegetable oils with a can be used to pro-
duce green diesel [102].
4.1.3. Catalysts for hydro-processing of vegetable oils and fats
Hancsok et al. [103] carried out isomerization and cracking of
pre-hydrogenated sunflower oil using a high pressure continuous
reactor. The pre-hydrogenated oil was isomerized and cracked over
0.55% Pt/HZSM-22/Al2O3 catalyst at temperature 320 °C and under
the pressure of 50–60 atm. Optimized final product contained n-
paraffin and iso-paraffin compounds, the product has an excellent
cetane number. This process for hydrocarbon-based green diesel is
a commercial process. Neste Oil company produces renewable die-
sel which is commercially known as NExBTL (Next Generation Bio-
to-Liquid) using a mixture of rapeseed oil, palm oil, and fat
[104,105].
Asikin-Mijan et al. [106] synthesized different Ni/Co catalyst
supported on multi-walled carbon nanotube (MWCNTs). They used
the prepared catalyst for the deoxygenation of Jatropha curcas oil
in a hydrogen free-environment. Three groups of catalysts are pre-
pared including: Ni/MWCNT, Co/MWCNT, and Ni-Co/MWCNT. The
highest selectivity is reported for the Ni-Co/MWCNT catalyst
towards C15-C17 hydrocarbons. The optimum composition of Ni-
Co/MWCNT was 20 wt% and 10 wt% for Ni and Co respectively.
The optimum catalyst maintained an overall oil conversion of
76% for four runs and a selectivity of green biodiesel >60%.
828 A. Amin / Ain Shams Engineering Journal 10 (2019) 821–839

Fig. 6. Hydro-treating of vegetable oil process [36].

The precious metals showed a reasonable activity towards
green biodiesel generation. Zhou and Lawal [107] developed differ-
ent catalysts for the hydro-deoxygenation of microalgae oil to pro-
duce green diesel in a micro-reactor. Three catalysts were prepared
namely: 1% Pt/Al2O3, 0.5% Rh/Al2O3 and NiMo/Al2O3. The highest
carbon yield was achieved using 1% Pt/Al2O3 at a temperature of
310 °C and a pressure of 33 atm. During the initial period of cata-
lyst operation, methane is produced then after catalyst reach sta-
bility green biodiesel (C15–C17) is produced. Increasing
residence time (optimum 1.5 s), temperature, pressure, and H2/
oil ratio (optimum 1000 ml/ml of oil) showed a positive effect
of yield.
Ni/cAl2O3 was studied extensively for producing green diesel by
deoxygenation in a hydrogen free environment. Kaewmeesri et al.
[108] employed Ni/cAl2O3 to produce green diesel from waste
chicken fats. In conclusion, Kaewmeesri et al. [108] found that a
low-cost feedstock like chicken fats can be used for producing
green diesel. Also, Jenistova et al. [109] employed 5 wt% Ni/cAl2O3
catalyst for producing green diesel from stearic acid. 99% conver-
sion of stearic acid was observed at 300 °C and a pressure of 30
bar, with a selectivity of 97%. Taromi and Kaliaguine [110] devel-
oped Ni-Mo/cAl2O3 catalyst for producing green diesel from canola
oil by hydro-deoxygenation at 31 bar and 325–400 °C. A complete
conversion of canola oil to green diesel range hydrocarbons is
achieved at 375 °C.
Different catalysts examined for green diesel process are sum-
marized in Table 5. In general, the catalysts are nickel based and
precious noble metal catalysts. Hsu et al. [111] tested Ni-Mo/
cAl2O3 catalyst for producing renewable diesel, the techno-
economical analysis showed that an expected liter price of $1.72.
However, Pt based catalysts have been used commercially [103–
105]. The optimum catalyst for the hydro-processing for a certain
feedstock/process should be selected according to bench/pilot
scale investigations.
4.1.4. Catalysts for hydro-processing of FAME biodiesel
In addition to vegetable oils and fat, catalytic hydro-processing/
upgrading is used to convert FAME into low range hydrocarbons
and fuels in a process similar to green diesel process. As a subse-
quent step after transesterification, several catalysts like Ni and
noble metals are examined to upgrade transesterification products
and to improve FAME biodiesel properties. FAME biodiesel upgrad-
ing aims to improve oxidation stability, kinematic viscosity, speci-
fic gravity, and low temperature performance [116–118]. FAME
biodiesel upgrading can be achieved using catalytic hydro-
deoxygenation step. Chen et al. [116] employed Ni supported on
zeolite for converting FAME biodiesel into diesel like alkanes
(C15–C18) at 270 °C and 10 bar for 8 h. The maximum alkane yield
achieved is 93.2% [116]. Rapeseed FAME biodiesel is converted to
alkanes through a hydro-deoxygenation process using Ni-Cu/ZrO2
at 280–350 °C and 5–20 bar [119]. Waste coking oil FAME biodiesel
is converted into C2–C4 hydrocarbons using Ni-Mo/Al2O3 catalyst
at 820 °C and 1 bar through hydro-processing followed by steam
cracking [120].

