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Applied Energy 264 (2020) 114753

Contents lists available at ScienceDirect

Applied Energy
journal homepage: www.elsevier.com/locate/apenergy

Production of biodiesel under supercritical conditions: State of the art and T


bibliometric analysis
Pedro Andreo-Martíneza,b, , Víctor Manuel Ortiz-Martínezc, , Nuria García-Martínezb,
⁎ ⁎

Antonia Pérez de los Ríosa, Francisco José Hernández-Fernándeza, Joaquín Quesada-Medinaa,


a
Department of Chemical Engineering, Faculty of Chemistry, University of Murcia, Campus of Espinardo, 30100 Murcia, Spain
b
Department of Agricultural Chemistry, Faculty of Chemistry, University of Murcia, Campus of Espinardo, 30100 Murcia, Spain
c
Department of Chemical and Environmental Engineering, Technical University of Cartagena, Campus Muralla del Mar, E-30202 Cartagena, Spain

HIGHLIGHTS GRAPHICAL ABSTRACT

• Bibliometric study on biodiesel pro-


duction research under supercritical
condition.
• Science Citation Index Expanded da-
tabase, from 2001 to 2019, was used.
• Growing research field with 608 arti-
cles and significant annual output in-
crease.
• China country, Sila Science institution
and Fuel journal ranked first in the
field.
• Transition from first- to third-genera-
tion biodiesel and reaction optimiza-
tion trends.

ARTICLE INFO ABSTRACT

Keywords: The demand for biodiesel as an alternative and potentially renewable fuel is constantly rising. Biodiesel pro-
Bibliometric analysis duction from lipids in supercritical conditions offers several advantages over other catalytic processes. These
Biodiesel advantages include high-efficiency production, environmental friendliness and the possibility of using a broad
Scientometric range of feedstock sources. As a consequence, there is a great interest in biodiesel production research using
Supercritical alcoholysis
supercritical fluids as a sustainable technology option. In this sense, bibliometric reviews can be very useful for
Web of Science©
the interpretation of scientific production and research trends in this field. Thus, this work presents a sciento-
Research trends
metric study on biodiesel production research under supercritical conditions from 2001 to 2019, based on the
Web of Science© database. 608 articles were analyzed and the parameters considered were: (i) publication type,
language and output characteristics, (ii) Lotka's Law, Price's index and h-index, (iii) authors, countries and
institutions collaboration analysis, (iv) publication performance by authors, journals, institutions and countries
and (v) author keywords, single title words and keywords Plus analysis. The productivity patterns of authors,
journals, institutions and authors keywords were found to fit Lotka's law. In terms of feedstock used in super-
critical conditions, the bibliometric analysis showed a clear transition from first- to third-generation biodiesel,
with special attention paid to the experimental study of supercritical reaction conditions. By contrast, further


Corresponding authors.
E-mail addresses: pam11@um.es (P. Andreo-Martínez), victor.ortiz@upct.es (V.M. Ortiz-Martínez), quesamed@um.es (J. Quesada-Medina).

https://doi.org/10.1016/j.apenergy.2020.114753
Received 24 October 2019; Received in revised form 21 February 2020; Accepted 26 February 2020
Available online 06 March 2020
0306-2619/ © 2020 Elsevier Ltd. All rights reserved.
P. Andreo-Martínez, et al. Applied Energy 264 (2020) 114753

process optimization, the reduction of the severity of the supercritical conditions through devised strategies to
lower energy consumption and further economic analysis are still needed, among other factors, for the real
implementation of the technology.

1. Introduction yields in shorter reaction times. Furthermore, it can be applied to a


wide variety of feedstock (even those with a high content of FFAs and
According to the American standard ASTM D6751, biodiesel is de- water) without any pretreatment requirement, using a wide range of
fined as “a fuel comprised of monoalkyl esters of long-chain fatty acids solvents. In addition, the separation and purification stages are rela-
derived from vegetable oils or animal fats, designated B100”. Biodiesel is tively easy to carry out [13–15]. Despite these advantages, supercritical
obtained through esterification and/or transesterification processes and biodiesel production poses several drawbacks including the need for
it is used as a total or partial substitute for fossil diesel. Chemically high oil-to-alcohol molar ratios and high temperature and pressure
speaking, biodiesel is a mixture of fatty acid methyl esters (FAMEs) conditions [12], which translates into high capital costs and energy
with chain lengths of C14:0-C24:3 [1,2]. Nowadays, biodiesel is a consumption due to the elevated pressures and temperatures. These
promising renewable source of energy as it is a clean-burning and re- high temperatures can also lead to the degradation of polyunsaturated
newable fuel, biodegradable, environmentally friendly [3] and poten- fatty acids and/or glycerol. Nevertheless, these drawbacks represent
tially neutral in relation to global warming since biodiesel can reduce interesting research challenges for the scientific community.
net CO2 emissions by 78% in comparison to fossil diesel [4]. The production of biodiesel under supercritical conditions is a re-
There is a wide range of oleaginous feedstocks suitable for biodiesel latively new method, as the first article within the field was published
production, including raw and organic waste materials. Selection of by Saka and Kusdiana in 2001 [16,17], although their preliminary re-
feedstock is the primary factor as it accounts for 75–80% of total pro- sults had been reported two years earlier at the 4th Biomass Conference
duction costs. In this sense, the use of non-edible vegetable oils, cooking of the Americas on Growth Opportunity in Green Energy and Value-
oil waste or waste-based feedstocks are favorable options. By contrast, Added Products [18]. However, biodiesel is not a new concept. The
the utilization of raw edible oils can lead to an increase in food market term was actually coined in 1937 by the Belgian scientist G. Chavanne
prices and can pose higher environmental impacts [5]. Depending on through his patent entitled “Procedure for the transformation of vege-
the type of feedstocks used in its production, biodiesel can generally be table oils for their uses as fuels” [19]. Previously, the transesterification
categorized into first, second and third generations [6,7]. First-gen- of vegetable oils was developed by Duffy [20], and Rudolf Diesel de-
eration biodiesel is obtained from food crops such as soy, wheat, ra- veloped an engine that ran on 100% peanut oil at the 1900 Paris World
peseed or corn. Second-generation biodiesel involves the use of non- Exhibition, which had been successfully tested seven years before in
edible vegetable oils, used cooking and frying oils, and animal fats. That Germany. Subsequently, the Chavanne's patent was applied on an in-
being the case, second-generation biodiesel avoids competition with dustrial level in Brazil by Expedito Parente and various standards on the
crops for food purposes, land clearing and water supply. Third-gen- quality of biodiesel such as the DIN51606 (German), ASTM D6751
eration biodiesel, derived from microalgae or macroalgae and meta- (American) and EN 14214 (European) were developed [4,21]. Despite
bolic engineering of photosynthetic organisms, respectively, has these facts, according to the bibliometric review on biodiesel research
emerged as one of the most sustainable alternatives. In comparison to published by Zhang, Gao [22], it was not until 1991 that the first
conventional crops, such types of feedstocks offer high growth rates and publication related to biodiesel was indexed by the Science Citation
high photosynthetic efficiency for biomass production. Index Expanded (SCI-E). From 1991 to 2015, a total of 18,204 pub-
The transesterification of triglycerides (TG) from oleaginous feed- lications on biodiesel research have been indexed.
stocks involves the reaction of TG with short-chain alcohols, such as Bibliometric reviews are common nowadays and, although the first
methanol or ethanol, to obtain FAMEs and low amounts of other by- bibliometric review was conducted by Cole and Eales [23], the term
products such as glycerol and intermediate products (mono- and di- bibliometric was coined by Pritchard [24] and it is defined as the
glycerides), which greatly influence final biodiesel quality [8]. To date, analysis of scientific publications using statistical methods in order to
several methods for the transesterification of oleaginous feedstocks into provide a general outline and overall structure of the research area.
biodiesel have been successfully proposed, including both homo- Early bibliometric reviews were carried out on very small scales and
geneous and heterogeneous catalysis (using acid or alkali catalysts), mostly restricted to disciplines within the natural sciences. The official
ultrasound- and microwave-assisted processes, enzymatic technology appearance of SCI in 1963 [25], which systematically compiles com-
and supercritical conditions [9,10]. In general, catalytic techniques are prehensive citation information regarding publications in science
time-consuming, generate large amounts of wastewater and soaps, and journals, allowed the rapid development of bibliometric reviews,
are highly sensitive to the presence of free fatty acids (FFAs) and/or proving that citation-based literature research is useful and effective
water (more than 0.5 and 0.06 wt%, respectively) together with the fact [26]. In this sense, the bibliometric review has become a widely used
that they require downstream separation, neutralization and purifica- tool for statistical and quantitative literature citation and for the in-
tion steps, which are highly costly [11]. Despite these limitations, the terpretation of scientific production and research trends in specific
alkali technology is widely used on an industrial scale [12]. Microwave- fields. Clear proof of this fact is the large number of bibliometric re-
and ultrasound-assisted methods include high energy consumption and views published in many disciplines of science and engineering such as
all the aforementioned limitations for catalytic transesterification, al- constructed wetlands [27], ecological restoration [28], shale gas [29],
though higher FAME yields can be achieved in shorter reaction times nuclear power [30], biomass [31] and biofuels [32]. In fact, several
and they present a more environmentally friendly approach. In com- bibliometric reviews of general biodiesel research trends [22] and mi-
parison, the supercritical transesterification method can overcome the croalga-derived biodiesel production [33] have been published re-
drawbacks of conventional catalytic approaches. In this case, high cently.
temperature and pressure conditions are used. Although catalysts are That being said, and to the best of the author's knowledge, no bib-
generally avoided in supercritical biodiesel production, heterogeneous liometric reviews of biodiesel production research under supercritical
catalysts can also be employed to increase conversion rates, which are conditions have been published yet. The aim of this work is to to
easier to handle than homogenous catalysts in terms of separation steps. evaluate the field of supercritical biodiesel production from 2001 to
In addition, biodiesel production under supercritical conditions offers 2019, based on the Web of Science© (WoS) database, through a com-
unique advantages, including the possibility of obtaining higher FAME prehensive bibliometric review. For this purpose, publication language

