Fuel 340 (2023) 127485

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New trends on crude glycerol purification: A review

Taha Attarbachi a, b, Martin D. Kingsley b, Vincenzo Spallina a, *
a
Department of Chemical Engineering, University of Manchester, M13 9PL Manchester, United Kingdom
b
Argent Energy Ltd., CH65 4BF Ellesmere Port, United Kingdom

A R T I C L E I N F O A B S T R A C T

Keywords: The increasing effort of the global community to reduce dependency on fossil fuels led to an increase in the
Crude glycerol production of biodiesel and therefore the oversupply of crude glycerol. Different steps are necessary to ensure
Purification this oversupply of highly impure, waste-based crude glycerol (approximately 680,000 tonnes by 2024) can be
Glycerol market
made suitable for applications. This review paper aims to give an overview of the recent developments of the
Biodiesel
global glycerol market and discusses advanced crude glycerol purification technologies (as compared to physio-
Pre-treatment
chemical treatments). The market overview involves information on the relevance of the global glycerol market
and the different grades of glycerol which are produced. Additionally, different application areas for glycerol are
detailed; including current industrial solutions, challenges, and outlooks. The second part reports newly pro­
posed crude glycerol purification technologies from industry and recent research since 2014, their advantages
and disadvantages, and feasibility in terms of industrial implementation at scale. The results of this review
suggest that pressure-, thermally- and electrochemically-driven membrane-based separation technologies could
solve the issue of expensive large scale vacuum distillation columns lowering capital and operating expenditures
reaching > 99 % of glycerol purity. However, the increase of lower quality glycerol generated resulting from 2nd
generation bio-diesel plants presents challenges due to the increasing ash and matter organic non-glycerol
(MONG) impurities (due to the use of waste-based feedstocks in biodiesel production). As result, hybrid solu­
tions may be needed since advanced purification technologies cannot be used as stand-alone solutions but need
to be accompanied by a proper pre-treatment.

glycerol during the last decade, which is mainly incinerated [6], used for
1. Introduction cattle feed [7,8], biogas generation [9,10], or even transferred to landfill
[11].
As the world population increases, the need for sustainable devel­ Glycerol (C3H8O3), also known as Propane-1,2,3-triol, is a major
opment in economic, environmental, and social terms is necessary [1]. component in many products used in our daily lives. It is a major
Biofuels are pillars of a sustainable society and will play a significant component in the personal care and pharmaceutical industry due to its
role in the coming decades and will ultimately supersede conventional mildly antimicrobial and antiviral properties, used as a sweetener in the
fossil fuels. The EU implemented the Renewable Energy Directive EC/ food industry. The use of crude glycerol has been considered also for
2009/28, which mandates a level of 10 % for renewable energy use in applications such as gasification for the production of hydrogen and
transport for 2020 [2]. This number will increase to 14 % by the year other products [12]. Some of the properties of glycerol are listed in
2030 [3]. Increasing the sustainability of how biofuels are produced will Table 1.
play a critical role as the target increases. Advanced biofuels are Early in the 20th century, glycerol was produced primarily as a by-
considered the same product as first-generation biofuels but utilise product of the saponification of fats (Fig. 1) and was used as a raw
waste-based, non-edible feedstocks [4]. In biodiesel production, this has material to produce nitro-glycerine. During the 1st world war, glycerol
led to a shift of using waste-feedstocks such as tallow or used cooking oil became a strategic resource, and therefore the demand exceeded the
instead of crop-based vegetable oils [5]. Biodiesel production involves a supply, leading to the first synthetic plants to produce glycerol by mi­
transesterification reaction, which yields crude glycerol as a by-product. crobial sugar fermentation. Furthermore, the replacement of natural
In the case of waste-based biodiesel feedstock, glycerol purity drops soaps with synthetic washing detergents has led to an increase in glyc­
drastically. This has led to an excess supply of highly impure crude erol demand which accelerated the shift towards competitive

* Corresponding author.
E-mail address: [email protected] (V. Spallina).

https://doi.org/10.1016/j.fuel.2023.127485
Received 28 August 2022; Received in revised form 26 November 2022; Accepted 8 January 2023
Available online 31 January 2023
0016-2361/© 2023 The Author(s). Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-
nc-nd/4.0/).
T. Attarbachi et al. Fuel 340 (2023) 127485

Nomenclature ICP Inductively coupled plasma

LCD Limiting current density
ABP Animal by-product MD Membrane distillation
AC Activated Carbon MOF Metal organic frameworks
AEM Anion exchange membrane MONG Matter organic non-glycerol
AGMD Air gap membrane distillation MT Metric ton
BED Bipolar Electrodialysis MWCO Molecular weight cut-off
CAT Category RSM Response Surface Methodology
CAGR Compound annual growth rate PTFE Polytetrafluirethylene
CEM Cation exchange membrane PVDF Polyvinylidene fluoride
CEMD Continuous-effect membrane distillation SGMD Sweeping gas membrane distillation
CG Crude glycerol TAG Triacylglyceride
DCMD Direct contact membrane distillation TEOS Tetraethylorthosilicat
ED Electrodialysis TFC Thin Film Composite
FCC Food Chemical Codex TMP Trans-membrane pressure
FFA Free fatty acids UCO Used cooking oil
FOGS Fats, oils and greases (mainly waste-water treatment USP United States Pharmacopeia
based) VMD Vacuum membrane distillation
GMO Genetically modified organism ZHP Zirconium hydrophosphate
GOR Gain output ratio
HVO Hydrogenated Vegetable Oils Greek letters
HZD Hydrated zirconium dioxide ηD Refractive Index

petrochemical (synthetic) production routes. The company I.G. Farben

Table 1 used high-temperature chlorination of propene to allyl chloride process
Main properties of glycerol at room temperature [13]. to produce synthetic glycerol [14]. About 25 % of the global glycerol
Properties
demand was met by petrochemical synthesis from propylene before the
acceleration of the biodiesel market in the early 1990s. The other 75 %
Chemical formula C3H8O3
was obtained by the saponification of fats [15].
Molar mass [g/mol] 92.094
Appearance Colourless hygroscopic liquid With the development of the biodiesel industry, crude glycerol has
Odour Odourless been produced as a by-product from bio-diesel production using vege­
Density [g/cm3] 1.261 table oils as well as waste animal fats, UCO (used cooking oil) and other
Melting point [◦ C] 17.8 waste fat as feedstocks [16]. During the transesterification reaction of
Boiling point [◦ C] 290
Solubility in water miscible
triglycerides with methanol, approximately 10 wt% of glycerol is pro­
Lower heating value [MJ/kg] 24 duced as a by-product [17].
Refractive Index (ηD) 1.4746 Since most of the crude glycerol cannot be utilized due to major
Viscosity [Pa•s] 1.412 impurities [18], this paper seeks to review conventional, recent, and
novel purification methods which can improve the quality further to
provide the global glycerol market with a feedstock with suitable purity.
Glycerol is produced as a by-product in four main reactions, which
are depicted in Fig. 1. All these reactions involve different chemicals and
produce different products and by-products, which influence its final
composition. This final composition has a significant effect on the pu­
rification effort, which must be delivered to valorise the crude glycerol
and subsequently convert it into higher-value chemicals. In Table 2, the
average glycerol compositions generated by three main reactions are
depicted. Typical impurities in crude glycerol are water (also moisture),
ashes (i.e., inorganic salts containing potassium, phosphorous, sodium,
iron, and others), and MONG (matter organic non-glycerol), which
usually consists of FFAs (free fatty acids), FAME (fatty acid methyl es­
Fig. 1. Conventional reactions of oils and fats in the oleochemical sector ters), glycerides (mono-, di- and triglycerides), alcohols such as meth­
yielding glycerol as by-product. The reaction mechanisms are given in Appen­ anol or ethanol and soaps (saponified fatty acids, i.e., fatty acid salts)
dix A. Figure adapted from reference [14]. [19] and other organic compounds (e.g. Aldehydes) [20]. In the case of
direct hydrogenation, it is not possible to determine the composition of
the crude glycerol due to the decomposition of the material. Hence, this
Table 2 process is not commercially implemented [21].
Average crude glycerol composition by different production processes [22]. The lowest purity of glycerol is obtained by the transesterification
Component Transesterification Saponification Hydrolysis reaction (in biodiesel production), which also yields the highest
[%] [%] [%] amounts of ashes due to alkali-based catalysts. This is highly problem­
Glycerol 30–60 83–84 88–90 atic since the inorganic ashes act as major inhibitors in many biotech­
Ash 10–19 8.5–9.5 0.7–1.0 nological applications [23] and often poison the heterogeneous catalysts
Water 6–7 8–9
≤10
of downstream chemical conversion units [24]. Furthermore, high
MONG ≤40 3–4 0.7–1.0
MONG content is being generated due to partially reacted glycerides,