Table 5
Summary of solid catalysts used for green diesel production.

Feedstock Catalyst used Pressure (bar) Temp. (°C) Reference

Sunflower (rapeseed oil, palm oil, and fat) 0.55% Pt/HZSM-22/Al2O3 35–80 320 [103–105]
Jatropha curcas oil Ni-Co/ multi-walled carbon nanotube 0.01 350 [106]
Microalgae oil 1% Pt/Al2O3 33.4 310 [107]
Waste chicken fats Ni/cAl2O3 30 300 [108]
Stearic acid Ni/cAl2O3 30 300 [109]
Canola oil Ni-Mo/cAl2O3 31 375 [110]
Microalgae oil NiMo/c-Al2O3 34 360 [112]
Beech wood Ru/C 100 and 200 250 and 350 [113]
Fast pyrolysis oil Pd/ZrO2 200 350 [114]
Microalgae oil Ni/ZrO2 40 260 [115]
 A. Amin / Ain Shams Engineering Journal 10 (2019) 821–839
Table 6
Summary of heterogeneous catalysts experiments for FAME biodiesel hydro-processing.
Feedstock Catalyst used
FAME biodiesel Ni/zeolite
Soybean oil FAME biodiesel Ni
Rapeseed oil FAME biodiesel Ni/ZrO2
Waste cooking oil FAME biodiesel Ni-Mo/Al2O3
Mixture of rapeseed oil and fish oil FAME biodiesel Pd-Pt/Yb-USY-Al2O3
Rapeseed oil FAME biodiesel Cu-Ni/Al2O3
Soybean oil FAME biodiesel Pd/Al2O3
Partial hydrogenation process is investigated to upgrade FAME
biodiesel, Abe et al. [121] conducted several experiments to
improve the oxidation stability of a mixture of rapeseed and fish
oil FAME biodiesel using Pd-Pt/Yb-USY-Al2O3 catalyst through par-
tial hydrogenation. Moser et al. [118] studied the upgrading of soy-
bean oil FAME biodiesel to improve the cold flow properties
though partial hydrogenation using nickel catalyst suspended in
hardened vegetable oil at 170 °C and 1 bar. Several studies were
found in literature, the feedstock and process conditions are sum-
marized in Table 6. Nickel catalysts are widely used compared to
noble metals in FAME biodiesel upgrading. By comparing Tables
5 and 6, FAME biodiesel is upgraded at mild conditions in terms
of temperature and pressure compared to green diesel process.
4.2. Fischer–Tropsch process
The Fischer–Tropsch (FT) technology is aimed to produce
hydrocarbon from coal, initiated by the Germans in the1920s
[125]. Coal is converted into hydrogen and carbon monoxide then
to hydrocarbons. FT process is used widely to produce fuels and
lubricating oils from biomass and natural gas. FT process is
employed to convert syngas into higher hydrocarbon [126]. In
industry, FT process is divided into Low-Temperature Fischer–
Tropsch using cobalt catalysts or High-Temperature Fischer–Trop-
sch [126,127]. While High-Temperature Fischer–Tropsch is oper-
ated using iron based catalyst [128]. High-Temperature Fischer–
Tropsch operation employs a temperature range of 330–350 °C
producing liquid fuels [128]. Liquid fuels produced by High-
Temperature Fischer–Tropsch are distinguished with excellent
cold flow properties [127]. Sasolin in South Africa used Fischer–
Tropsch technology to produce liquid fuels from coal [128].
Current research trends focus on employing Fischer-Tropsch
from several types of biomass using slurry or fixed bed reactor
by employing cobalt or iron catalysts. Iron catalyst is cheaper
and showed better tolerance for impurities. Cobalt catalysts
showed a better conversion and stability [129]. Finnish paper
and pulp manufacturer UPM (Biofore Company) produced renew-
able diesel via the converting paper and pulp and forestry residues
by Fischer–Tropsch prorcess [130]. The produced fuel is distin-
guished with favourable characteristics to be used in regular diesel
engines [131].
Three steps are required for producing renewable diesel using
FT process including: syngas generation, catalytic syngas conver-
sion, and hydro-processing [126–133]. FT process is used to con-
vert syngas from different sources to wax and hydrocarbons
[128]. FT process has the advantage of employing various raw
materials and consistent quality of produced fuels [128,133]. Dif-
ferent biomass raw materials can be used in FT process including:
wood, coal, natural gas, paper industry, and forestry residues [133].
While, hydrocracking process has the advantage of combining cat-