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and output characteristics, Lotka's law, Price's index, h-index, colla- ratio. In addition, thermal decomposition reactions of FAMEs may
boration analysis and publication performance by authors, journals, occur due to the high temperatures used (usually higher than 300 °C),
countries and institutions were analyzed to dissect publication patterns. thus resulting in low yields of biodiesel [35,49].
Finally, author keywords, single title words, and WoS keywords were The optimum temperature and reaction time to reach maximum
analyzed to explore the research trends and to identify hot topics in the yields of biodiesel are in the range of 290–400 °C and 5–75 min, re-
field. spectively, depending on the type of reactor and the oil used [12,48].
The pressure reached under supercritical conditions to produce
2. State of the art of biodiesel production under supercritical biodiesel depends on the type of feedstock, the reaction temperature,
conditions technology the type of reactor (batch-type or flow-type) and the agitation speed of
the medium [48]. Generally, pressure is not a specific control variable
Biodiesel production under supercritical conditions technology is a because it is a consequence of the mixture conditions for a given tem-
potential and exciting alternative to classical biodiesel production perature. Further, it is generally observed that when pressure is high
technologies, such as catalytic transesterification, as it allows for si- enough to maintain the reaction in a homogenous state and the reaction
multaneous TG transesterification and FFA esterification, it does not time is suitable to reach equilibrium conversion, the effect of pressure
require a catalyst, and has a high reaction rate and a higher FAMEs does not provide significant improvement on FAMEs yield. In this sense,
yield with fewer operational steps. Furthermore, it is applicable to a although it is widely known that the reaction pressure positively affects
wide variety of feedstock, is more tolerant to the presence of FFA and the yield of FAMEs, it has been reported that the influence of pressure
water, and is well-disposed to continuous operations [12]. yield becomes smaller between 15.5 and 25 MPa, and negligible above
The classic transesterification reaction of TGs to produce FAMEs and 25 MPa [47,50].
glycerol, in the presence of methanol, occurs in three consecutive and In regards to the solvent-to-oil molar ratio, there is a clear consensus
reversible stages. During this process, a total of 3 mol of methyl ester that the optimal solvent-to-oil molar ratio ranges from 40:1 to 45:1,
are produced (1 mol in each stage) and the final product is a mixture of regardless of the type of oil or fat used [1,12].
mono-, di- and TGs, glycerol, thermal degradation products and FAMEs Thermal decomposition of FAMEs is a very frequent phenomenon in
[34]. The glycerol causes problems in classical catalytic transester- biodiesel production under supercritical conditions. This phenomenon
ification as further steps are necessary in order to separate glycerol and is observed only at reaction temperatures equal to or higher than 300 °C
FAMEs. However, under supercritical conditions, glycerol thermally and leads to a decrease in biodiesel yield. Besides, it is known that only
decomposes and reacts with methanol through etherification reactions polyunsaturated FAMEs undergo thermal decomposition at 300 °C,
at temperatures and pressures above 270 °C and 10 MPa, respectively, while monounsaturated FAMEs are relatively stable at this temperature
and reaction times longer than 45 min and forms methyl glycerol [51]. In this sense, the fatty acid composition of the fat or oil used to
ethers, diglycerols and alcohols, which are miscible in biodiesel. These produce biodiesel under supercritical condition is important to take
low-molecular weight compounds presence can improve the cold flow into account as it has been also reported that tri-unsaturated fatty acid
properties and the viscosity of the biodiesel produced [35,36]. In ad- TGs react at a lower reaction rate than those of di-unsaturated fatty
dition, the use of other organic solvents without glycerol production, acids, which in turn also react at a lower reaction rate than those of
including methyl acetate, have also been proposed. This solvent pro- monounsaturated ones [1,52]. Further, the main thermal decomposi-
duces triacetin instead of glycerol as a by-product, which is also soluble tion reactions that can occur during the supercritical methanol trans-
with FAME [37,38]. esterification are isomerization (275–400 °C), hydrogenation
Besides methanol and methyl acetate, other organic solvents such as (> 325 °C), pyrolysis (> 350 °C) and polymerization (Diels–Alder re-
ethanol [39–41], methyl tertbutyl ether [42,43] and dimethyl carbo- action) (300–425 °C) of the FAMEs generated, which were all stable
nate [44,45] have been successfully used to produce biodiesel under below 275 °C [48,53].
supercritical conditions. Some of them have advantages over methanol. On the other hand, in order balance the severity of supercritical
For example, ethanol is renewable in nature, less toxic, shows fewer conditions, several strategies such as the use of heterogeneous catalyst
safety risks than methanol, and works as both a reactant and an acid or co-solvents have been proposed. The addition of a co-solvent can
catalyst under supercritical conditions [46]. However, the most widely increase the mutual solubility between TGs and organic solvent, al-
used organic solvent is methanol due, mainly, to the fact that it pro- lowing biodiesel to be produced under milder conditions. Some of the
vides a higher reaction rate and biodiesel production yield under the co-solvents that have been tested include non-polar compressed gases
same reaction conditions [43], because it is less bulky with decreased such as propane [54], carbon dioxide [54,55], ethane, n-butane, n-
steric hindrance [42,43], and its cost remains significantly lower than hexane [46,56], chloroform [56], n-heptane [54], tetrahydrofuran
other organic solvents [47]. [57], diethyl ether [56] and/or ionic liquids [58]. The use of catalysts
The critical temperatures and pressures of methanol, ethanol, me- also improves biodiesel production under supercritical conditions [9]
thyl tertbutyl ether, methyl acetate and dimethyl carbonate are because it increases the transesterification reaction rate and softens
239.2 °C and 8.09 MPa [15], 241.6 °C and 6.27 MPa [39], 224 °C and supercritical requirements. Some of the catalysts that have been tested
3.49 MPa [42], 233.7 °C and 4.7 MPa [37], and 275 °C and 4.63 MPa include SO4–ZrO2 [59], weak acids [60], micro-NaOH [61], liquid or-
[44], respectively. Crossing those critical conditions, extreme changes ganic amine [62], zeolite [63], Cs-doped heteropolyacid [64], nano-
in the mass density of solvent occur, leading to changes in its solubility MgO [65] or NaOH [66]. As can be observed, the use of homogeneous
and mass-transfer characteristics. Under supercritical conditions, TGs catalysts (trace amounts) was also studied due to the fact that only a
and solvents become a single phase due to an increase in the density of few heterogeneous catalysts, such as zinc aluminate and zirconia sup-
solvent and a decrease in its dielectric constant. The increase in density ported metal oxide catalysts, are stable under these conditions [12].
leads to a diminishing polarity in solvent because hydrogen bonding in Finally, the supercritical technology to produce biodiesel has been
the molecules is weakened and they can then act as free monomers. successfully tested for a wide range of feedstocks, ranging from first- to
Thus, non-polar TG is better dissolved in solvent under supercritical third-biodiesel generation. The first biodiesel generation feedstocks
conditions to form a homogeneous phase [12]. In other words, under include soybean oil [67,68], sunflower oil [69–71], groundnut oil [52],
supercritical conditions, a single homogeneous phase is generated in Camelina sativa oil [46,71], Brassica napus oil [72,73], cottonseed oil
the reactor, so interface mass transfer limitations are avoided and the [71], linseed oil [74], coconut oil [54,75], rice bran oil [69] or palm oil
reaction can be carried out at a high reaction rate [48]. [59,75]. The second biodiesel generation feedstocks include Ricinus
The main parameters influencing the supercritical transesterifica- communis oil [76,77], Jatropha curcas oil [61,78], Pongamia pinnata oil
tion are temperature, reaction time, pressure, and solvent-to-oil molar [51,52], Simmondsia chinensis oil [79], Nicotiana tabacum oil [35],