2
T. Attarbachi et al. Fuel 340 (2023) 127485

of low-cost, waste-based feedstocks such as sewage sludge, FOGs (fats,

oils and greases), animal fats and tallow are interesting due to their high
oil content. Their use does not just reduce the cost of feedstock but alters
the usually acceptable purity of the by-product of crude glycerol as it
decreases its purity down to 30 % wt. as reported by industrial exam­
ples.1 To improve the environmental and economic performance, crude
glycerol valorisation through proper purification methods has been
proposed and is currently under consideration by research and industry.
This paper reviews the current and recent global glycerol market
(section 2) and particularly focuses on novel purification methods
(section 3) discussed in the recent scientific literature sources. A special
focus is set on new technologies recently proposed in 2014 mostly
Fig. 2. Global biodiesel and glycerol production Biodiesel values for focused on pressure-, thermal- and electrochemical-driven processes
2020–2025 are calculated based on a density of 880 kg/m3 (density at 25 ◦ C). which were not compared comprehensively before. This work provides
Glycerol values are based on 10 wt% of the production of biodiesel. The total the foreground and industrial guidance to implement develop and scale
production is deduced from the assumption/simplification that from 2009 to
up new technologies which could reduce costs and technical challenges
2025 biodiesel supplies 64 % of the entire glycerol market. Data taken from
for the bio-diesel industry.
reference [34,35].

2. Market overview

2.1. Global biodiesel and glycerol production

The global glycerol market had a market volume of $2,500 million in

2018 and it is expected to increase to $3,300 million by 2023 [28],
having a CAGR of 5.7 %. Due to the versatility of glycerol and its
application in the personal hygiene sector, this demand is likely to be
maintained. Most of the glycerol that is supplied on the market is
derived from the biodiesel industry. As can be seen in Fig. 2, the bio­
diesel market has grown dramatically in the last 30 years since its
market introduction (early 1990s [29]). This is largely influenced by
governments wanting to continuously increase the uptake of renewable
fuels and fulfil their sustainability goals [30]. In 2009, approximately
Fig. 3. Major biodiesel-producing countries (2016) in %. Data taken from 64 % of the glycerol was supplied by the biodiesel industry compared to
reference [25] and adapted. the original 9 % in 1999 [15]. This number did not change significantly
and remained high at 63 % in 2018 [28]. The remaining glycerol is
supplied mostly by the soap or fatty acid industries, available already at
high purity. The major biodiesel producers such as Indonesia [31]
planned to increase their biodiesel mandate up to B40 (which is equal to
40 vol-% of biodiesel mixed with conventional diesel). The cost associ­
ated with fuel blending has led to a failure or delay in similar plans in
Malaysia [32] and Brazil [33]. The biodiesel market experienced a
downturn in 2020 due to the COVID-19 pandemic, but it is expected to
reach 40 million tonnes per year in the next 3 years (Fig. 2). As a result,
about 6.3 million tonnes of crude glycerol will be produced by 2025.
The European Union is the biggest single contributor to the biodiesel
market with 26 %, followed by the United States and Brazil (Fig. 3). At
the same time, the EU has the highest cost of production with 0.82 USD/
litre compared to 0.47 USD/litre in the United States [36]. Generally,
biodiesel producers are differentiated based on the feedstocks used for
Fig. 4. Feedstocks used in world biodiesel production (2016) in %. Data taken the transesterification process. First-generation biodiesel producers use
from reference [51] and adapted. edible oil feedstocks [37] such as palm oil or rapeseed oil, while second-
generation biodiesel producers use waste-based feedstocks [38] such as
residual FAME, fatty alcohol, or fatty acids which are used in the animal fats, tallow, UCO, or sewage material such as FOGs [39].
transesterification reaction reducing the glycerol content even further. Currently, research is being undertaken for algae utilization to become
The usual pH value of crude glycerol in the transesterification lies above the third generation of biodiesel [40] and GMOs to become the fourth
7 due to the usage of alkali catalysts such as sodium hydroxide, potas­ generation feedstocks for biofuels [41].
sium hydroxide, or sodium methoxide [25] but can also be acidic if a The high cost of production and feedstock/commodity, as well as
neutralisation step of the crude glycerol takes place. environmental pressure to refrain from edible oils such as palm oil as
The quality of crude glycerol from biodiesel industry varies consid­ feedstocks, has led to an increase in waste-based feedstocks to produce
erably (Table 2). Usually, the crude glycerol produced from biodiesel biodiesel [42] (Fig. 3). Currently, animal fat and UCO account for 17 %
refineries using edible oils or purified used cooking oils yields crude of the entire feedstock, Fig. 4, which means that from the 4.04 million
glycerol with acceptable purities (60–80 %) [27]. However, there is a tonnes of bio-glycerol which will be produced by the end of 2025 (64 %
trend among producers to utilize waste-based feedstocks due to their
cheapness, availability, abundance and sustainability (as it does not
compete with food prices such as edible oils) [26]. Particularly, the use 1
Argent Energy glycerol purity available from 30% to 70% depending on the
feedstock.

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T. Attarbachi et al. Fuel 340 (2023) 127485