alytic and hydrogenation processes in one direct step. Successive
fractionation/hydrogenation steps are used to produce high quality
renewable fuels [133].
829
Pressure (bar) Temp. (°C) Reference
10 270 [116]
1 170 [118]
5–20 280–350 [119]
1 820 [120]
5 80–120 [121,122]
6–20 180 [122,123]
30–100 27–60 [122,124]
FT diesel meets the international standards of biodiesel and
exhibits properties similar to petro-diesel [133]. FT diesel has a
heating value of 43–45 MJ/kg which is higher than fossil diesel
and other bio-diesel fuels [128,133]. FT fuel contains low sulfur
and nitrogen levels [128,129]. FT fuel is distinguished with low
aromatic content leading to cleaner combustion and excellent
auto-ignition characteristics [129,131]. Compared to petro-diesel,
implementing FT diesel has reduced NOx and particulate matter
emissions by 12% and 24% respectively [131]. FT fuels can be used
unmodified in existing diesel engines or by mixing with other fossil
fuels [129,131]. FT fuels contribute a major portion of South Afri-
ca’s demand of gasoline and diesel [128].
4.3. White diesel process
Waste cooking oil can be used to produce white diesel through
a single catalytic hydro-treatment step. This process is developed
by the Research and Technology Hellas-Greece (CERTH) [28,29].
White diesel was used initially to operate garbage in Thessaloniki,
Greece. White diesel has negligible sulphur levels of 1.54 ppm.
White diesel is a paraffinic fuel containing no aromatics [132]. Bez-
ergianni et al. [133] focuses on comparing the single step (hydro-
treatment) - vs. the two-step (hydro-treatment + isomerization)
of WCO regarding their quality and sustainability characteristics.
Initially, WCO was subjected to a first catalytic hydro-treatment
step by using a commercial NiMo hydro-treating catalyst and then
the liquid product is further processed via a second hydro-
isomerization step, using a commercial isomerization catalyst.
The product fuel properties from both approaches were excellent,
abiding by the newly established CEN TS (European Technical Stan-
dards) 15940:2012 standard for Hydro-treated Vegetable Oil
(HVO) fuels. The only consideration of the single-step product
regarding its increased cold flow properties was addressed by the
second isomerization step or by blending with fossil diesel (<10%
v/v). Due to the additional energy and hydrogen requirements of
the second isomerization step, the two-step product has reduced
sustainability compared to the one-step product as indicated by
life cycle assessment.
4.4. Hybrid biodiesel process
Hybrid process depends on co-processing of vegetable oil with
petroleum oil in petroleum refineries. Different vegetable oils have
been co-processed with petroleum streams including Jatropha,
coconut, rapeseed, palm and soybean oil [134]. Compared to pro-
cess each oil separately, several studies have reported an increase
in the overall hybrid biodiesel yield [134,135]. Sebos et al. [136]
hydro-processed desulphurized diesel mixed with 10 wt% of cot-
tonseed oil. Hydro-processing was conducted using CoMo/Al2O3
and under temperature and pressure of 305–355 °C, 30 atm. The
produced diesel has +3 cetane units copared to petro-diesel.
Huber et al. [15] conducted a hydro-processing study for heavy
vacuum oil with 5–50 wt% sunflower oil at (300–450 °C, 50 atm)
using NiMo/Al2O3. The results showed that a temperature higher
830 A. Amin / Ain Shams Engineering Journal 10 (2019) 821–839
than 350 °C is needed to achieve a remarkable conversion. Com-
mercially, hydro-processing of vegetable oil with petroleum is
known as H-Bio [137]. Šimacek et al. studied [138] hydro-
processing of petroleum vacuum distillate, at 400–420 °C and a
pressure of 180 atm, with 5 wt% of rapeseed oil using hydrogen.
The catalyst employed was a commercial Ni–Mo catalyst. Kero-
sene, gas oil and residual char are produced.
Biswas and Sharma [139] investigated the co-processing of
three components including: vacuum residue, jatropha oil and high
density polyethylene. A tubular batch reactor was employed for