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Calophyllum inophyllum oil [5,80], Cerbera odollam oil [81], Raphanus institutions having at least h citations each and the other Np-h authors,
sativus oil [82], Ceiba pentandra oil [83], neem and mahua oil [42], journals, countries and institutions having ≤h citations each) using the
animal fats [84,85], waste frying oil or used vegetable oil [63,86] or Web of Science© records, and (viii) biodiesel production research
leather tanning waste [87]. The third-generation biodiesel feedstocks under supercritical condition trends obtained by author keywords,
include microalgae oil [88–90]. Most of the aforementioned feedstocks single title words, and WoS keyword analysis.
contain a high amount of free fatty acids (> 0.5 wt%) and/or water
(> 0.06 wt%), which reduces the FAME yield and leads to the forma- 3.1.1. Limitations
tion of soaps which complicates the separation of glycerol and FAMEs The present comprehensive bibliometric review has associated
when using conventional catalytic processes for biodiesel production. limitations as other bibliometric studies. These limitations are a result
However, a high amount of free fatty acids and water have positive of by the database used, the Boolean strings chosen, the manual stan-
effects when biodiesel is produced under supercritical conditions. The dardization of author's names, institutions and keywords, the selection
FFAs are directly converted into FAMEs, leading to an increase in the of only “articles” as type of publication to perform the analysis, and the
transesterification yield, and moderate water contents can favor the bibliometric parameters used to analyze the publications selected,
transesterification process through hydrolysis and esterification reac- among others. For example, the choice of the database to perform a
tions. Furthermore, the presence of water in the process can allow a bibliometric analysis can pose a bias risk. The search for publications on
lower solvent-to-oil molar ratio to be used, which also would reduce the biodiesel production under supercritical conditions was carried out
cost of purification processes (ie. removal of solvent) [47]. only in the WoS database, which excludes non-SCI journals; therefore,
the articles published in journals not indexed in the WoS database and
3. Bibliometric analysis their citations may have been excluded. The Boolean strings chosen for
a specific research topic can also pose a risk of bias. In this sense,
3.1. Research methodology and data statistics predefined keywords are more limiting than freely chosen keywords as
they vary from person to person. Inconsistencies may exist between the
The Science Citation Index Expanded (SCI-E), Web of Science© keywords selected by the authors of the article, the content of the ar-
(https://webofknowledge.com/) was used to obtain the scientific ticle and the Boolean strings chosen to perform a bibliometric review.
output information for the present bibliographic review. The temporary
search period was from inception to February 10th, 2020. The Boolean 3.2. Results and discussion
strings chosen were: theme: (“biodiesel” OR “bio-diesel” OR “bio
diesel”) AND theme: (“Supercritical transesterification” OR 3.2.1. Publication patterns
“Supercritical condition*” OR “Supercritical methanol” OR 3.2.1.1. Type of document and language of publications. A total of 793
“Supercritical ethanol” OR “Supercritical alcoholysis”) in all databases. documents related to biodiesel production under supercritical
The publication characteristics were analyzed using Microsoft Excel conditions met the selection criteria established for the present
(v. 2019). BibExcel [91] was used to perform the frequency analysis bibliometric review; however, 780 records from the Main Collection
and network diagrams for cooperation analysis were generated using of the WoS were selected for further analysis since the database offers
Pajek 1.0.0.1 [92], and VOSviewer [93] software's. broader download options for bibliometric parameters. The remaining
Journal Citation Reports (JCR) Science Edition 2018 was used to records were: 5 from Korean Journal Database, 4 from Derwent
obtain the journal impact factor (IF). The 2018 Journal Citation Reports Innovations Index, 3 from Russian Science Citation Index and 1 from
(JCR) provides statistical citation data, indexing 11,877 journals across Medline. In addition, no duplicate publications were found.
236 scientific disciplines and 81 countries [94]. The number of documents found in the present bibliometric review
Country and institution productions were evaluated by the affilia- was lower than that reported in other bibliometric reviews [27,33,95].
tion address [first (FP) or corresponding author (RP)] of at least one This can be explained by the fact that the production of biodiesel under
author of the published article. The names of authors (i.e. Ríos, APD by supercritical conditions is a relatively new research field; as commented
de los Ríos, AP; Akgun, NA by Akgun, N; or Hossain, AABMS by above, the first article in the field was published in 2001 by Saka and
Hossain, ABMS, checked with e-mail and affiliation), institutions (i.e. Kusdiana [16]. In addition, the selected research focus within this field
the Indian Institutes of Technology from different locations, i.e. is more limited in comparison to other bibliometric reviews. Just as a
Varanasi or Guwahati, by Indian Institute of Technology, National note, it is not surprising that biodiesel production under supercritical
Tsing Hua University by National Tsinghua University, Widya Mandala conditions appeared for the first time in Japan, since this country was
Surabaya Cathol Univ by Widya Mandala Surabaya Catholic Univ, or first place for new patent applications on supercritical fluids during the
Sila Science by all the institutions of Trabzon in Turkey), author key- seven years between 1998 and 2005 [96]. In addition, the Price's index
words (i.e. trans-esterification and (Trans)esterification by transester- value (48.8%) can corroborate the newness of this research field since
ification, FFA by Free Fatty Acid or plural by singular), single title this index approaches 50% in disciplines in which current literature is
words (i.e. plural by singular or lowercase by capital letters) and WoS more abundant. On the contrary, when the historical literature grows,
keywords (i.e. also plural by singular and lowercase by capital letters or the Price's index decreases below this value [97]. The Price's index is an
Bio-diesel by Biodiesel) were conscientiously standardized. indicator of obsolescence defined as the percentage of references that
The bibliometric parameters used to analyze the publications re- are less than 5 years old and it is calculated considering the percentage
lated to biodiesel production research under supercritical conditions of citations that are less than 5 years old and older than 5 years old,
over the past 19 years were: (i) type and language of the documents, (ii) respectively. This index also suggests that science production develops
publication characteristics (total publications, number of authors, at a faster pace than other human activities, duplicating in size every
average number of authors per article, number of references cited, 10–15 years. However, the time of duplication is not the same in all
number of references per article, number of pages per article, and scientific fields as some disciplines grow faster than others [98].
average number of pages per article), (iii) authors performance, (iv) The 780 documents related to biodiesel production under super-
journal publication patterns (number of publications, JCR impact factor critical conditions included 9 document types. Research articles (608;
-IF, JCR journal subject category, and journal position by JCR cate- 77.9%) were the dominant type followed by review articles (71; 9.1%),
gories), (v) WoS categories; publication patterns for countries and in- proceeding papers (36; 4.6%), article and proceeding papers (33;
stitutions; collaboration and co-citation analysis, (vi) founding analysis, 4.2%), article and book chapters (20; 2.6%), meeting abstracts (9;
(vii) Lotka's law, Price's index, h-index of authors, journals, countries 1.1%), review and book chapters (1; 0.1%), corrections (1; 0.1%), and
and institutions (defined as the h of Np authors, journals, countries and letters (1; 0.1%). In addition, there were about 8.5 research articles per

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review and 16.9 research articles per proceeding papers. Since the re- intervals, respectively, describing the correlations between the
search articles were the predominant publication type on biodiesel number of accumulated articles per year for the two intervals
production under supercritical conditions, 608 articles published until considered. The number of articles showed a high correlation with
2019 were used for further analysis in the present bibliometric study. the year of publication for the models mentioned (R2 = 0.9497 for the
The 608 articles were published in 8 different languages, of which 2001–2006 interval and R2 = 0.9992 for the 2007–2019 interval). The
600 (98.7%) were in English, 2 (0.3%) in Portuguese, 1 (0.2%) in fitted linear and two-order polynomial models are Y = 4.7714·X – 4.2,
Russian, 1 (0.2%) in Serbo-Croatian, 1 (0.2%) in Turkish, 1 (0.2%) in and Y = 0.2707·X2 + 40.17·X – 242.37, respectively (the number of
Spanish, 1 (0.2%) in Chinese, and 1 (0.2%) in Polish. The fact that years since 2001 is X and the number of articles accumulated per year is
English is the universal scientific language can be due, in part, to eco- Y).
nomic factors and historical and political reasons which favored English The linear model displayed in Fig. 1B shows a low increase in ar-
over other languages such as Russian, French or German [99]. ticles published in the first interval (2001–2006). However, using the
two-order polynomial model corresponding to the second interval
3.2.1.2. Output characteristics of the publications and author (2007–2019), an increase in the number of accumulative articles re-
performance. No additional search to dissect publication patterns was lated to biodiesel production under supercritical conditions can be
needed since there are no publications on biodiesel production under predicted for 2024, with an estimated number of 878 articles, which
supercritical conditions dating before 1999 [18]. As can be observed in accounts for almost than one and half times the articles published in
Fig. 1A, the total annual number of publications related to biodiesel 2019 (608). The authors of the present bibliometric study have suc-
production under supercritical conditions increased from 1 in 1999 to cessfully checked the effectiveness of the extrapolation method to es-
70 and 41 in 2017 and 2020, respectively. The number of articles timate the number of future publications by verifying the predictions
increased from 3 in 2001 to 56 and 31 in 2017 and 2019, respectively. made in previous bibliometric studies. For instance, Zhi and Ji [27]
There was an evident and significant rise in both the number of stated in their bibliometric review on constructed wetland research, for
publications and the number of articles from 2005–2006 to the period from 1991 to 2011, that the number of articles published in
2008–2009. Since then, a stabilization in the number of publications 2015 and 2017 would double and triple, respectively, in comparison to
with a slightly increasing trend over time can be observed. In addition, those published in 2011 (3787). The search carried out in WoS revealed
two different intervals, from 2001 to 2006 and from 2007 to 2019, can that the articles published in 2015 and 2017 were 7113 and 8770, re-
be identified in terms of accumulative trends. In this way, Fig. 1B shows spectively. Further, using the prediction model reported in a biblio-
a linear model and a two-order polynomial model for these two metric study on industrial wastewater research from 1991 to 2014 [95],

Fig. 1. A) The number of publications and articles on biodiesel production under supercritical conditions from 1999 to 2019. B) The correlations between the number
of accumulated articles per year and the year of publication, since 2001.