Table 3 biodiesel production, especially in Europe and other developed coun­

Different grades of glycerol, after [52]. tries, will increase the need for suitable vegetable-based crude glycerol
Grades of glycerol Glycerol content [wt.%] supply which can be used in the refined glycerol market for hygiene
applications, and it may even be possible, though unlikely, for chemical
Crude glycerol 30–90
Technical grade 95.5 companies to re-enter the market again to produce synthetic glycerol to
United States Pharmacopeia (USP) 96 (tallow-based) sustain the demand for refined glycerol as DOW chemical did in 2008
96–99 (vegetable-based) [50].
Food Chemical Codex (FCC) 99.5 USP/FCC-Kosher It can be concluded that the excessive development of the biodiesel
99.7 USP/FCC-Kosher
industry led to an excess supply of mostly impure (bio-)glycerol. This
excess supply of crude glycerol consequently led to an imbalance in
supply and demand, potentially leaving a much higher supply in 2025 of
Table 4 approximately 6.33 million tonnes, from which 680 kilo-tonnes are
Animal by-products (ABP) categories [55]. highly impure, to a much lower demand of 4 million tonnes in 2025,
ABP Risk Content making supply and demand effectively independent from each other.
categories The consequences are very low prices for impure crude glycerol with the
Cat 1 High • Carcasses of (wild) animals suspected of being probability of it becoming even a waste stream.
risk infected with TSE or other diseases that humans/
animals could contract
2.2. Glycerol grades
• Zoo/circus animals
• Animals used in experiments
Cat 2 High • Carcasses containing residues from authorised The industry distinguishes between different grades of glycerol,
risk treatments, of animals killed for disease control based on its purity (by wt.%). An overview of the different grades is
purposes, of dead livestock given in Table 3.
• Manure
• Digestive tract content
Glycerol grades for non-food applications are termed technical grade
Cat 3 Low • Carcasses passed fit for humans to eat at a and the maximum purity reaches 95 %wt. USP grade glycerol has a
risk slaughterhouse purity of 96–99 % wt. and is used for food and pharmaceutical appli­
• Products/Foods of animal origin originally meant for cations. The highest purity has the FCC grade with a purity of 99.5–99.7
human consumption but withdrawn for commercial
% wt. The application area for this glycerol is mainly in kosher foods.
reasons
• Domestic catering waste The high range of crude glycerol is due to the different feedstocks which
• Hides/skins from slaughterhouses can be used to produce biodiesel. Biodiesel producers using waste
• Eggs and egg by-products feedstocks such as ABP (Animal by-products) have legal problems to sell
their glycerol to the pharmaceutical and hygiene industries [53]. ABP
can be considered as parts of the animal which are not meant for human
Table 5 consumption, mainly consisting of abattoir waste. ABP is categorised in
Refined and crude glycerol prices for different relevant global areas (June/ three different ways, which are listed in Table 4. The price per ton de­
December 2020). creases with lower categories due to the limited applications of by-
Product USA Europe China product glycerol which can only be used to make compost, biogas, or
[€/tonne] [€/tonne] [€/tonne] other low-value products. In many cases, the crude glycerol must be
Refined glycerol (99.7 %, kosher grade) 705 650 565 disposed, thus resulting in a net cost such as in Brazil where incineration
Refined glycerol (99.5 %, technical grade) 660 520 505 is 15 $/tonne [54]. Nevertheless, there is no regulation on the usage of
Crude glycerol (80 %, vegetable-based) 200–280 395 295 ABP categories (Table 4) such as Cat 1 and Cat 2 to produce energy or
Crude glycerol (75 %, non-vegetable- 180–240 150–250 145–175 high value intermediate chemicals, making them an interesting alter­
based)
native (green) feedstock for these applications.

of entire glycerol production), approximately 680,000 tonnes of crude 2.3. The US, European, and China glycerol market
glycerol (17 % of the bio-glycerol production) will be with a maximum
purity of 76.6 % [27] and cannot be used for personal care, food or other The global glycerol market is highly fragmented due to the various
traditional glycerol application sectors. This amount likely increases grades that exist. As depicted in Fig. 3, the most relevant areas in the
further in the future due to legislative issues as well as deforestation biodiesel market and consequently also in the glycerol market are the
concerns [43] and the competition for food [44], which are inherent US, the European Union, and other international countries. In case of
when using edible oils as feedstocks [45]. On the other hand, crude glycerol, China is the biggest country to consume glycerol [56].
glycerol consumption from 2010 to 2019 in the North America and EU Generally, different spot prices (intended as market prices) are available
market combined have been on average 450,000 tonnes annually [46] for refined, technical, and crude glycerol for different regions in the
and global glycerol consumption is expected to reach 4 million tonnes by world. The historical price development of kosher grade glycerol with a
2024 [47] outstripping the supply by over 2 million tonnes. purity of 99.7 % for the period of 1995 to 2020 in the US and EU markets
However, the crude glycerol market will change significantly within show that spikes in both markets are synchronized, and the prices follow
the next two decades, especially in the regions of Europe, the US, and the same trend ranging between 400 and 800 €/tonne [57]. The entire
China as electric cars are replacing internal combustion engines. Addi­ market surged during 2020, especially due to the COVID-19 pandemic,
tionally, pressure is being created by competing technologies such as where many countries required high-grade glycerol for the pharma­
renewable diesel, which does not produce glycerol within their supply ceutical and health industries [58]. Refined and crude glycerol prices for
chain [48]. These factors are pressuring the biodiesel industry, and it the year 2020 and different areas are listed in Table 5 [59,56]. It also
remains unclear whether the market will favour HVO (hydrogenated shows why the valorisation of crude glycerol to refined technical glyc­
vegetable oil) or biodiesel in the long term. While in general the market erol is economically reasonable despite the existing cost of purification
is expected to grow during the next decade due to an increasing trend to and refining. It is important to mention that crude glycerol from pro­
replace fossil fuels with biofuels [49], renewable diesel could partially cessing plants using feedstocks from ABP has a much lower value and
slow down the total production. The further shift towards waste-based reaches a negative value [60].
The glycerol market, in general, is highly volatile and subject to

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T. Attarbachi et al. Fuel 340 (2023) 127485

Table 6 2.4. Application areas of glycerol

Research on crude glycerol valorisation to valued-added chemicals
(2019–2021). The references next to the authors are referring to the academic Glycerol can be sold by producers as a refined commodity on the
papers. global market as well as be used in various other applications. Current
Author Year Research Product Price market applications which exist and have large-scale use (pharma and
Focus [US personal care 42%, Alkyd resins 13%, Food and Beverage 14%, Poly­
$/kg]
ether polyols 10%, tobacco 9.5%, others 11.5%) [28]. Pharmaceuticals
Kumar et al. 2021 Chemical Polyhydroxybutyrate (PHB) 4.75 and personal care are overwhelmingly the largest area for refined high-
[70] Industry [71] grade glycerol with a share of over 40 % where glycerol is used due to its
Hassan 2019 Biotechnology Hydrogen 0.79
et al. ButanolPolyhydroxyalkanoate [73]
antimicrobial and antiviral properties [61], followed by the alkyd resin
[72] (PHA) 0.89 market, which uses technical grade glycerol [62], the food industry
[74] where glycerol is used as a humectant, solvent and even sweetener [63].
2.40 In the tobacco industry, glycerol is used to preserve the tobacco and keep
[75]
it moisturized [64]. Other application areas include cattle feed, incin­
Almuharef 2019 Biotechnology 2,3-butanediol 10–50
et al. Acetoin [77] eration for energy generation, or anaerobic digestion [65], especially for
[76] waste-based biodiesel feedstocks (ABP feedstocks). Additionally to the
10–30 above uses, glycerol is already used or subject to research to produce
[77] important chemicals such as epichlorohydrin [66], propylene glycol
Veiga et al. 2020 Energy Hydrogen 0.79
[67], or bio-methanol [68]. New routes for the production of chemicals
[78] [79]
Zahid et al. 2021 Chemical Solketal 3 [81] such as acrylic acid are being investigated as well [69]. Especially, crude
[80] Industry glycerol has been the focus of many different research papers during the
Sittijunda 2020 Biotechnology Hydrogen 0.79 last years. Due to the excess supply and its low price, researchers all over
et al. 1,3-propanediol [79]
the world try to develop novel methods to valorise and subsequently
[82] Ethanol 1.45
[83] convert crude glycerol into very high-value chemicals via (bio-) chem­
1.06 ical routes.
[84] Research is mainly taking place in the areas of biotechnology,
Genieva 2020 Chemical Alkyd Paints – chemical, and energy industries. While in the chemical and energy in­
et al. Industry
dustries, the focus is to convert it into bulk chemicals, in the area of
[85]
Yao et al. 2020 Biotechnology β-farnesene 8.6 × biotechnology, the focus lies on speciality chemicals, which are sold in
[86] 106 1) the ranges of milligrams but have a very high price per unit mass as
[87] shown in Table 6.
Wang et al. 2020 Chemical Alanine –
[88] Industry
Tian et al. 2020 Biotechnology Lipase – 3. Advanced glycerol purification techniques
[89]
Shahrin 2019 Biotechnology Monolaurin 1.55 × The problems associated with crude glycerol derived from biodiesel
et al. 106 1) are the significant amounts of impurities it contains, such as methanol,
[90]
Abd Rahim 2019 Biotechnology Lovastatin 6. ×
salts, and a high MONG content, namely soaps, FFAs and esters. Since
et al. (+)-geodin 106 1) the purification of crude glycerol is costly and often not economical for
[91] Sulochrin [92] small and medium-sized biodiesel plants [99], crude glycerol is disposed
810 × at cost [100]. Several techniques are available for the purification of
106 1)
crude glycerol. Depending on the scale and composition of the crude
[93]
145 × glycerol, a combination of different purification routes is applied. A big
106 1) problem in crude glycerol purification remains the volatility of the crude
[94] glycerol composition, making it complicated to find a standardized
Wu et al. 2019 Biotechnology Levoglucosan 150 × method of purification. Purification techniques include sequential
[95] 106 1)
[96]
physio-chemical treatments such as saponification, acidification, phase
Wang et al. 2019 Biotechnology Polysaccharide production – separation, neutralization and anti-solvent treatment with a solvent
[97] [101–103]. Furthermore, advanced refining technologies are applied to
Rodrigues 2020 Energy Hydrogen 0.79 purify crude glycerol, such as vacuum distillation [104], ion exchange
et al. [79]
[105], membrane separation [22], adsorption [106], electrodialysis
[98]
[107] and membrane distillation [108].
1) Prices are related to small quantities (100 mg), here recalculated to kg. Conventionally, four refining steps are necessary to purify the glyc­
erol [52]:
constant change. For the European market in the second half of 2020,
crude glycerol (80 %) for kosher applications experienced a fall from 1. Reduction of MONG and salt content through saponification, acidi­
approximately 500 €/tonneGly to 400 €/tonneGly while crude glycerol of fication, and subsequent neutralization [22,101,102,109]
80 % purity increased from 160 €/tonneGly to almost 250 €/tonneGly. 2. Anti-solvent treatment with a solvent/alcohol [110]
The same trend can be observed with refined glycerol. Prices plummeted 3. Evaporation of solvent/alcohol and water to concentrate the solute
for kosher grade glycerol from 825 €/tonneGly to almost 550 €/tonneGly [111]
and recovered by the end of 2020 to a price of slightly below 700 4. Adsorption with activated carbon to remove colour and odour
€/tonneGly. A similar course showed the technical grade glycerol, which [112,113]
started at 650 €/tonneGly in the second half and plummeted to 475
€/tonneGly, reaching a value of 625 €/tonneGly at the end of 2020 [46]. A comprehensive review of physio-chemical treatments up to 2014
has been conducted by Ardi et al. [52] and appendix B presents an
overview of purification experiments which have been conducted by
various authors after 2014, providing information on the purification