conducting experimental work using a nitrogen flow rate of 120
ml/h. The reactor is a fixed bed reactor. Products included liquid
fuels, gases and char. The co-processing of the three mixed oils
showed synergism in their co-cracking reaction. The produced liq-
uid is composed mainly of diesel range hydrocarbons, though
cracked liquid of vacuum residue high density polyethylene. Liquid
produced from cracking of vacuum residue, jatropha oil and high
density polyethylene contains 22% gasoline range hydrocarbons.
The gaseous product obtained is composed of the following gases:
CH4, n-butane, iso-butane, n-pentane, 2-methyl butane and uncon-
densed components. The analysis of the solids remains showed the
existence of nickel, iron, vanadium, magnesium and potassium.
The results showed that interactive reactions take place between
the reactive molecules generated during co-processing.
5. Biodiesel kinetics
The kinetic studies available in literature for biodiesel produc-
tion are still limited compared to the experimental studies. The
kinetic models and rate equations are very specific to the particular
reaction conditions which used for developing the model.
5.1. Kinetics of transesterification process
During transesterification reaction, triglycerides are converted
to fatty acid alkyl esters and glycerol. The intermediates through-
out different reaction steps are diglycerides and monoglycerides
[41,140]. The transesterification reaction is a reversible reaction,
so an excess methanol is needed to shift the reaction towards the
formation of FAME biodiesel (Esters) [7,39,41]. Bashiri and Pour-
beiram [141] found that the transesterification mechanism that
Fig. 7. A schematic diagram for the production of FAME biodiesel throughout the transesterification process [142].
agree well with the experimental data (transesterification of Bras-
sica Carinata oil using methanol and KOH as a catalyst) is a three
steps mechanisms as follows, Eqs. (1)–(3):
TG þ CH3 OH ! DG þ ME ð1Þ
DG þ CH3 OH ! MG þ ME ð2Þ
MG þ CH3 OH ! GL þ ME ð3Þ
where TG is the triglyceride, DG is the diglyceride, MG is the mono-
glyceride, ME is the FAME biodiesel (methyl esters), and GL is the
glycerol.
Boucher et al. [142] presented a simplified approach for the
transesterification process kinetics of soybean oil using a homoge-
nous alkaline catalyst for producing the FAME biodiesel under
heating and stirring, this approach is shown in Fig. 7:
When the alkaline catalyst is added to methanol, the strong
organic base (alkoxide) is formed leading to the cleavage of the
triglyceride bond to form glycerol. However, all chemical reactions
are theoretically reversible, glycerol and methyl esters reverse
reaction is shown in Fig. 8:
Overall, six reaction steps (three forward reactions and three
reverse reactions-Eqs. (1)–(3)) are encountered in the reaction
mixture; the reaction steps are controlling the reaction rate. So
to fully describe the kinetics of transesterification, six parameters
should be fitted as shown in the model presented below as an
example (Fig. 9).
Assuming perfect mixing and no diffusion limitations, the above
model can predict optimum time of reaction. The trans-
esterification reaction is slightly exothermic, however having a
temperature controller and a heating system, the isothermal
assumption is valid. Mono-glycerides, diglycerides, triglycerides,
methyl esters, and Glycerol are denoted by MG, DG, TG, ME, and
Glycl respectively. Time and temperature are given in min. and K
respectively.
Berrios et al. [143] developed a kinetic model for the production
of FAME biodiesel from the sunflower oil transesterification using
methanol using KOH as a catalyst. Berrios et al. [143] developed
the model based on the following assumptions: (i) the reaction rate
is controlled by chemical reaction neglecting any diffusion effect;
(ii): the reaction rate without catalyst is negligible; (iii) the oil
phase is the phase at which the reaction is taking place; (iv) there
 A. Amin / Ain Shams Engineering Journal 10 (2019) 821–839 831