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it was forecast that 44,268 articles would be published in 2018 and the conditions. Therefore, according to Lotka's law, and considering that
search carried out in WOS produced 42,765 articles in the field. more than 35 countries, including the USA, several members of Eur-
Therefore, this analysis is a reasonably effective tool to predict the opean Union, China and Brazil, have recently implemented policies to
number of future publications in a research field. promote biofuel production and use [32], it can be expected that more
Table 1 shows the characteristics of the publications from 2001 to scientists will be involved in this research field.
2019. The annual number of authors increased considerably from 6 in Of the 608 articles found in the present bibliometric review, 428
2001 to 237 in 2018. The rise in the average number of authors and (70.4%) cited themselves (local citations). The article that received the
references cited (from 43 in 2001 to 2469 in 2018) also indicates an highest number of local citations (279) was Saka and Kusdiana [16],
increase in scientific production and collaboration within the target which is logical given that these authors are pioneers in biodiesel
fields of the present bibliometric review. Considering the most recent production under supercritical conditions, followed by Kusdiana and
data from 2019, a decrease in the number of publications can be ob- Saka [102], which was locally cited 231 times. Nine (1.5%), eighteen
served in comparison to previous years. The average number of pages (3.0%), sixty-two (10.2%) and one hundred and sixteen (19.0%) arti-
per article (8.1) ranged from 6.0 in 2001 to 11.0 in 2019. cles were cited more than 100, 50, 20 and 10 times, respectively. A co-
1533 different authors signed the 608 articles found in the present citation analysis was also performed. Co-citation analysis measures the
bibliometric review. Since it has been reported that there may be bias in number of documents that have cited any given pair of documents. This
this type of study due to the possibility that the same author appears analysis showed 442,912 unique pairs and Appendix Fig. A.2 shows co-
with different names in several articles [27,100], an exhaustive stan- citation networks for frequencies ≥35. The most common co-citation
dardization work was done for this analysis to minimize the bias risk. number was 1 (92.1%), followed by 2 (5.3%) and 3 (1.3%). The greater
Among the 1533 authors, 1136 (74.1%) appeared in one article, fol- co-citation number was Saka and Kusdiana [16] and Kusdiana and Saka
lowed by 217 (14.2%) in two, 76 (5.0%) in three, and 27 (1.8%) in four [102] (146), followed by Saka and Kusdiana [16] and Kusdiana and
articles. Saka [103] (110), and Kusdiana and Saka [103] and Kusdiana and Saka
Forty-five articles (7.4%) had a single author. Twelve (1; 0.2%) was [102] (99).
the highest number of authors in one article, followed by 11 (1; 0.2%),
10 (5; 0.8%) and 9 (9; 1.5%). The most common number of authors per 3.2.1.3. Journal publication patterns and WoS subject category. 139
article was three (130; 21.4%), followed by four (117; 19.2%), five (91; different journals published the 608 articles found in the present
15.0%) and two (87; 14.3%). Sixty-three (10.4%), thirty-nine (6.4%), bibliometric review. The 10 most productive journals together with
and twenty (3.3%) articles were authored by six, seven, and eight au- article number and percentage, h-index, IF (2018), journal category,
thors, respectively. and journal position by categories according to JCR are listed in
Table 2 shows the top 10 authors in the field according to the Table 3. 10 journals were responsible for 62.8% of the 608 articles.
number of publications, indicating their h-index together with the total The Fuel journal ranked first for number of published articles (69,
number of publications (TP), the number of times they appear as first 12.4%), followed by Bioresource Technology (49, 8.8%), and Journal of
authors in the publications (FP), and the number of times they appear Supercritical Fluids (48, 8.6%). Fuel had the highest h-index value (32),
as corresponding authors. Demirbas, A. contributed the highest number followed by Bioresource Technology (27) and Energy Conversion and
of articles (36; 5.9%) with an h-index of 20, followed by Saka, S. (21; Management (23). These results are in line with those published by
3.5%) with an h-index of 18, Lee, K.T. (16; 2.6%) and Deng, S.G. (14; Zhang, Gao [22]. As can be observed in Fig. 3A, the annual publication
2.3%) with an h-index of 12, respectively, Patil, P. (11; 1.8%), Oliveira, pattern for the top 6 most productive journals exhibited a sharp
J.V. (12; 2.0), and Quesada-Medina, J. (14; 2.3%) with an h-index of increase from 2001 to 2008, when the maximum was reached (27).
11, respectively, da Silva, C. (18; 3.0%) with an h-index of 10, and From 2009 to 2015 this growing trend showed slight fluctuations
Olivares-Carrillo, P. (11; 1.8%) and Tavlarides, L.L. (10; 1.6) with an h- around 21 publications.
index of 9, respectively. Seventy-nine (56.8%) journals published one article on biodiesel
The analysis of author collaboration showed a total of 4104 colla-
borations. Appendix Fig. A.1 shows collaboration networks for fre- Table 1
quencies ≥ 4. The most common collaboration number was 1 (3487; Characteristics by article year from 2001 to 2019.
85.0%), followed by 2 (423; 10.3%) and 3 (111; 2.7%). The greatest
PY TP AU AU/TP NR NR/TP PG PG/TP
number of author collaboration was 11 (0.02%): Patil, P.D. and Deng,
S.G. [both from New Mexico State University (USA)]; followed by 10 2001 3 6 2.0 43 14.3 18 6.0
(0.02%): Sawangkeaw, R. and Ngamprasertsith, S. [both from 2002 2 2 1.0 18 9.0 15 7.5
Chulalongkorn University (Thailand)]; and 9 (0.05%): Oliveira, J.V. 2003 3 14 4.7 83 27.7 23 7.7
2004 5 17 3.4 140 28.0 35 7.0
and da Silva, C., [from Regional Integrada Alto Uruguai & Missoes 2005 6 11 1.8 170 28.3 43 7.2
University (Brazil) and University Estadual of Maringa (Brazil), re- 2006 8 28 3.5 168 21.0 58 7.3
spectively], and Quesada-Medina, J. and Olivares-Carrillo, P. [both 2007 28 101 3.6 709 25.3 231 8.3
from University of Murcia (Spain)]. As can be observed, except for 2008 40 132 3.3 930 23.3 293 7.3
2009 46 166 3.6 1360 29.6 319 6.9
Demirbas, A., Sawangkeaw, R., Ngamprasertsith, S., and Saka, S., those
2010 41 166 4.0 1516 37.0 317 7.7
6 authors were also among the most productive and had the highest h- 2011 53 228 4.3 1713 32.3 426 8.0
index. 2012 46 174 3.8 1412 30.7 331 7.2
The Lotka's Law is a bibliometric law on the distribution of authors 2013 41 176 4.3 1316 32.1 317 7.7
according to their productivity and it is described as Xn·Y = C [101]. 2014 50 226 4.5 2163 43.3 460 9.2
2015 44 202 4.6 1911 43.4 443 10.1
The number of articles is represented by X, the number of authors 2016 55 237 4.3 2002 36.4 452 8.2
publishing X articles is Y, with n commonly ranging between 1.2 and 2017 56 234 4.2 2336 41.7 540 9.6
3.5, and C depending on the field of knowledge [27]. Fig. 2A shows 2018 50 237 4.7 2469 49.4 494 9.9
Lotka's Law (X2.51·Y = 1169.6) to elucidate the correlation of the 2019 31 140 4.5 1470 47.4 342 11.0
Average 3.7 31.6 8.1
number of authors with the number of articles published. The range
Total 608 2497 21,929 5157
from 1 to 6 articles (only 2.2% of the 1533 authors published more than
six articles) showed a high correlation (R2 = 0.9712). Fig. 2A also TP: total publications; AU: authors number; AU/TP: average of authors per
shows that an adequate number from 1 to 3 authors greatly contributed article; NR: cited reference count; NR/TP: average of reference per article; PG:
(93.2%) to biodiesel production research under supercritical page count; PG/TP: average of pages per article.

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Table 2
10 most productive authors ordered by h-index from 2001 to 2019.
Author Affiliation h-index (R) TP (R) RP (R) FP (R)

Demirbas, A. Sila Science, Turkey 20 (1) 36 (1) 36 (1) 34 (1)


King Abdulaziz University, Saudi Arabia
Saka, S. Kyoto University, Japan 18 (2) 21 (2) 20 (2) 4 (9)
Lee, K.T. Chungnam National University, South Korea 12 (3) 16 (4) 11 (5) N/A
Deng, S.G. American Refining Group Inc, USA 12 (3) 14 (5) 13 (3) N/A
Quesada-Medina, J. University of Murcia, Spain 11 (5) 14 (5) 10 (7) 1 (97)
Oliveira, J.V. Federal University of Santa Catarina, Brazil 11 (5) 12 (7) 3 (35) N/A
Patil, P. New Mexico State University, USA 11 (5) 11 (8) N/A 7 (3)
da Silva, C. Maringa State University, Brazil 10 (8) 18 (3) 12 (4) 3 (20)
Olivares-Carrillo, P. University of Murcia, Spain 9 (9) 11 (8) 1 (91) 3 (20)
Tavlarides, L.L. Syracuse University, USA 9 (9) 10 (14) 9 (9) N/A

TP: total publications; FP: publication with first author; RP: publication with corresponding author; R: Rank.

production under supercritical conditions, and 19 (13.7%) and 13 Microbiology (74), and Thermodynamics (71). Zhang, Gao [22] re-
(9.4%) journals published two and three articles, respectively. The ported a greater number of subject categories (81) in their bibliometric
Lotka's Law of Fig. 2B shows a good correlation of journals with a review on biodiesel research for the period 1991–2015, since their field
number of articles in the range from one to six articles (only 10.1% of of study was broader and, as discussed before, biodiesel production
the 139 journals published more than six articles) with a good de- under supercritical conditions is a relatively new research field. How-
termination coefficient (R2 = 0.954). Therefore, a broader variety of ever, they also reported a strong increase of both Engineering and En-
subject areas for biodiesel production under supercritical conditions is ergy & Fuels subject categories from 2005 onward, in agreement with
expected in future publications. the results found in the present bibliometric review, proving that those
The 608 articles were published in 35 different subject categories of are the most productive categories in the study of biodiesel and that it
the WoS. This fact implies that biodiesel production under supercritical will be hard for other categories to surpass them in the near future.
condition research is multidisciplinary in nature. Fig. 4 shows the top
five WoS categories from 2001 to 2019, with “Engineering, Chemical”
contributing the most with 346 articles, followed by Energy & Fuels 3.2.1.4. Country and institution publication performance. Fig. 5 shows the
(340), “Chemistry, Physical” (78), Biotechnology & Applied 608 articles representing 60 countries and, as can be observed, Africa
was the continent with the fewest countries involved in the publication

Fig. 2. A) Lotka's Law to elucidate the correlation of the number of authors with the articles published; B) Lotka's Law to elucidate the correlation between the
journals number and the articles published; C) Lotka's Law to elucidate the correlation of the institutions number with the articles published; D) Lotka's Law to
characterize the total author's keywords percentage and its frequency of utilization.