5
T. Attarbachi et al. Fuel 340 (2023) 127485

Table 7
Overview of adsorbents used by different authors for the purification of crude glycerol.
Adsorbent/Source Year BET Pore Micro-pore Optimal Contact Operating Comment Ref.
surface size volume Ratio/ time [h] Temperature
area [m2/ [nm] [cm3/g] Dosage [◦ C]
g]

Bentonite 2018 n/a n/a n/a 12 % 1.25 60 Particle size: 60 mesh (0.2 [115]
mm)
Tea Waste 2018 n/a n/a n/a 12 % 1.5 60 Particle size: 180 µm [116]
Reactivated spent bleaching 2021 73.1 n/a 0.164 10 wt% 1 50 Removal rate: 93 % (FFA, [118]
earth/Solid waste from palm cartenoid, chlorophyll
oil refinery removed)
Activated Charcoal/Acrocomia 2020 627 2.5 0.09 10 g/L 2 25 Column packed with activated [120]
aculeate endocarp carbon (h = 15 cm, d = 1 cm,
mAC = 10 g)
Activated Carbon/Wastewater 2017 107 n/a 0.09 67 g/L 2 30 AC adsorption followed [102]
treatment sludge Langmuir isotherm
Activated Carbon 2016 n/a n/a n/a 0.933 g / 2 n/a Bleaching Earth used as [122]
10 mL comparison to AC
Organo-bentonite and 2011 n/a n/a n/a 1%+1% 1 50 Organoclays have limited [117]
activated carbon efficiencies in the removal of
colour, only useable as co-
adsorbents
Dead yeast cells immobilized 2014 n/a n/a n/a 10 g/L 0.67 n/a Use of microwave irradiation [119]
on chitosan/Saccharomycess using a microwave oven at
cereviceae, chitosan-based 2.56 GHz
biosorbent
Electrospun chitosan/poly 2018 n/a n/a n/a n/a n/a n/a Relative high adsorption [114]
(ethylene oxide) nanofibers/ capacity compared with
chitosan-based biosorbent chitosan powders/films (120/
g)
Activated Charcoal 2019 n/a n/a n/a n/a n/a 60 Equilibrium, thermodynamic [123]
and kinetic study on the use of
AC
Activated Carbon/Oil palm 2021 26 80.13 0.17 2.5 wt% 1 n/a Colour removal: >89 % [100]
empty fruit bunch (OPEFB)

route and the final purities of all relevant components such as glycerol, activated carbon and 1 % of microwave dried organoclay is as effective
water, ash, and MONG. as 3 % of fresh activated carbon when conducted at 50 ◦ C and 1 h contact
Recently, the focus has shifted to more advanced purification tech­ time. Hence, a reduction of 60 % in material usage could be shown with
nologies to achieve a more economically feasible purification of indus­ the usage of organo-bentonites as co-adsorbents. Isalmi Aziz et al. [116]
trial waste-based crude glycerol. Advanced glycerol purification used tea waste as an adsorbent which was activated by 0.05 M sodium
techniques are usually applied in combination with a physio-chemical hydroxide and varied the contact time (30–120 min), the adsorption
pre-treatment [22,111]. temperature (30–75 ◦ C), the bio-sorbent concentration (6–18 %), and
bio-sorbent particle size (180–630 µm). Before this, the crude glycerol
mixture was acidified with phosphoric acid. The highest glycerol purity
3.1. Adsorption using waste-based biogenic materials of 95.95 % wt. was achieved by setting the contact time to 90 min,
adsorption temperature to 60 ◦ C, bio-sorbent concentration at 12 %, and
Adsorption is preferably used as a final step after other separation particle size at 180 µm. A different bio-sorbent was used by Hunsom
techniques to reduce the colour as well as the odour by removing mainly et al. [113]. A wastewater treatment sludge-derived KOH-activated
smaller fatty acids from the glycerol mixture [114]. Usually, a porous carbon was used with various KOH:char ratios (1–6 w/w), KOH soaking
material is used, such as commercially activated carbon, but the focus times (5–25 h) and activation temperatures (500–900 ◦ C) used to pre­
shifted during the last years more towards waste adsorbents such as pare the material. The best material was obtained by using a KOH:char
bentonite [115] or tea waste [116]. An important step for the utilization ratio of 5 with a soaking time of 25 h and an activation temperature of
of waste-based adsorbents is the proper chemical or physical activation. 800 ◦ C which was used to upgrade glycerol to a purity of 93 wt% when
With ultraviolet–visible spectroscopy, the colour reduction and trans­ used at a dose of 67 g/L for a contact time of 2 h and stirred at 250 rpm.
parency of (crude) glycerol can be measured at a wavelength of Hunsom et al. [112] published earlier similar experiments by investi­
200–800 nm [109]. Pure glycerol has a low absorbance rate compared to gating the influence of different chemical activating agents such as
crude glycerol, which is one variable to determine the degree of purity in phosphoric acid, potassium carbonate and potassium hydroxide but
the glycerol mixture. Variables which are investigated in adsorption came to similar results as in the previous paper that using KOH as
experiments are the contact time, the temperature, type of adsorbent, reactivating agent yields the best surface properties. Different materials
(re-)activation as well as activated carbon loading. were used by other authors such as spent bleaching earth [113,118] or
Anzar et al. [115] used bentonite, which was activated with 1.5 M spent activated carbon [106] after reactivation, bio-sorbent synthesized
sulphuric acid after acidification. Therefore, 100 g of crude glycerol was from dead yeast cells immobilized on chitosan [119], activated carbon
mixed with 12 g of bentonite. The mixture was investigated at different from Acrocomia culueata endocarp [120] or from oil palm biomass
stirring rates (30–90 min), bentonite concentrations (3–15 % wt. based [121] and synthetically produced electrospun chitosan/poly(ethylene
on crude glycerol weight), and temperatures (30–70 ◦ C). The optimum oxide) nanofibers [114]. Table 7 gives a general overview of adsorbents
conditions of adsorption were stirring at 75 min, 12 % wt. bentonite used by different authors as well as the optimal conditions that were
concentration, and a temperature of 60 ◦ C, leading to a glycerol purity of used.
89.5 % wt. Organo-bentonites were also used by Kocak et al. [117] to The general shift to waste-based adsorbents involves different
replace fresh activated carbon with the result that a mixture of 1 % of