Fig. 8. Reverse reaction between esters and glycerol [142].

is no change in concentration of methanol during the reaction; and
(v): the forward reaction direction is a first-order reaction, while
the reverse reaction is second-order. The net rate of reaction is
the sum of the forward reaction rate and the reverse reaction rate:
d½A
¼ k1 ½A  k2 ½F ½W 
dt
where [A] = the free fatty acid concentration in mgKOH/g oil; [F] =
the concentration of fatty acid methyl ester; [W] = water concentra-
tion; k1 = forward reaction rate constant; k2 = reverse reaction rate
constant.
For a low quality feed stock such as rapeseed oil mixed with
oleic acid using methanol and H2SO4 as a catalyst, the diffusion
was found to have a dominant effect on reaction rate as indicated
by reaction rate constant change with time [144–147]. The palm
fatty acids transesterification was studied using sulfuric acid as a
homogenous catalyst. The alcohol used was either methanol or
ethanol, and the reaction was carried out in a batch reactor. Aranda
et al. [148] developed the following equation to represent the reac-
tion kinetics:
ðrA Þ ¼ kC aFFA C bALC ð5Þ
where C FFA is the free fatty acid concentration, and C ALC is the alco-
ð4Þ hol concentration.
In a newly published article, Kanda et al. [149] investigated the
non-catalytic transesterification of lauric, stearic and oleic acids
(high free fatty acid feedstock) using ethyl alcohol in a Parr reactor.
They considered the non-catalytic transesterification as an auto-
catalytic process; different studies have indicated that free fatty
acids may act as an acidic catalyst [150,151]. Kanda et al. [149]
developed a kinetic model for the non-catalytic transesterification
assuming a constant volume reactor according to the following
chemical reaction:
k1 =k2
FFA þ E þ FFA $ FAEE þ W þ FFA ð6Þ

Fig. 9. A kinetic model for the transesterification process [142].

832 A. Amin / Ain Shams Engineering Journal 10 (2019) 821–839
where FFA is the free fatty acids, and E is ethanol, FAEE is the free
acidic ethyl ester, and W is the water produced from the reaction.
Based on the previous chemical reaction, the kinetic rate equation
for the non-catalytic transesterification can be written as:
r FFA ¼ k1 C 2FFA C E  k2 C W C FAEE C FFA
The reaction rate is written as a function of concentration, since
it is easier for design and modelling purposes. The forward reaction
has a second order dependency on the free fatty acid
concentration.
Kanda et al. [149] also developed a kinetic rate equation for the
catalytic transesterification of lauric, stearic and oleic acids using
the acidic commercial catalyst montmorillonite K10 (containing
Na, Sa, Al, Mg, and Ca) and ethanol. Ethyl alcohol is assumed to
adsorb on the catalyst surface while the free fatty acid reacts from
bulk phase. The rate equation for the catalytic transesterification
can be written as follows:
qcat keff 2
cat ðk1 C FFA C E  k2 C W C FAEE C FFA Þ
r FFA ¼  Pn  ð8Þ
1þ K iCi
i
where qcat is the catalyst density,
eff
kcat
is the effective reaction rate
constant considering mass transfer limitation, and K i and C i are
the adsorption constant and concentration for the adsorbed species
respectively.
Ma et al. [152] studied the kinetics of transesterification of
waste cooking oil using FeCl3 under methanol/oil ratio of 10/1 at
90 °C. They fitted different models to the experimental data; how-
ever the best model that can fit the data is a two steps reaction
mechanism:
Step 1: Adsorption of oil
A þ S $ AS
Step 2: Reaction between adsorbed free fatty acid and methanol
AS þ M $ FAME þ S
where A is the free fatty acid, M is methanol, S is the vacant site, and
FAME is the free acidic methyl ester biodiesel. After fitting to reac-
tion data and considering the statistical analysis, the following
equation is developed to calculate the rate:
r FFA ¼ kC FFA
For a transesterification process catalyzed by a solid catalyst,
the rate equation indicates that the reaction is first order in oil con-