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Table 3
Top 10 productive journals, total number of articles (percentage), h-index, IF (2018), journal categories, and journal position by categories according to JCR from
2001 to 2019.
Journal name TP (%) h-index (R) IF (2018) Subject category Position

Fuel 69 (12.4) 32 (1) 5.128 Energy & Fuels 20/103


Engineering, Chemical 13/138
Bioresource Technology 49 (8.8) 27 (2) 6.669 Agricultural Engineering 1/13
Biotechnology & Applied Microbiology 13/162
Energy & Fuels 7/81
Journal of Supercritical Fluids 48 (8.6) 19 (4) 3.481 Chemical, Physical 56/148
Engineering, Chemical 29/138
Energy Conversion and Management 45 (8.1) 23 (3) 7.181 Thermodynamics 2/60
Energy & Fuels 12/103
Mechanics 3/134
Energy Sources Part A-Recovery Utilization and Environmental Effects 37 (6.6) 15 (7) 0.894 Energy & Fuels 93/103
Engineering, Chemical 108/138
Energy & Fuels 34 (6.1) 19 (4) 3.021 Energy & Fuels 52/103
Engineering, Chemical 36/137
Industrial & Engineering Chemistry Research 24 (4.3) 12 (8) 3.375 Engineering, Chemical 33/138
Fuel Processing Technology 21 (3.8) 16 (6) 4.507 Chemistry, applied 11/71
Energy & Fuels 27/103
Engineering, Chemical 19/138
Applied Energy 11 (2.0) 11 (9) 8.426 Energy & Fuels 8/103
Engineering, Chemical 5/138
Chemical Engineering journal 11 (2.0) 10 (10) 8.355 Engineering, Environmental 2/52
Engineering, Chemical 6/138

TP (%): total publications and percentage of total publications; IF: Impact factor.

of articles on biodiesel production under supercritical conditions over production research under supercritical conditions. China ranked first
the last 19 years. It is worth mentioning that, although one article with 96 (15.8%) articles, followed by Japan (58; 9.5%), the USA (54;
lacked affiliation [104], it was manually added and the names of the 8.8%), and Brazil (53; 8.7%). Among the top 20 most productive
institutions were exhaustively standardized in order to avoid bias, as countries, Japan had the highest h-index value (29), followed by China
discussed before. (27), Turkey (25) and the USA (25). Zhang, Gao [22], in their biblio-
Table 4 shows the 20 most productive countries in biodiesel metric review on biodiesel research until 2015, reported that the USA

Fig. 3. A) Annual publication patter of the six most productive journals; B) Annual publication patter of the six most productive countries.

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Fig. 4. Top five productive Web of Science categories from 2001 to 2019.

occupied the first place in the ranking for the period of 1991–2015, country in biodiesel research. This can be explained by the fact that the
closely followed by China, with a dominant role of China in biodiesel Chinese government started to promulgate policies on the use of bio-
research. Later, Ma, Gao [33], in their bibliometric review on micro- fuels as an important energy strategy in 2015 [106]. These policies
alga-derived biodiesel until 2016, also reported that the USA ranked translate more rapidly into scientific production than into industrial
first in terms of published articles, followed by China; however, China production mainly due to the temporary limitations on the im-
surpassed the USA in 2015 and held this position in 2016 mainly due to plementation of the developed technologies, among other factors. Fi-
the China's effective guidance policies. Thus, the position of China as a nally, Table 4 also includes the research production in terms of pub-
leading country in terms of articles published on biodiesel observed by lications per country normalized to inhabitant population (million)
these authors is also confirmed in the present bibliometric review. In (ratio R). Taking into account this ratio, China ranked 17th instead of
addition, Fig. 3B shows that, only considering the TP of the top 6 most first place.
productive countries for the last 19 years, China held a predominant The majority of the articles (499; 82.1%) were single-country pub-
position since 2010 until 2018, being surpassed by Brazil in 2019. The lications and 109 (17.9%) were international joint publications. The
cases of Japan and Turkey are particularly interesting because these correlation of the top 20 most productive countries in single-country
countries offered the largest number of articles published until 2009, articles with the accumulative percentage of single-country articles is
but they were also outstripped by China from 2010 onwards. On the shown in Appendix Fig. A.3, offering a good correlation (R2 = 0.9847)
other hand, the largest producers of biodiesel in 2016 were the Eur- in the range from 1 to 20 countries. In addition, these 20 countries
opean Union (26.0%) followed by the USA (17.9%), Brazil (12.3%), published almost all the articles (92.8%) related to biodiesel production
Argentina and Indonesia (9.7%) and Thailand (4.5%) [105]. As can be research under supercritical conditions.
observed, the largest producers of biodiesel are listed among the 20 The country collaboration analysis found a total of 86 collaborations
most productive countries included in Table 4. As a special case, China and Fig. 6 shows collaboration networks for frequencies ≥2. As can be
is not among the largest producers of biodiesel despite being a leading observed, there are seven regional groups varying in size of countries

Fig. 5. Choropleth global map of total number of articles on biodiesel production under supercritical conditions from 2001 to 2019.

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Table 4
20 most productive article publishing countries from 2001 to 2019.
Country TP TP R (%) h-index (R) SP R (%) CP R (%) FP R (%) RP R (%) CP CP (%) Ratio (R)

China 96 1 (15.7) 27 (2) 1 (15.8) 2 (15.5) 1 (14.4) 1 (14.8) 17 17.7 0.06 (17)
Japan 58 2 (9.5) 29 (1) 4 (9.0) 4 (11.9) 2 (9.0) 2 (8.0) 13 22.4 0.45 (8)
USA 54 3 (8.8) 25 (3) 5 (7.2) 1 (16.5) 5 (5.9) 4 (7.7) 18 33.3 0.16 (15)
Brazil 53 4 (8.7) 20 (5) 3 (9.2) 9 (6.4) 3 (8.7) 3 (7.8) 7 13.2 0.25 (11)
Turkey 49 5 (8.0) 25 (3) 2 (9.4) 29 (1.8) 4 (7.7) 4 (7.7) 2 4.1 0.61 (7)
South Korea 38 6 (6.2) 13 (8) 7 (5.8) 8 (8.2) 7 (4.9) 6 (6.0) 9 23.7 0.73 (5)
India 35 7 (5.7) 11 (12) 6 (6.6) 29 (1.8) 6 (5.5) 7 (5.5) 2 5.7 0.02 (20)
Malaysia 35 7 (5.7) 18 (6) 8 (5.0) 7 (9.1) 8 (4.6) 8 (5.4) 10 28.6 1.1 (2)
Spain 32 9 (5.2) 16 (7) 10 (3.2) 3 (14.6) 10 (3.1) 9 (4.6) 16 50.0 0.68 (6)
Thailand 24 10 (3.9) 13 (8) 9 (4.2) 22 (2.7) 9 (3.6) 10 (3.7) 3 12.5 0.34 (9)
Taiwan 22 11 (3.6) 12 (10) 15 (1.8) 4 (11.9) 15 (2.1) 11 (3.1) 13 59.1 0.92 (4)
Serbia 20 12 (3.2) 12 (10) 11 (3.0) 15 (4.5) 12 (2.4) 11 (3.1) 5 25.0 2.81 (1)
Iran 18 13 (2.9) 9 (14) 14 (2.4) 13 (5.5) 11 (2.7) 13 (2.6) 6 33.3 0.22 (13)
Russia 16 14 (2.6) 6 (18) 11 (3.0) 40 (0.9) 12 (2.4) 14 (2.3) 1 6.3 0.11 (16)
Indonesia 14 15 (2.3) 8 (15) 23 (0.4) 6 (11.0) 16 (1.9) 18 (1.1) 12 85.7 0.05 (19)
Argentina 14 15 (2.3) 11 (12) 13 (2.6) 40 (0.9) 14 (2.3) 14 (2.3) 1 7.1 0.31 (10)
Portugal 11 17 (1.8) 8 (15) 18 (0.8) 9 (6.4) 17 (1.6) 19 (0.9) 7 63.6 1.06 (3)
UK 11 17 (1.8) 8 (15) 18 (0.8) 9 (6.4) 28 (0.6) 16 (1.4) 7 63.6 0.16 (14)
Mexico 8 19 (1.3) 5 (20) 16 (1.2) 29 (1.8) 18 (1.3) 17 (1.3) 2 25.0 0.06 (18)
Saudi Arabia 8 19 (1.3) 4 (23) 18 (0.8) 18 (3.6) 22 (0.8) 19 (0.9) 4 50.0 0.24 (12)

TP: total publications; SP: single country publication; CP: internationally collaborative publication; FP: publication with first author; RP: publication with corre-
sponding author; R (%): Rank and share in publication; CP%: the percentage of internationally collaborative publications in total publications for each country; R:
ratio of TP per inhabitant population (million).

and articles. The most collaborative country was China (5), followed by was also carried out taking into account the country of the first author
both the USA (4) and Spain (4). The most common collaboration (FP), in order to determine the increasing interest in biodiesel pro-
number was 1 (61; 70.9%), followed by 2 (14; 16.3%) and 3 (4; 4.7%). duction under supercritical conditions. Among the 608 articles, 221
Indonesian-Taiwanese collaborations ranked first (9; 0.1%) and In- (36.3%) did not report research funds. The first article declaring re-
donesia also showed the maximum collaborative rate (87.5%), followed search funds [Sila Science (Turkey)] was published in 2008 [107]. This
by both Portugal (63.6%) and United Kingdom (63.6%) (Table 4). date coincides with the second interval of Fig. 1.B, highlighting the
Therefore, as can be observed, the research on biodiesel production increasing interest in biodiesel production under supercritical condi-
under supercritical conditions was centralized in Asia, followed by tions from 2007. Mexico (8; 100%) and Malaysia (28; 100%) reported
America. research funds in all its published articles, followed by Spain (19;
An analysis of the number of publications reporting research funds 94.7%), Portugal (10; 90%), South Korea (30; 86.7%), Serbia (15;

Fig. 6. Country collaboration network for frequencies ≥2. The circle size represents the number of articles, two different colors represent the presence of a significant
connection between two groups of countries.