6
T. Attarbachi et al. Fuel 340 (2023) 127485

some glycerol. Overall, the entire process has been seen as a simple way
of purifying crude glycerol, albeit with a very high vacuum applied.
Isahak et al. [126] used the same configuration but with prior pre-
treatment to achieve a purity of 96.6 % wt. at an optimum pH of
smaller than 5 to avoid foaming just as with Ooi et al. [104]. Their work
also clarified that at high temperatures, free sodium hydroxide reacts
with the fatty acids to form short and medium chained soaps and that
higher pH levels intensify this reaction. The same configuration was
used by Yong et al. [104], which yielded the same purity at a pH of 3.5.
Pitt et al. [11] used a vacuum distillation step at 120 ◦ C to remove water
and alcohol fraction after neutralization and vacuum filtration and prior
to the adsorption step. According to the experiment, the distillation step
provided the greatest increase in density due to the removal of lower
density components which increased the density from 1.1243 g/cm3 to
1.2460 g/cm3.
Fig. 5. Working principle of vacuum distillation for crude glycerol purification.
Vacuum distillation has proven itself as the only suitable industrial
purification method to treat comparably pure, crude glycerol. It can be
applied as a single purification step (if sweet water containing 10–20 %
wt. of glycerol is used as feedstock) or within different purification steps.
Nevertheless, vacuums applied in the research experiments are far too
low to be applied in real-life applications – e.g., crude oil vacuum
distillation works at a very high vacuum of 10–30 mbar [127].
Furthermore, highly impure crude glycerol containing high MONG and
ash contents require different pre-treatments to increase the glycerol
purity which will increase the operating costs of vacuum distillation.

3.3. Ion-exchange resins

Ion-exchange resins are mostly used as an additional step for refining

in the purification route. Ion-exchange resins are mainly used to remove
low amounts of salts from aqueous solutions [128]. The principle of ion
exchange is depicted in Fig. 6: the cations and anions of the crude
Fig. 6. Working principle of ion-exchange resins for the purification of glycerol solution are exchanged by the cationic and anionic ions in the
crude glycerol. resin resulting in the formation of water which must be subsequently
removed from the purified glycerol solution. The process is not energy
positive and negative aspects which must be considered for the purifi­ intensive, and the resins can be regenerated [13]. Typical parameters
cation process. The material is abundantly available and cheap. Never­ which are varied are the bed height, residence time or operating tem­
theless, its preparation requires the addition of external chemicals which perature. Table 8 gives an overview of different ion-exchange resins
generate additional wastes, which must be considered during the puri­ which have been used for the purification of crude glycerol by different
fication step. Furthermore, their reactivation requires the addition of authors.
solvents which must be treated subsequently as well [113]. Abdul Raman et al. [12] used as a pre-treatment step acidification
and subsequent ion-exchange resin to purify crude glycerol from an
3.2. Vacuum distillation initial purity of 35.6 % wt. to 98.20 % wt. Therefore, a cation exchange
H + resin was used (Amberlyst 15), and the optimal operating condi­
Crude glycerol can be purified by vacuum distillation as depicted in tions were determined as 40 g of resin, a flow rate of 15 mL/min, and 60
Fig. 5 due to its sensitivity and preference for undesirable reactions at % of solvent. Isahak et al. [126] used Amberlite IRN-78 and Amberlite
high temperature. Three possible unwanted side reactions can take 200C to remove free ions from crude glycerol after neutralization and
place. At high pH values, polymerization of glycerol to polyglycerol can microfiltration. Furthermore, silica beads were added to reduce the
take place if an excess of sodium hydroxide is used and the temperature moisture content. After the treatment, the resin was regenerated by
is higher than 200 ◦ C [124]. At low pH values, glycerol can dehydrate washing with diluted sodium hydroxide for Amberlite IRN-78 and
into acrolein [125]. diluted sodium chloride for Amberlite 200C. The purity of the initial
Furthermore, it can oxidize to glycerose, which is a mixture of 77.4 wt% could be increased to 99.4 wt% and subsequently reduce the
glyceraldehyde and dihydroxyacetone [104]. Nevertheless, vacuum amount of ash by 99.9 % wt. An increase of 59.3 % wt. crude glycerol to
distillation is effective at recovering glycerol from crude glycerol in the 85 % wt. of ion-exchange treated glycerol was achieved by Lopes et al.
presence of high salt and MONG content. A big disadvantage is the high [20] by applying a three-step ion exchange method consisting of a
energy input for vaporization, maintaining a high vacuum, and high cationic step followed by two anionic steps. Priya et al. [105] used ion-
capital expenditure, making the process uneconomical for small and exchange resins in a column to purify 18 % crude glycerol up to 40 %
medium-sized plants [52]. Furthermore, the use of vacuum distillation (crude) glycerol by using a bed height of 6 cm at 40 ◦ C.
for highly impure crude glycerol is questionable due to the low yield and A more fundamental study was conducted by Carmona et al. [128].
the possible clogging of the bottom. The most thorough analysis of crude The aim was to obtain the equilibrium and kinetic data for an ion ex­
glycerol purification via vacuum distillation was done by Ooi et al. change process using 0.5 L of a glycerol-water mixture (90 % wt. glyc­
almost 20 years ago [104]. 1 kg of crude glycerol was used for vacuum erol and 10 % wt. water) with 0.1 mol/l sodium chloride by applying a
distillation at 120–126 ◦ C and pressure of 0.4 – 0.04 mbar and obtained strong acid Amberlite-252 resin. Therefore, the equilibria were studied
141.8 g of glycerol with a purity of 97 %. The entire one-step purifica­ at three different temperatures (303 K, 318 K, 333 K), and the effective
tion was done at a pH smaller than 5 to avoid any foaming. The bottom diffusion coefficient of sodium in the resin was studied to obtain the
of the column contained mainly salts, high boiling point MONGs, and kinetic data. The equilibrium results showed that selectivity for sodium

7
T. Attarbachi et al. Fuel 340 (2023) 127485

Table 8
Overview of ion-exchange resins used by different authors for the purification of crude glycerol.
Cation Anion Year Temperature Amount of Flow rate Amount of Mode Comment Ref.
Exchange Exchange [◦ C] resin [g] [mL/min] solvent [%]
Resin Resin

Amberlite 252 n/a 2009 60 n/a n/a n/a n/a Investigation of equilibrium, kinetic [128]
data for removal of sodium ions
Amberlyst 15 n/a 2019 22 40 15 60 Column Flow rate most important variable [125]
Amberlite IRA Amberlite IRA 2019 n/a n/a n/a n/a n/a Use of one cationic exchange step [20]
120Na 410Cl followed by two anionic exchange
steps
Amberlite 200C Amberlite IRN- 2016 n/a 2.5 n/a n/a Column Regeneration with diluted NaOH for [126]
78 Amberlite IRN-78, NaCl for Amberlite
200C
n/a n/a 2019 40 n/a n/a n/a Column Ion-exchange resin produced by [105]
Thermochem Corp PVT. ltd RT Nagar;