centration and not dependent on methanol concentration which is
attributed to the higher methanol to oil ratio employed 10/1.
The factors affecting the reaction rate and kinetics are; temper-
ature, type and concentration of catalyst, alcohol type, alcohol/oil,
presence of free fatty acids, residence time and moisture [153]. A
first order kinetics of triglyceride concentration is usually assumed
for the transesterification reaction [151,154,155]. Amin et al. [153]
developed a kinetic model for the production of FAME biodiesel
from triglycerides and low molecular weight alcohols reaction
under supercritical conditions. The supercritical conditions ensures
a homogenous reacting mixture reducing the mass transfer limita-
tions established due to immiscibility of alcohols and triglycerides
in the alkali process [156].
Amin et al. [153] built the model to study triglyceride conver-
sion to FAME biodiesel in algae using a high pressure batch reactor.
The parameters considered in the model are methanol/algae ratio,
temperature, time of reaction, assuming the following reaction
[157]:
1 mol Triglyceride þ 3 mol Methanol
! 3 mol FAME þ 1 mol Glycerol
The batch reactor design equation can be written as:
dx ðrAÞ  Vr
¼  ð13Þ
dt NA
where: Conversion is calculated as:
ð7Þ
Mass of FAME produced
x¼ ð14Þ
Mass of algae used  fraction of oil in algae
t: Time. min
Vr: Volume of reactor in m3
NA°: FAMEs number of moles used initially
rA: Reaction rate in mol/min /m3
NA
rA ¼ k  ð15Þ
Vr
where
k: Reaction rate constant in min1, according to a modified
Arrhenius equation:
9:91  103
k ¼ 2:2602 T 0:3493 expð Þ ð16Þ
R T
T: Temperature in K, NA: FAME number of moles inside the reactor
at time t, and R: universal gas constant = 8.314 J/mol/K.
Amin et al. [153] reported that the transesterification reaction
under supercritical conditions can be represented by a first order
forward reaction [158]. A clear effect of methanol and reaction
time was observed on both rate of reaction and triglycerides con-
ð9Þ version. The activation energy is fitted at 9.91 kJ/mol. Madras
et al. [159] and He et al. [154] found that the activation energy
at 2 and 56 kJ/mol respectively for a first order rate equation devel-
ð10Þ oped under supercritical transesterification. For Amin et al. [153]
model showed a good agreement with experimental data. Model
indicates that optimum reaction time and optimum methanol to
algae ratio 27 and 26 min respectively, and a complete conversion
at 600 K.
ð11Þ 5.2. Kinetics of renewable diesel production:
The reaction kinetics and pathways of free fatty acids and
triglycerides conversion to hydrocarbons are discussed in different
articles [108,134,160,161]. Feedstocks containing triglycerides free
fatty acids can be transformed into bio-diesel through catalyzed
deoxygenation reaction by breaking CAO bond either under inert
atmosphere or by using hydrogen (hydro-deoxygenation) [106].
In a fixed bed reactor, the reacting system is a three phase system:
the liquid feed dribbles down using hydrogen gas over catalyst.
C@C bonds is hydrogenated first then oxygen is removed leading
to alkanes production [162].
Fig. 10 shows the reaction pathway for Jatropha curcas oil con-
version [106]. Two reactions may prevails, decarboxylation or
decarbonylation. Throughout the decarboxylation reaction, free
fatty acids are transformed to saturated hydrocarbons including
n-pentadecanes (C15H32) and n-heptadecanes (C17H36) and to
unsaturated n-heptadecenes (mono-unsaturated and di-
unsaturated). In decarboxylation reaction, which is the favoured
reaction, oxygen is removed as carbon di-oxide (reaction b in
Fig. 10). The produced hydrocarbons from decarboxylation can be
mixed directly with diesel or even can be used as a replacement
for petro-diesel.
Reaction c in Fig. 10 represents the decarbonylation
ð12Þ
reaction. Throughout the decarbonylation reaction, the free
 A. Amin / Ain Shams Engineering Journal 10 (2019) 821–839 833