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P. Andreo-Martínez, et al. Applied Energy 264 (2020) 114753

86.7%), Taiwan (13; 84.6%), Indonesia (12; 83.3%); Australia (6; University (Brazil), National Taiwan University of Science and
83.3%), USA (36; 77.8%), Brazil (53; 77.4%) and China (88; 77.3%). Technology (Taiwan), and Widya Mandala Surabaya Catholic
On the contrary, Saudi Arabia (5), Algeria (1), Austria (2), Bangladesh University (Indonesia)] published all their articles in collaboration with
(2), Belgium (1), Finland (1), Greece (2), Israel (2), Nigeria (1), Poland other institutions while Sila Science published only two inter-institu-
(1), South Africa (1) and Switzerland (1) did not publish research funds tional articles and all the articles of both Indian Institute of Science and
in any of its articles. Hiroshima University were single institution articles. Finally, the in-
Table 5 shows the 20 most productive institutions performing re- stitution collaboration was higher than the country collaboration, as
search on biodiesel production under supercritical conditions. The 608 reported elsewhere [27,32].
articles represented 490 institutions from 60 countries. Among the 608 Lotka's law of Fig. 2C shows a good correlation of institutions with a
articles, 347 (57.1%) were independent institution publications, and number of articles published in the range from one to eight articles
261 (42.9%) were inter-institutional collaborative publications. Among (only 2.8% of the 490 institutions published more than eight articles)
the 490 institutions, 337 (55.4%) had only one article related to bio- with a good determination coefficient (R2 = 0.9208). This analysis
diesel production research under supercritical conditions, 65 (10.7%) showed that 398 (81.2%) institutions published less than three articles
two articles, and 26 (4.3%) three articles. related to biodiesel production under supercritical conditions over the
Among the top 20 most productive institutions, three institutions last 19 years. In this sense, it can be forecast that the number of in-
were located in China proving the leading and dominant role of this stitutions implicated in the production of biodiesel under supercritical
country in the field. This finding corroborates the results reported by conditions will increase as the number of articles also rises; however,
Zhang, Gao [22]. Brazil, the USA, Japan and Serbia had two institutions significant changes in the positions of the top 20 most productive in-
in the top 20 most productive institutions, and the countries India, stitutions cannot be expected in the coming years.
Indonesia, Malaysia, Russia, South Korea, Spain, Thailand, Taiwan, and
Turkey ranked with one institution in the top 20 most productive in- 3.3. Research trends
stitutions. The Sila Science Institution (27; 4.4%), Kyoto University (22;
3.6%), Chulalongkorn University (18; 2.9%), Sains Malaysia University The single title words and author keywords provide detailed in-
(16; 2.6%), University of Murcia (14; 2.3%), and New Mexico State formation about the subject of the articles while the WoS keywords
University (13; 2.1%), were the top six research institutions. The Sila provide more detailed and varied information on the articles. Garfield
Science together with Kyoto University had the highest h-index value [108] reported that the frequencies of author keywords and single title
(18), followed by both Sains Malaysia University and New Mexico State words can be statistically analyzed to identify the leading fields of re-
University (12). search and to suggest future science directions. In addition, the bib-
The institution collaboration analysis found a total of 458 colla- liometric study of single title words, WoS keywords and author key-
borations and Appendix Fig. A.4 shows collaboration networks for words can minimize the incomplete meaning of single words in the title,
frequencies ≥3. As can be observed, there are twelve groups varying in the indirect relationship between WoS keywords and research em-
size of institutions and articles. The most collaborative institutions are phases, and the small sample size for author keywords, respectively
the National Taiwan University of Science and Technology (3) followed [109]. In this sense, the 608 articles found in the present bibliometric
by Regional Integrada Alto Uruguai & Missoes University together with review were analyzed in terms of author's keywords, single title words
Maringa State University (2). The most common institutions colla- and WoS keywords.
boration number was 1 (392; 85.6%), followed by 2 (48; 10.5%) and 3
(11; 2.4%). The two institutions that published the largest number of 3.3.1. Author keyword analysis
articles in collaboration were National Taiwan University Science and Fig. 2D shows Lotka's law to elucidate the correlation of the per-
Technology (Taiwan) and Widya Mandala Surabaya Catholic University centage of total author keywords with the frequency that an author
(Indonesia) (7; 0.2%). keyword was used. The range from 1 to 6 times showed a good de-
Three institutions [Regional Integrada Alto Uruguai & Missoes termination coefficient (R2 = 0.9744). A total of 964 unique author

Table 5
20 most productive article publishing institutions from 2001 to 2019.
Institution TP TP R (%) h-index (R) SP R (%) CP R (%) FP R (%) RP R (%) CP CP (%)

Sila Science, Turkey 27 1 (4.4) 18 (1) 1 (7.2) 53 (0.7) 1 (4.2) 1 (4.1) 2 7.4
Kyoto University, Japan 22 2 (3.6) 18 (1) 2 (5.7) 53 (0.7) 2 (3.6) 2 (3.2) 2 9.1
Chulalongkorn University, Thailand 18 3 (2.9) 11 (5) 3 (3.7) 15 (1.9) 3 (2.7) 3 (2.6) 5 27.8
Sains Malaysia University, Malaysia 16 4 (2.6) 12 (3) 4 (3.1) 15 (1.9) 4 (2.1) 5 (1.9) 5 31.3
University of Murcia, Spain 14 5 (2.3) 11 (5) 12 (1.4) 3 (3.4) 13 (0.9) 6 (1.6) 9 64.3
New Mexico State University, USA 13 6 (2.1) 12 (3) 8 (2.0) 8 (2.2) 7 (1.3) 4 (2.1) 6 46.2
Estadual Maringa University, Brazil 12 7 (1.9) 5 (21) 52 (0.2) 2 (4.2) 19 (0.8) 9 (1.4) 11 91.7
National Taiwan University of Science and Technology, Taiwan 12 7 (1.9) 7 (9) N/A 1 (4.5) 13 (0.9) 9 (1.4) 12 100.0
University of Belgrade, Serbia 11 9 (1.8) 9 (7) 12 (1.4) 8 (2.2) 9 (1.1) 9 (1.4) 6 54.5
Syracuse University, USA 10 10 (1.6) 9 (7) 6 (2.3) 53 (0.7) 5 (1.6) 6 (1.6) 2 20.0
Indian Institute of Science, India 10 10 (1.6) 4 (35) 5 (2.8) N/A 5 (1.6) 6 (1.6) 0 0.0
Widya Mandala Catholic University, Indonesia 9 12 (1.4) 7 (9) N/A 3 (3.4) N/A 32 (0.6) 9 100.0
Russian Academy of Science, Russia 9 12 (1.4) 5 (21) 9 (1.7) 34 (1.1) 13 (0.9) 20 (0.9) 3 33.3
Xi’an Jiaotong University, China 8 14 (1.3) 4 (35) 52 (0.2) 5 (2.6) 94 (0.1) 15 (1.1) 7 87.5
Dalian University of Technology, China 8 14 (1.3) 7 (9) 12 (1.4) 34 (1.1) 19 (0.8) 12 (1.3) 3 37.5
University of Novi Sad, Serbia 8 14 (1.3) 5 (21) 52 (0.2) 5 (2.6) 94 (0.1) 12 (1.3) 7 87.5
Zhejiang University, China 8 14 (1.3) 7 (9) 9 (1.7) 53 (0.7) 13 (0.9) 20 (0.9) 2 25.0
Hiroshima University, Japan 8 14 (1.3) 7 (9) 6 (2.3) N/A 7 (1.3) 12 (1.3) 0 0.0
Regional Integrada Alto Uruguai & Missoes University, Brazil 7 19 (1.1) 6 (14) N/A 5 (2.6) 37 (0.4) 59 (0.3) 7 100.0
Kongju National University, South Korea 7 19 (1.1) 4 (35) 52 (0.2) 8 (2.2) 94 (0.1) 20 (0.9) 6 85.7

TP: total publications; SP: single institute publication; CP: inter-institutionally collaborative publication; FP: publication with first author; RP: publication with
corresponding author; R (%): Rank and share in publication; CP%: the percentage of inter-institutionally collaborative publications in total publications for each
institute.