Optimum bed height: 6 cm

Fig. 7. Working principle of coagulation and flocculation for the purification of crude glycerol.

uptake is favoured at lower temperatures (303 K instead of 333 K) and This method is interesting for the removal of ions in crude glycerol but
experimental data can be described satisfactorily with the Langmuir has not been fully investigated. Lopes et al. [20] used, in a pre-treatment
model or mass action laws. The kinetic study showed that higher tem­ step, a cationic condensed tannin polymer derivative as a coagulant
peratures favour the ion-exchange process and a kinetic model based on agent to treat crude glycerol from a biodiesel process using frying oil to a
homogeneous reaction allows to obtain the diffusion coefficients at each purity of 77.3 % wt. The step can successfully replace routes such as
temperature. The study concluded that Amberlite-252 is a good choice acidification, bleaching, deodorization, or salting-out by reducing ions
to remove sodium ions from glycerol-water solutions with high salt such as chloride, iron, aluminium, and magnesium.
concentrations. Despite concentrations and volumes used to conduct the
experiment were quite low compared to usual glycerol solutions.
3.5. Membrane separation technologies
Ion exchange resins remain an interesting option for the purification
of crude glycerol, especially for the treatment of solutions with low salt
Membranes belong to the emerging technologies in the purification
contents [129]. It is already being applied in the production of deionised
of crude glycerol. They are highly interesting due to their low energy
water [130] and even on very large scales for cane sugar decolourization
requirement compared to conventional vacuum distillation and the
[131]. Nevertheless, high salt contents of the glycerol solution make the
avoidance of additional chemicals [129]. Currently, most of the research
process uneconomical due to the chemical regeneration cost [111],
is being undertaken around pressure-driven membrane technologies.
especially when glycerol contains >5–7 % wt. salt [132].
A relatively new technique for crude glycerol is based on thermally
driven membranes such as membrane distillation (MD). MD generates
3.4. Coagulation and flocculation different temperatures on both sides of the membrane, making the
vapour pressure the driving force of this process. In general, four
Coagulation and flocculation can be used as purification methods to different MD processes have been established: direct contact membrane
destabilize and aggregate (charged) colloidal particles in a suspension distillation (DCMD), air gap membrane distillation (AGMD), sweep gas
through the interaction between the coagulants and the colloids (coag­ membrane distillation (SGMD), and vacuum membrane distillation
ulation) and their subsequent sedimentation via flocculation (Fig. 7). (VMD).

8
T. Attarbachi et al. Fuel 340 (2023) 127485

Table 9
Overview of membranes used by different authors for the purification of crude glycerol.
Membrane Mode Year Membrane Type Material Glycerol Comment Ref.
purity [wt.
%]

Cross-flow filtration 2018 Ultrafiltration tubular Ceramic composed of ZuO2-TiO2 with TiO2 support 93.7 Optimal conditions: [22]
(Semi-continuous) membrane
Manufacturer: Tami MWCO = 5 kDA
Industries T = 50 ◦ C
p = 700 kPa
V = 50 mL/min
Dead-end filtration 2016 Ultrafiltration/Fine Ceramic composed of ZrO2ATiO2 with TiO2 support 97.5 Optimal conditions: [111]
Ultrafiltration MWCO = 1 kDA
Manufacturer: Tami T = 60 ◦ C
Industries p = 350 kPa
Vacuum Membrane 2016 Flat sheet PVDF n/a Glycerol rejection: 99.9 % [13]
Distillation hydrophobic
Vacuum filtration 2016 Manufacturer: Cellulose acetate 90.4 Optimal conditions: [122]
Sartorius Stedim pH = 3.26
Biotech S.A. mAC = 0.933 g
Phosphoric acid
Dead-end filtration 2013 Hybride membrane Polyvinyl alcohol n/a NaCl rejection: 43.98 % [133]
with thin film Polyethylene glycol
composite Polysulfone resin
Tetraethylorthosilicate
Electrodialysis 2017 Composite Heterogeneous Polymer membranes, modification n/a Decrease of salt concentration by [140]
membranes with Hydrated zirconium dioxide (HZD) and 100 times; modification increases
CMI 7000 and Amorphous zirconium hydrophosphate (ZHP) stability against fouling
AMI7000
Manufacturer:
Membrane
International
Electrodialysis 2017 Composite Heterogeneous Polymer membranes, modification n/a 90 % desalination of solution [139]
membranes with Hydrated zirconium dioxide (HZD) and
CMI 7000 and Amorphous zirconium hydrophosphate (ZHP)
AMI7000
Manufacturer:
Membrane
International
Sweeping gas 2014 Microporous flat-sheet PTFE n/a Solute rejection: 99 % [108]
membrane membrane
distillation Manufacturer:
Millipore
Continuous- 2015 Hollow fibre air-gab Polypropylene n/a Glycerol rejection efficiency: 99.9 % [136]
membrane membrane (AGMD)
distillation Manufacturer: Accurel
Membrana,
Chembrane
Engineering and
Technology
Bipolar 2003 Bipolar membranes n/a 95 80 % demineralization of a 65 % [107]
Electrodialysis BP-1 glycerol solution
(BED) ACM anionic
membrane
CMB cationic
membrane
Manufacturer:
Tokuyama Soda

Lastly, Electrodialysis (ED) is a membrane-based electrochemical

process consisting of a stack of different, alternating cationic exchange
and anionic exchange membranes, which separate the cations and an­
ions of the incoming crude or pre-treated glycerol solution due to an
applied external power source. This leads to alternating chambers which
consist of desalinated glycerol and concentrated chambers consisting of
anions or cations. An overview of different membrane modules and
types which have been used to purify crude glycerol is given in Table 9.

3.5.1. Membrane separation (pressure-driven)

The working principle of a dead-end filtration module for the puri­
Fig. 8. Working principle of a dead-end membrane filtration module for the fication of crude glycerol is depicted in Fig. 8. The main factors studied
purification of crude glycerol. in membrane separation are the type of membrane (polymeric, ceramic
or hybrid), temperature, tans-membrane pressure (TMP), MWCO,
rejection and permeate fluxes.