Fig. 10. Deoxygenation reaction pathway for producing diesel [106].

fatty acids are converted to the unsaturated n-pentadecanes and n- Liquid phase reactions:
heptadecenes including mono-unsaturated (C15H30, C17H34), di-
Decarboxylation : R  COOH ! R  H þ CO2 ð17Þ
unsaturated (C17H32) and poly-unsaturated (C17H28).
The produced hydrocarbons can be further subjected to a crack- 0

ing reaction to produce shorter chain hydrocarbons by breaking Decarbonylation : R  COOH ! R  H þ CO þ H2 O ð18Þ
CAC bond (as indicated by reaction d). Reaction e shows that the
cracking process can be conducted directly using the raw free fatty
Hydrogenation : R  COOH þ H2 ! R  H þ CO þ H2 O ð19Þ
acids to produce shorter chain hydrocarbons C8–C10. Products of
reactions d and e represent a bio- replacement for conventional
Hydrogenation : R  COOH þ 3H2 ! R  CH3 þ 2H2 O ð20Þ
jet fuel. Gas phase reactions:
The reaction detailed mechanism is discussed by Lestari et al.
[163]. Lestari et al. [163] developed a reaction mechanism for the
Water gas shift reaction : CO þ H2 O ! H2 þ CO2 ð21Þ
inert deoxygenation of saturated fatty acids in the presence of a
Methanation : CO2 þ 4H2 ! CH4 þ 2H2 O ð22Þ
metallic catalyst. As reported by Asikin-Mijan [106], Lestari et al.
[163] proposed a reaction mechanism that indicate several reac-
Methanation : CO þ 3H2 ! CH4 þ H2 O ð23Þ
tion pathways. Hydrogen is generated during the reaction by dehy-
drogenation of free fatty acids forming unsaturated compounds or Jenistova et al. [109] studied the kinetics of green diesel produc-
through the water-gas shift reaction [161]. The reaction mecha- tion over 5 wt% Ni/cAl2O3 catalyst, the feedstock was stearic acid.
nism takes place in the liquid and gas phases. In the liquid phase, The catalyst performance was studied by varying reacting mixture,
four steps may occur simultaneously: decarboxylation (reaction temperature, and hydrogen pressure. 99% conversion of stearic
(17)), decarbonylation (reaction (18)), and hydrogenation (reac- acid was observed at 300 °C and a pressure of 30 bar, with a selec-
tions (19) and (20)). Decarboxylation and hydrogenation are the tivity of 97%. The main product was heptadecane, C17. Similar
source of alkanes, while decarbonylation produces alkenes. Carbon results were observed when oil fatty acids were used instead of
monoxide, carbon dioxide, and water produced from Reactions stearic acid.
(17)–(20) undergo water-gas shift and methanation reactions in Using the described experimental data, Jenistova et al. [109]
the gas phase producing hydrogen and methane as shown by reac- developed a kinetic model for the hydro-treatment of steric
tions (21)–(23). acid/ oil fatty acids to produce green diesel. Since the selectivity
834 A. Amin / Ain Shams Engineering Journal 10 (2019) 821–839

Table 7 6. Industrial case studies

The model fitted parameters 5 wt% Ni/cAl2O3 at 300 °C [109]

Parameter Unit Value Industrial applications of biodiesel production are increasing

k1 1
min bar 1 3
1.56 * 10 rapidly throughout the world. Different countries are shifting con-
k2 min1 bar1 7.83 * 104 ventional power stations to renewable energy based stations [166].
KA L/mol 1.36 * 102 Throughout this section, industrial units for producing biodiesel
KH bar1 1.58 * 102 from vegetable oils and fats are discussed briefly:

6.1. Neste Renewable (NEXBTL) [36,167,168]

is high enough, we can neglect any side products. The reaction is

Raw Material:
completed over two consecutive steps: (1) formation of stearyl
A mixture of waste fat, rapeseed oil, and palm oil
alcohol, and (2) formation of octadecane. The two reaction steps
Annual production volume:
can be expressed mathematically using two rate equations assum-
4 units are in service (1.2 million tons/year)
ing non-competitive adsorption of hydrogen and stearic acid (SA).
Plant location:
The proposed two rate equations are:
Finland, Singapore, and
Netherland
k1 C SA PH2 Start year:
r1 ¼   ð24Þ
ð1 þ K S C s Þ 1 þ K H P H 2 2011
Products:
Renewable diesel (1 ton/ 1.21 ton of feed/ 1.18 after bleaching),
k2 C O PH2 in addition to light gases and naphtha
r2 ¼   ð25Þ
ð1 þ K S C SA Þ 1 þ K H PH2
Process details, Fig. 11:
where C O is the concentration of octadecane in mol/l, C SA is the con-
centration of stearyl alcohol in mol/l, and P H2 is the hydrogen partial – The feedstock is stored, and bleached before hydro-treatment to
pressure in bar. remove impurities.
The two rate equations were fitted to the experimental data, – The bleached feedstock is hydro-treated with hydrogen to pro-
and the kinetic model showed excellent fir and representation duce renewable diesel.
for the experimental data. The fitting parameters values are listed – The renewable diesel is isomerized to improve the cold proper-
below in Table 7 at 300 °C. ties by catalytic treatment under hydrogen atmosphere.
Different studies have indicated that deoxygenation of veg- – Finally, the produced mixture is separated to diesel, naphtha,
etable oils under inert atmosphere in the presence of a metallic and light gas.
catalyst (palladium, ceria-zirconia) follows a first order rate law.
The reaction rate is a function of triglyceride/free fatty acid concen- The overall material balance of the process can be expressed as:
tration. The reaction rate constant follows Arrhenius type equation 1:18 kg C 57 H102 O6 þ 0:035 kg H2
which indicates that adsorption isotherm does not have an effect
! 1 kg P þ 0:05 kg CO2 þ 0:1 kg H2 O þ 0:06 kg C 3 H8
on the reaction rate [161,164,165].

Fig. 11. NEXBTL process.

 A. Amin / Ain Shams Engineering Journal 10 (2019) 821–839 835

Fig. 12. Ecofining process flow diagram.