11
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keywords were found and 155 (16.1%) were used three or more times. “heterogeneous catalyst” maintained the position 19 in the third and
Zhi and Ji [27] explained that this fact can be attributed to the non- fourth intervals, showing the general interest in the study of the
standardization in the use of synonymous terms, spelling variations and transesterification reaction rates (biodiesel production under super-
abbreviations. critical conditions is faster than classical biodiesel production) and the
Table 6 shows the top 20 author keywords from 2001 to 2019, using attempt to soften the supercritical reaction conditions to reduce energy
5-year intervals to ensure a rational period of time and to try to reduce requirements thus improving environmental advantages.
annual fluctuations. Excluding the topic search keywords (i.e. biodiesel
or supercritical methanol and related words such as biofuel, production
3.3.2. Single title words analysis
or fuel), “transesterification” (152; 15.7%), “esterification” (32; 3.3%),
1153 unique words were found in the analysis of single title words,
“vegetable oil” (30; 3.1%), “kinetics” (22; 2.2%), “methyl esters” (20;
in which terms such as prepositions and articles were discarded. Table 7
2.0%), and both “free fatty acids” and “heterogeneous catalyst” (18;
shows the 20 most used single words in titles from 2001 to 2019 using
1.8%) were the five most frequently used author's keywords. “Trans-
5-year intervals. Excluding the topic search keywords, as previously
esterification” maintained a constant position (2–3) in the four 5-year
mentioned, “oil” (264; 22.8%), “transesterification” (168; 14.5%),
intervals and “esterification” climbed from position 9 (2.6%) in the first
“process” (84; 7.2%), “acid” (76; 6.5%), and “condition” (66; 5.7%)
interval (2001–2005) to position 5 (2.9%) in the second interval
were the five most frequently used single title words. “Oil” remained
(2006–2010), descended to position 8 (1.9%) in the third interval
around a constant position in the four intervals studied due to the fact
(2011–2015) but climbed again to position 4 (3.0%) in the fourth in-
that is the feedstock used to produce biodiesel under supercritical
terval (2016–2019). However, “vegetable oil” descended from position
conditions. The decrease of “soybean” from position 10 (4.9%) in the
5 (6.7%) and 4 (4.2%) in the first and the second intervals, respectively,
first interval to position 31 (1.4%) in the fourth interval also revealed
to position 11 (1.7%) and 15 (1.4%) in the third and the fourth inter-
the obsolescence of first-generation biodiesel. “Transesterification” re-
vals, respectively. By contrast, “microalga” did not appear in the first
mained in a virtually constant position (6) in the four intervals studied
interval but climbed from position 66 (0.3%) in the second interval to
and “catalyst” climbed from position 22 (1.6%) in the first interval to
position 11 (1.7%) and 12 (1.6%) in the third and the fourth intervals,
position 10 (4.0%) in the fourth interval studied, both being consistent
respectively. This fact can demonstrate the transition from first-gen-
with the analysis of author keywords, since catalysts in supercritical
eration biodiesel to third-generation biodiesel [6,7]. In this sense, mi-
conditions can be used to smooth reaction conditions. “Process” was not
croalgae utilization has been identified as a promising technology for
present in the first interval but climbing to position 8 (4.1%) in the
biodiesel production, wastewater treatment, the development of high
fourth interval, and “condition” climbed from position 22 (1.6%) in the
value-added products and CO2 capture; although the oil content in
first interval to position 8 (4.1%) in the fourth interval. This fact can
microalgae is similar to that found in other feedstocks, the global an-
suggest that optimization reaction conditions have become primary
nual output is larger and the growth rates are faster [110–112]. The
research focuses.
cultivation of microalgae presents some drawbacks that would need to
be overcome in order to increase its sustainability. In this sense, it is
essential to improve the Net Energy Ratio of the production process of 3.3.3. WoS keywords analysis
microalgae, which would lead to the reduction of greenhouse gases 929 unique words were found in the WoS keyword analysis and the
emissions. The cultivation of microalgae in photobioreactors requires 20 most utilized WoS keywords, from 2001 to 2019 using 5-year in-
high energy consumption, which makes it unsustainable. Nevertheless, tervals, are shown in Table 8. Excluding the topic search keywords,
the use of open ponds or raceways combined with wastewater treat- “transesterification” (252; 27.1%), “rapeseed” (241; 25.9%), “vegetable
ment could help to perform the process in a more sustainable way oil” (220; 23.6%), “soybean oil” (203; 21.8%), and “Fuel” (200; 21.5%)
[113,114]. were the five most frequently used WoS keywords. As WoS keywords
The author keyword “kinetics” climbed from positions 10 (1.6%) are generated by an ISI algorithm, from words or expressions in the
and 19 (1.3%) in the second and the third intervals, respectively, to article's reference titles [108], it is logical that “rapeseed” appears in
position 6 (2.3%) in the fourth interval. The author keyword the second position of most-used WoS keywords since the most cited
article was “Biodiesel fuel from rapeseed oil as prepared in supercritical

Table 6
20 most used author's keywords from 2001 to 2019.
Author keywords TP 2001–2019 R (%) 2001–2005 R (%) 2006–2010 R (%) 2011–2015 R (%) 2016–2019 R (%)

Biodiesel 353 1 (36.6) 1 (21.0) 1 (33.4) 1 (31.6) 1 (23.2)


Transesterification 152 2 (15.7) 3 (18.4) 2 (14.9) 2 (13.9) 2 (8.4)
Supercritical Methanol 102 3 (10.5) 1 (21.0) 3 (8.4) 3 (8.4) 3 (7.0)
Esterification 32 4 (3.3) 9 (2.6) 5 (2.9) 8 (1.9) 4 (3.0)
Supercritical 30 5 (3.1) 9 (2.6) 10 (1.6) 4 (3.0) 6 (2.3)
Vegetable Oil 30 5 (3.1) 5 (7.8) 4 (4.2) 11 (1.7) 15 (1.4)
Methanol 24 7 (2.4) 9 (2.6) 7 (2.5) 5 (2.4) 21 (0.9)
Kinetic 22 8 (2.2) 9 (2.6) 10 (1.6) 19 (1.3) 6 (2.3)
Ethanol 22 8 (2.2) N/A 32 (0.6) 8 (1.9) 5 (2.5)
Supercritical Ethanol 21 10 (2.1) 9 (2.6) 16 (1.2) 19 (1.3) 6 (2.3)
Supercritical Fluid 21 10 (2.1) 9 (2.6) 66 (0.3) 6 (2.2) 9 (2.1)
Methyl Esters 20 12 (2.0) 3 (18.4) 10 (1.6) 32 (0.8) 21 (0.9)
Free Fatty Acids 18 13 (1.8) 9 (2.6) 21 (0.9) 19 (1.3) 10 (1.8)
Heterogeneous Catalyst 18 13 (1.8) 9 (2.6) 9 (1.9) 19 (1.3) 19 (1.1)
Response Surface Methodolog 17 15 (1.7) N/A 32 (0.6) 8 (1.9) 15 (1.4)
Supercritical Transesterification 17 15 (1.7) N/A 16 (1.2) 24 (1.1) 10 (1.8)
Microalga 16 17 (1.6) N/A 66 (0.3) 11 (1.7) 12 (1.6)
Fatty Acid Methyl Esters 16 17 (1.6) N/A 10 (1.6) 14 (1.5) 21 (0.9)
Biofuel 15 19 (1.5) N/A 32 (0.6) 14 (1.5) 15 (1.4)
Optimization 15 19 (1.5) N/A 66 (0.3) 6 (2.2) 21 (0.9)

TP: total publications; R (%): rank and share of the author keyword; N/A: not available due to the reason that the author keyword did not appear in the study period.

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P. Andreo-Martínez, et al. Applied Energy 264 (2020) 114753

Table 7
20 most used title words from 2001 to 2019.
Single title words TP 2001–2019 R (%) 2001–2005 R (%) 2006–2010 R (%) 2011–2015 R (%) 2016–2019 R (%)

Biodiesel 376 1 (32.6) 3 (18.0) 1 (25.4) 1 (24.1) 1 (16.8)


Supercritical 298 2 (25.8) 2 (19.6) 3 (16.0) 2 (20.1) 2 (14.9)
Production 278 3 (24.1) 6 (6.5) 4 (14.9) 3 (19.4) 3 (14.4)
Oil 264 4 (22.8) 1 (21.3) 2 (16.2) 4 (15.5) 4 (13.4)
Methanol 194 5 (16.8) 4 (14.7) 5 (11.1) 5 (12.8) 5 (9.1)
Transesterification 168 6 (14.5) 6 (6.5) 6 (9.2) 6 (12.2) 6 (7.8)
Process 84 7 (7.2) N/A 8 (4.3) 7 (6.3) 8 (4.1)
Acid 76 8 (6.5) 11 (3.2) 11 (3.2) 10 (4.5) 7 (5.1)
Condition 66 9 (5.7) 22 (1.6) 23 (1.7) 9 (5.1) 8 (4.1)
Catalyst 65 10 (5.6) 22 (1.6) 14 (2.8) 11 (4.3) 10 (4.0)
Ethanol 65 10 (5.6) N/A 15 (2.6) 8 (5.5) 13 (3.2)
Fatty 57 12 (4.9) 11 (3.2) 17 (2.4) 12 (3.8) 11 (3.3)
Continuous 54 13 (4.6) N/A 13 (3.0) 15 (3.6) 17 (2.8)
Fuel 51 14 (4.4) 5 (9.8) 7 (5.4) 34 (1.8) 31 (1.4)
Synthesis 51 14 (4.4) 22 (1.6) 9 (4.1) 17 (3.3) 26 (1.7)
Under 50 16 (4.3) 22 (1.6) 34 (1.3) 12 (3.8) 13 (3.2)
Soybean 49 17 (4.2) 10 (4.9) 10 (3.9) 21 (3.1) 31 (1.4)
Kinetic 46 18 (3.9) 11 (3.2) 23 (1.7) 12 (3.8) 23 (2.0)
Vegetable 44 19 (3.8) 6 (6.5) 11 (3.2) 28 (2.5) 27 (1.6)
Non-Catalytic 44 19 (3.8) N/A 18 (1.9) 26 (2.6) 15 (3.0)

TP: total publications; R (%): rank and share of the word in the title; N/A: not available due to the reason that the word did not appear in the title for the study period.