9
T. Attarbachi et al. Fuel 340 (2023) 127485

was found at 50 ◦ C, a TMP of 700 kPa, and a flow rate of 50 mL/min

yielding a purity of 93.7 % wt. Ceramic membranes have many advan­
tages, such as resistance to chemical, mechanical and thermal degra­
dation, combined with higher permeability rates and easier cleaning
compared to polymer membranes. Furthermore, a techno-economic
analysis was conducted with the unit cost and revenue of crude glyc­
erol purification of 50.85 USD/kg and 80.36 USD/kg, respectively.
A different trend in membrane purification has been seen in hybrid
membranes reported in Shaari et al. [133]. The advantage of hybrid
membranes is their higher mechanical and thermal stability in combi­
nation with enhanced hydrophilicity associated with permeation of
water-soluble material. In this study, a thin film composite (TFC) was
used with three different hybrid membrane formulations (consisting of
polyvinyl alcohol, polyethylene glycol, tetraethylorthosilicate (TEOS))
as a barrier layer and studied the effects of flux rate measurement,
percentage glycerol permeated and NaCl rejection to increase NaCl
Fig. 9. Working principle of a membrane vacuum distillation for the purifica­ rejection and increase recovery of glycerol while maintaining a suffi­
tion of crude glycerol. ciently high flux. For the third membrane glycerol was incorporated to
see any relevant changes. The results showed a >40 % NaCl rejection
Dhabhai et al. [111] used the membrane separation step as a sub­ when glycerol was incorporated into the membrane as it increased the
sequent step to a physio-chemical treatment. Ceramic membranes such porosity and thermal stability of the barrier layer.
as a dead-end filtration with by-pass composed of ZrO2-TiO2 with TiO2 A more fundamental study was undertaken by Mah et al. [134] about
support with a molecular weight cut-off (MWCO) of 1–15 kDa were filtration modes using reverse osmosis (RO) membranes investigating
used. The membranes were cleaned with methanol periodically. In their the glycerol rejection and water permeability in dead-end and crossflow
experiments, the effect of temperature (25–60 ◦ C), transmembrane filtration. The results showed a higher rejection and permeability of
pressure difference (50–350 kPa), and MWCO (1–15 kDa) were inves­ crossflow filtration. Reverse osmosis membrane with high surface
tigated. The results showed that the highest glycerol purity was achieved roughness, high negative charge in glycerol solution, low water contact
at 60 ◦ C (equal to 97.5 % wt.) due to the lower viscosity and a MWCO of angle, high water affinity and small pore radius showed better perfor­
1 kDa, which lead to greater glycerol enrichment than greater MWCO. mance. The highest rejection and permeation were achieved at tem­
This would result in incomplete filtration due to the increased pore size peratures of 40 ◦ C by crossflow membrane with TFC-HR membranes
leading to impurities in the filtrate. Concerning the TMP, it was shown (consisting of proprietary thin film composite polyamide material) with
that at 100 kPa, generally a higher glycerol content was obtained than at a rejection of 99.81 %, having a permeate flux of 11.86 kg/m2•h
350 kPa for any membrane, except for a 1 kDa membrane where the compared to dead-end filtration with a separation of 96.37 % and
glycerol content increased with pressure. An increased MWCO at fixed permeate flux of 4.93 kg/m2•h.
pressure shows a lower purity to the impurities which can pass the In general, membranes are an interesting alternative to the conven­
membrane. tional purification route. While ceramic ultra-filtration membranes are
Chol et al. [22] used a 5 kDa ultrafiltration ceramic tubular mem­ efficient and offer ease of separation and robustness, polymeric mem­
brane made of the same material as above and investigated temperature branes show excellent behaviour towards permeability and selectivity
(25–50 ◦ C), TMP (345–1380 kPa), and flow rate (50–200 mL/min). for water [135]. Lower energy consumption with less capital expendi­
Compared to Dhabhai et al. [111], a cross-flow filtration in semi- ture compared to a vacuum column makes this option attractive for
continuous mode was used achieving similar results. The optimum small and medium-sized plants. A major drawback of membranes

Fig. 10. Working principle of electrodialysis for the purification of crude glycerol.

10
T. Attarbachi et al. Fuel 340 (2023) 127485

Table 10 adds additional costs which must be considered.

Advantages and disadvantages of various crude glycerol purification routes.
Techniques Advantages Disadvantages 3.5.2. Membrane separation (thermally-driven)
The working principle of a vacuum membrane distillation (VMD) for
Vacuum • Established way of industrial • High CAPEX [15]
Distillation glycerol purification [141] • High OPEX (energy the purification of crude glycerol can be seen in Fig. 9. Possible variables
• Very high glycerol purity intensive) [15] which are studied for membrane distillation are the feed temperature,
[145] • Not suitable for small and feed inlet concentration and feed circulation rate and vacuum.
• No pre-treatments are medium size plants [15] Pal et al. [13] used a vacuum membrane distillation process to purify
required [104]
• Good for high content of salt
a glycerol-water mixture using flat sheet PVDF membranes which were
and MONG [104] prepared in the lab. Therefore, membrane rejection which is the ability
Adsorption with • Decolourization [102] • Removal of loaded of the membrane to retain the desired component was investigated.
activated • Removal of odour [109] adsorbent requires Within a feed concentration of 10–90 % glycerol and water mixture, a
carbon additional steps such as
membrane rejection of 99.9 % of glycerol was achieved with feed tem­
filtration [146]
• Inefficient for other perature between 25 and 30 ◦ C and permeate side vacuum pressure of
impurities smaller than 0.007 bar. The glycerol concentration in the permeate stream was 0.07
glycerol [102] vol% yielding a highly pure permeate side consisting mainly of water.
• Used as the final polishing A different process was reported by Shirazi et al. [108] using sweep
step [52]
Ion-Exchange • Effective removal of ions • Regeneration of resins
gas membrane distillation (SGMD). The purpose of this experiment was
[128] necessary [132] to concentrate diluted glycerol from wastewater (dewatering). There­
• Reliable industrial • Waste stream produced is fore, a microporous hydrophobic flat-sheet PTFE membrane was used,
implementation [132] not recoverable [52] and operating parameters such as feed temperature, glycerol concen­
• Low energy consumption • Only economical for low
tration in the aqueous phase, feed and sweep gas flow rate were studied.
[133] salt content material <5-7
wt.% [132] The optimal results have been achieved at 65 ◦ C, 400 mL/min, 1 % wt. of
Electrodialysis • Effective removal of ions • Industrially implemented glycerol and 0.453 Nm3/h, and the process is particularly low cost in
[140] only for aqueous systems terms of energy, making it interesting for further investigation.
• Continuous process [147] [148] A similar study was conducted by Zhang et al. [136] to concentrate
• High yields possible [139] • Pre-treatment is necessary
aqueous glycerol solution by using continuous-effect membrane distil­
[137]
• Issues associated with lation (CEMD) which enables higher energy efficiency and lower oper­
membranes such as ating cost compared to other MD solutions. A hollow fibre air gap
concentration membrane distillation (AGMD) module was used (using two different
polarization, water
types of porous hollow fibres and dense-wall hollow fibres made from
splitting on monopolar
membranes, and scale-up polypropylene) to concentrate a feed of 10 g/L up to about 400 g/L with
[148] a rejection efficiency of >99.9 %, a trans-membrane flux of 5.7 L/m2h
Membrane • High purities are achievable • Pore wetting [13] and a maximum value of gain output ratio (GOR: a measure of how
(Thermally- [135] • Heat recovery is negligible much thermal energy is consumed in a desalination process) of 16.2
driven) • Lower heat loss through [13]
which is 33 % higher compared to conventional seven-effect evapora­
membrane matrix [13]
• Lower operating pressure tion (which is a type of multiple-effect evaporators). Nevertheless, the
and temperature compared system provided a comparable GOR for concentrations of up to 350 g/L
to pressure-driven mem­ (GOR = 5.3) with a trans-membrane flux of 3.1 L/m2•h. Problems
brane processes [135]
started at an increasing glycerol concentration of 300 g/L as the vis­
• Required equipment for MD
can be much smaller [108]
cosity started to increase and subsequently the vapour pressure of water
• Use of energy sources such to decrease. The process showed high selectivity to separate aqueous
as waste thermal energy in solution of non-volatile solutes such as glycerol leading to a distillate
industrial plants, solar, wind which was consisting almost purely of water and results indicated that
or geothermal energies can
the more porous membrane exhibited better features due to the reduc­
be used to operate MD [108]
Membrane • High rate of flux [13] • MONG content can cause tion of heat loss by conduction and reduction of mass transfer resistance.
(Pressure- • Economically feasible [22] fouling [52] Furthermore, a long-term test of 60 days showed good stability of the
driven) • High-pressure operation process.
[13]
Membrane distillation seems to be an interesting application for the
• Disposal problem [13]
• Pre-treatment step
dewatering of crude glycerol which usually requires more energy. The
necessary [22] process features lower energy consumption compared to conventional
• The membrane must be distillation and lower operating temperature than phase separation by
flushed with solvent to evaporation [135]. It can’t be compared directly to pressure-driven
avoid MONG [22]
membrane processes as the permeate (product) produced usually con­
Coagulation • One-step removal of charged • Considerable quantities of
colloids [20] coagulant are needed to sists entirely of water and other volatile matter which could pass the
• Mild treatment conditions achieve an appropriate membrane. Hence, MD leaves a retentate behind consisting of glycerol,
[20] level of flocculation [149] non-volatile MONG and ashes. Currently, the application of membrane
• Some quantity of sludge distillation in academia is solely focusing on concentrating dilute
formed must be processed
externally [149]
aqueous glycerol mixtures and not addressing any ash or MONG sepa­
ration, making them unsuitable for the purification of highly impure
crude glycerol [108].
remains fouling behaviour which can reduce the filtration area and
hence the performance of the membrane [22]. Therefore, a pressure- 3.5.3. Electrodialysis
driven membrane separation needs a pre-treatment step as well, to The schematic of electrodialysis applied to glycerol purification is
reduce the MONG content as much as possible. Furthermore, the peri­ depicted in Fig. 10. Different relevant factors which are investigated in
odical exchange of the membranes and their cleaning with methanol ED purification are the limiting current density (LCD), different