Hydro-deoxygenation as an alternative approach for FAME bio-
diesel production is an interesting route to convert vegetable oils
into hydrocarbons (mainly C15–C18) a temperature range 300–
400 °C, and more energy. Hydrocracking yields fuels with
increased oxidation stability, better properties and composition
similar to petro-diesel, and higher cetane numbers.
6.2. Honeywell UOP green diesel unit (Ecofining process) [167]
This unit employs a batch process to convert waste oil and fats
into FAME biodiesel throughout the transesterification reaction.
Fats and oils are converted to FAME biodiesel and glycerol, almost
92% of feed is converted. Remaining amount (8%) is burned to pro-
vide some of the power requirements. The process design provides
some advantages due to low energy utilization, flexibility in feed-
stock consumption, reduced capital cost, and faster reaction by
employing accelerated transesterification.

Raw Material: 6.4. AGROPODNIK unit, akciová společnost [163]

Flexible (any combination of fats, greases, and oils)
Annual production volume: Raw Material:
UOP is a technology vendor not a producer, different annual Rapeseed oil, fresh rapeseed is harvested and transported to the
volumes according to needs, as shown in Fig. 12. unit. The oil is extracted using onsite mill to cover 50% of oil
Location: needed annually; the remaining needed oil is purchased from
Alabama, USA the market.
Products: Annual production volume:
Renewable diesel, jet fuel, and light gases 50,000 ton of biodiesel/year
Start year:
Process details: 1994 and expanded at 2001
Location, Fig. 14:
– The feedstock is hydro-treated with hydrogen to produce Jihlava, Czech Republic
renewable diesel. Products:
– The produced mixture is refined by separating acid gas and FAME biodiesel, and glycerol
water Process details:
– The renewable diesel is isomerized to improve the cold proper-
ties by catalytic treatment under hydrogen atmosphere.
– Finally the produced mixture is separated into diesel, jet fuel,
and light gas.

6.3. Biodiesel Kärnten GmbH [167,169]

Raw Material:
Waste oil and fats from different industries (around 20% animal
fats)
Annual production volume:
50,000 ton of biodiesel/year
Start year:
2003
Location, Fig. 13:
Arnoldstein, Austria

Products:

FAME biodiesel, and glycerol

Process details: Fig. 13. Biodiesel Kärnten GmbH unit.
836 A. Amin / Ain Shams Engineering Journal 10 (2019) 821–839
Fig. 14. Rapeseed storage and mill.
The process is batch process to convert rapeseed fresh oil into
FAME biodiesel throughout the transesterification reaction. Rape-
seed oil is converted to FAME biodiesel and glycerol, the yield is
around 98%. A high yield levels and quality level are assured by
the flexible and reliable process control. The final biodiesel product
is washed, dried and filtered for further upgrading. 80% concentra-
tion stream of glycerine is produced which can be sold at a reason-
able price.
7. Conclusions
Biodiesel can be produced commercially by transesterification
(FAME), or by hydro-deoxygenation (renewable) of fats, vegetable
oils, and waste cooking oil. The FAME biodiesel can be produced by
one of the following methods: mechanical stirring, ultra-
sonication, and supercritical alcohol. Renewable diesel can be pro-
duced using one of the following processes: green diesel process,
Fischer–Tropsch biodiesel process, White diesel process, and
hybrid biodiesel process. Catalyst plays an important role in
increasing yield and conversion; in addition to saving energy
required to run the reaction at higher temperature without a cata-
lyst. Liquid catalyst like acids and alkalis are widely used for pro-
ducing FAME biodiesel. Transition metal and noble metal based
solid catalysts are used for producing renewable fuels. The kinetic
studies indicated that the transesterification process and the green
diesel process follow a reaction rate that is mostly first order in
terms of the feedstock concentration with dependency on the
adsorption isotherm in case of solid catalysts. Commercial units
are in service around the world producing huge amount of biodie-
sel annually, which shows that biodiesel is a mature technology for
industrial applications especially for countries where biomass is
available in huge quantities.
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Ashraf Mukhtar Lotfi Amin Currently, Dr. Amin is an

associate professor at the Chemical Engineering
Department, NRC Egypt. He received B.Sc. in Chemical
Engineering from El-Minia University (1999). Dr. Amin
received his master degree from Cairo University (2004),
Chemical Engineering Department. He got his PhD from
the University of Waterloo, Chemical Engineering
Department (2011). He continued his research after PhD
at the University of Waterloo. Dr. Amin gained a great
deal of experience in different aspects of chemical
engineering: Mathematical modeling, conversion, reac-
tion engineering, catalysis, and renewable energy.