methanol” [16] followed by “Kinetics of transesterification in rapeseed analysis of author keywords and the “optimization” of reaction condi-
oil to biodiesel fuel as treated in supercritical methanol” [102], both tions, discussed in the single title word analysis, because “optimization”
containing “rapeseed” in the title. This fact shows a certain degree of did not appear in the first interval but climbed to position 9 (5.6%) in
temporal delay between the analysis of the WoS keywords and the the third interval. The optimization of supercritical conditions can in-
analysis of the author's keywords or the analysis of single title words. clude the use of heterogeneous catalysts or co-solvents in order to
For this reason, it can be also explained that “soybean oil” and “vege- smooth out the supercritical reaction conditions. The use of energy
table oil” remained in a constant position in the four intervals studied recovery devices could also reduce the energy requirements and the
and that it would not descend in the fourth interval as it happened for study of the process through response surface methodology as well as
the author keywords and in the analysis of single title words. In addi- the study of the kinetics of the supercritical reactions could also con-
tion, this fact can also provide an additional explanation for the results tribute to the development of this technology. In addition, LCA can be
published by Ho [115] in “Comments on “Past, current and future of used as a holistic decision-support technique to qualify and quantify the
biomass energy research: A bibliometric analysis” by Mao et al. (2015)” economic, environmental and societal implications of various bio-re-
regarding the appearance of unrelated publications on the field pro- finery processes, feedstock and integration options [22]. Nevertheless,
vided by WoS keywords. although supercritical technology is not yet ready to be used on an
“Waste cooking oil” (67; 7.2%), a second-generation biodiesel industrial scale, as discussed before, pilot-scale research units have
feedstock, maintained a constant position (around 11) in the four in- begun to be studied.
tervals studied, highlighting the transition from first-generation bio- In summary, the analyses of author keywords, single title words and
diesel to second-generation biodiesel, results that are in line with those WoS keywords showed a clear transition from first-generation biodiesel
reported by Zhang, Gao [22]. “Kinetics” was also consistent with the to second- and third-generation biodiesel with special attention on the

Table 8
20 most used WoS keywords from 2001 to 2019.
WoS keyword TP 2001–2019 R (%) 2001–2005 R (%) 2006–2010 R (%) 2011–2015 R (%) 2016–2019 R (%)

Transesterification 252 1 (27.1) 2 (16.6) 3 (32.9) 1 (20.2) 1 (11.9)


Rapessed 241 2 (25.9) 1 (22.2) 1 (36.1) 2 (20.0) 7 (8.1)
Supercritical Methanol 241 2 (25.9) 4 (11.1) 2 (34.1) 4 (17.8) 1 (11.9)
Vegetable-Oil 220 4 (23.6) 3 (12.9) 4 (31.7) 6 (15.3) 4 (11.2)
Soybean Oil 203 5 (21.8) 7 (9.2) 5 (22.6) 5 (16.8) 3 (11.3)
Fuel 200 6 (21.5) 7 (9.2) 6 (19.4) 3 (19.1) 5 (10.3)
Biodiesel Production 135 7 (14.5) 18 (1.8) 10 (7.9) 7 (12.7) 6 (9.9)
Kinetics 133 8 (14.3) 4 (11.1) 7 (17.0) 8 (10.7) 8 (6.1)
Methanol 84 9 (9.0) 10 (5.5) 13 (6.7) 9 (9.0) 12 (3.9)
Optimization 74 10 (7.9) N/A 24 (3.5) 10 (7.3) 9 (5.6)
Biodiesel 73 11 (7.8) 4 (11.1) 9 (9.5) 13 (5.3) 15 (3.2)
Waste Cooking Oil 67 12 (7.2) 11 (3.7) 15 (6.3) 11 (5.6) 11 (4.1)
Esters 58 13 (6.2) 9 (7.4) 12 (7.1) 15 (4.9) 25 (2.3)
Water 58 13 (6.2) 11 (3.7) 18 (5.9) 14 (5.1) 17 (3.0)
Esterification 54 15 (5.8) 18 (1.8) 26 (3.1) 15 (4.9) 12 (3.9)
Free Fatty-Acid 52 16 (5.5) 18 (1.8) 22 (3.9) 19 (4.0) 12 (3.9)
Sunflower 50 17 (5.3) 18 (1.8) 20 (5.1) 17 (4.7) 21 (2.5)
Fatty-Acid 49 18 (5.2) N/A 10 (7.9) 22 (3.2) 21 (2.5)
Palm 48 19 (5.1) N/A 28 (2.3) 11 (5.6) 19 (2.8)
Oil 46 20 (4.9) N/A 26 (3.1) 23 (3.0) 10 (4.3)

TP: total publications; R (%): rank and share of the WoS keywords; N/A: not available due to the reason that the WoS keywords did not appear in the study period.

13
P. Andreo-Martínez, et al. Applied Energy 264 (2020) 114753

optimization of supercritical reaction conditions. These results are in lipids. Supercritical conditions allow the extraction of microalgae oil
line with those recently reported in previous bibliometric reviews on with subsequent transesterification in a single-step process. These re-
biodiesel [22,32], proving the effectiveness of this type of analysis. cognized advantages will translate into a shift of research focus on
Finally, in order to compare the research trend of biodiesel pro- microalgae utilization.
duction under supercritical conditions with those of other production
methods, the bibliometric analysis for the period 1991–2015 [22] was 5. Conclusions
taken into account. This study reported that “heterogenous catalyst”
was listed in the top 30 most frequently used author keywords from The present work offers the first bibliometric review on the pro-
1991 to 2015, reaching position 21 in 2015, while “lipase” reached duction of biodiesel under supercritical conditions from 2001 to 2019,
position 10 in the same period of time. On the contrary, the word mapping the state of the art in the field over this period and identifying
“supercritical” was not listed in the top 30 most frequently used author current research trends and gaps. In this analysis, a total of 608 articles
keywords. This can be explained by the fact that alkali technology is on biodiesel production under supercritical conditions were found,
widely used on an industrial scale and that biodiesel production via based on the Web of Science© database. The productivity patterns for
enzymatic processes is a growing research field. In addition, these data authors, journals, institution productivity and author keywords fit
corroborate the newness of supercritical biodiesel production tech- Lotka's law. The Price's index value (48.8%) reflected the newness of
nology, as discussed in Section 3.1.1. the field. Fuel (12.4%; h-index: 32), China (15.7%; h-index: 27) and Sila
Science (4.4%; h-index: 18) ranked first as journal, country and in-
4. Future perspectives and research gaps stitution, respectively, in terms of total publications in the topic. The
analyses of author keywords, single title words and WoS keywords
The production of biodiesel under supercritical conditions has been showed a clear transition from first-generation biodiesel to third-gen-
shown to offer numerous benefits and has created high expectations eration biodiesel, in terms of feedstock employed for supercritical
among the scientific community; thus, intensive research is being done biodiesel production, and the increasing interest and necessity of the
worldwide in this field according to the results presented above. With optimization of supercritical reaction conditions in order to reduce the
supercritical conditions, high conversion rates can be achieved in short severity of operation and associated costs. While great attention has
reaction times. This process requires a lower number of unit operation been paid to the study of feedstock and solvent types and of operational
steps in comparison to conventional catalytic processes and has proven parameters such as temperature, pressure, reaction time and solvent-to-
to be suitable to exploit inexpensive low-grade feedstocks like waste oil oil molar ratio, other critical aspects such as economic analysis,
sources. Nevertheless, there are remaining limitations and research mathematical optimization and the reduction of the severity of condi-
gaps that need to be addressed in order to make the technology com- tions through devised strategies (heterogeneous catalysis and use of co-
mercially feasible. solvents in supercritical conditions) needs to be further explored and
Economic analysis and optimization are identified as crucial future addressed in the future so that the technology becomes commercially
research lines. Since there is a lack of economic analysis on biodiesel available. On the other hand, a remarkable decrease in the number of
production in supercritical conditions, it is expected that future efforts total publications was observed in 2019. This may be explained by the
will focus on this critical aspect as lab-scale experimental tests cannot intensive experimental research performed in the lasts years, while
be directly linked to their viability on an industrial scale. On the other process optimization and concrete remaining challenges such as high-
hand, mathematical optimization through modeling tools is required to energy consumption in the process, which narrows the scope of re-
assess the main parameters of the supercritical process, especially in search, can be expected to be the focus of future studies.
terms of temperature, feedstock composition, reaction time and solvent-
to-oil ratio. Systematic approaches through optimization, together with Declaration of Competing Interest
economical analysis, will greatly contribute to the practical im-
plementation of supercritical processes for biodiesel generation by The authors declare that they have no known competing financial
identifying the trade-offs of the technology. In addition, there is still a interests or personal relationships that could have appeared to influ-
necessity to fully understand the reaction mechanisms involved, and ence the work reported in this paper.
the kinetics of supercritical reactions have not yet been resolved.
Moreover, the development of proper reactor models is necessary to be Acknowledgements
used for process design and decision-making. Also, the environmental
impacts of supercritical technology have to be studied in greater depth This research was funded by the Fundación Séneca, grant number
with respect to conventional catalytic transesterification processes. 20957/PI/18 and The Ministry of Economy and Competitiveness
The high temperatures required in supercritical biodiesel produc- (MINECO) grant number RTI2018-099011-B-I00. The authors would
tion are associated with high energy consumption, which increases like to thank Ms. Seonaid McNabb for the revision of English.
operational costs. In addition, temperature is a key parameter to control
the final conversion yield. While high temperatures can generally in- Appendix A. Supplementary material
crease conversion rates over time, several strategies can be im-
plemented in order to balance reaction conditions, such as the use of co- Supplementary data to this article can be found online at https://
solvents. On the other hand, high temperatures can lead to the de- doi.org/10.1016/j.apenergy.2020.114753.
gradation of the product obtained in the process, which needs to be
further examined in future research works. References
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