11
T. Attarbachi et al. Fuel 340 (2023) 127485

Table 11
Appendix B.
Main Separation Year Glyt ¼ Glyt Asht ¼ Asht ¼ MONGt MONGt Watert Watert Comments Ref.
Route 0 [wt. ¼1 0 [wt. 1 [wt. ¼ 0 [wt. ¼ 1 [wt. ¼ 0 [wt. ¼ 1 [wt.
%] [wt. %] %] %] %] %] %]
%]

Neutralization 2018 67.7 89.5 17.85 3.6 n/a n/a 38.6 4.3 Use of bentonite as adsorbent [115]
Adsorption
Acidification 2019 74.72 92.04 12 8 11.31 1.14 1.98 0.2183 Use of ethylene glycol as [153]
Extraction solvent
Acidification 2018 67 96 11.6 0.3 5.2 0.7 16.2 3 Use of tea waste as adsorbent [116]
Adsorption
Acidification 2014 13 96 5.6 1.04 70.2 1.09 9.2 1.30 Decreasing trend of ASH and [109]
Neutralization MONG contents with
Evaporation decreasing pH
Anti-solvent
treatment
Adsorption
Acidification 2020 61 79.64 n/a n/a n/a n/a n/a n/a Acetylation process after [154]
Adsorption glycerol purification
Distillation
Neutralization 2016 35.66 97.37 4.08 1.1 47.86 n/a 12.4 n/a Glycerol from a UCO biodiesel [146]
Distillation plant
Anti-solvent
treatment
Adsorption
Distillation
Extraction 2015 74 99.2 n/a n/a 12.5 0.3 13.5 0.5 Use of Petroleum ether and [155]
Adsorption Toluene as solvents (hazard)
Saponification 2018 40 98.07 4.90 1.2 55.91 0.17 5 3 Use of ceramic membranes [22]
Acidification
Anti-solvent
treatment
Membrane
Adsorption
Electrodialysis 2019 n/a n/a n/a n/a n/a n/a n/a n/a Fundamental study on [138]
different membranes used for
electrodialysis
Electrodialysis 2015 n/a n/a n/a n/a n/a n/a n/a n/a Novel process with 95 % salt [137]
removal after removal of
MeOH, Soaps
Acidification 2019 35.6 98.2 4.73 0.39 50.29 0.78 9.38 0.63 Optimization of experiment [125]
Neutralization by Taguchi method
Ion-Exchange
Anti-solvent 2019 n/a n/a n/a n/a n/a n/a n/a n/a Purification of salts by [156]
treatment / different solvents investigated
Extraction
Coagulation/ 2019 53.9 94.5 n/a n/a n/a n/a n/a n/a Flocculation as alternative for [20]
Flocculation acidfication; very efficient to
Ion-Exchange remove metal content
Evaporation
Saponification 2016 40 97.5 4.9 n/a 55 0.3 5 2.2 Viscosity must be high during [111]
Acidification membrane step / high
Neutralization Glycerol purity of 88.6 wt%
Membrane after physiochemical
Adsorption treatment
Neutralization 2020 22.88 98.5 3.52 0.21 73.6 1.23 0 0.01 Citric Acid use inefficient / [157]
Evaporation Use of “Green Metrics” to
assess ecological factor
Vacuum Distillation 2019 51.88 78.72 n/a n/a n/a n/a n/a n/a Distillation is best purification [11]
Adsorption step
Neutralization 2016 77.4 99.4 2.4 0.002 17.7 0.3 2.5 0.25 Silica beads enabled [126]
Ion-Exchange reduction of moisture
Acidification 2013 n/a 98.1 n/a 0.0002 n/a n/a n/a n/a Complex reaction conducted [158]
Reaction to remove further impurities
Vacuum distillation
Adsorption
Saponification 2021 40.7 98.2 5.4 0.4 45.22 ≪1 5.3 0.8 Synthetic Crude Glycerol [100]
Acidification
Anti-solvent AC from oil palm empty fruit
treatment bunch
Adsorption
Adsorption 2021 96.79 98.67 0.10 0.08 1.37 0.69 1.62 0.42 Use of reactivated spent [118]
bleaching earth from palm oil
refineries as adsorbents
Saponification 2018 n/a n/a n/a Nil n/a n/a n/a 0.02 Generated sodium phosphates [159]
Acidification used in biodiesel production
(continued on next page)

12
T. Attarbachi et al. Fuel 340 (2023) 127485

Table 11 (continued )
Main Separation Year Glyt ¼ Glyt Asht ¼ Asht ¼ MONGt MONGt Watert Watert Comments Ref.
Route 0 [wt. ¼1 0 [wt. 1 [wt. ¼ 0 [wt. ¼ 1 [wt. ¼ 0 [wt. ¼ 1 [wt.
%] [wt. %] %] %] %] %] %]
%]

Neutralization
Anti-solvent
treatment
Adsorption
Acidification 2021 n/a n/a n/a n/a n/a n/a n/a n/a Purified glycerol used as [160]
Neutralization carbon source for microbial
Anti-solvent oil production
treatment
Evaporation
Acidification 2016 51.68 93.89 5.76 0.23 12.9 5.22 29.4 0.15 Synthetic Crude Glycerol [122]
Neutralization
Anti-solvent RSM used to optimize the
treatment purification process
Adsorption Membrane used as final
Membrane purification stage
Acidification 2020 n/a 95.99 n/a n/a n/a n/a n/a 4.01 Synthetic Crude Glycerol [120]
Neutralized
Anti-solvent Paper has main focus on
treatment adsorption and preparation of
Adsorption adsorbent
Evaporation
Physio-chemical pre- 2017 27.2 93 36.2 7 n/a n/a n/a n/a Optimum condition: [113]
treatment
(according to AC dose: 67 g/L
Manosak et al.) Contact time: 2 h
Adsorption Shaking rate: 250 rpm
Sludge-derived KOH-
activated carbon
Neutralization 2020 54.8 98.4 residual n/a 43.8 residual residual residual Use of microreactor [161]
Extraction
Electrodialysis 2017 n/a n/a n/a n/a 8 n/a 10 n/a Current efficiency of 95–98 % [140]

1000 mol/m3 NaCl

Acidification 2018 20 n/a 6.4 0.1 n/a n/a 10.2 0 Crude glycerol refined up to [162]
Neutralization pharmaceutical grade
Adsorption
Electrodialysis 2017 90 n/a n/a n/a 8 n/a 10 n/a 90 % desalination of solution [139]

First a glycerol-water mixture

was added based on this
impurities were added, 1000
mol/m3 NaCl
Membrane Distillation 2014 n/a n/a n/a n/a n/a n/a n/a n/a Solute rejection of 99 % [108]
Membrane Distillation 2015 n/a n/a n/a n/a n/a n/a n/a n/a Glycerol rejection efficiency: [136]
99.9 %

Feed of 10 g/L successfully

concentrated to about 400 g/L
Microwave 2014 35.4 94.2 3.3 0.002 53.5 0.001 12.3 0.01 Bio-adsorbent synthesized [119]
Irradiation from dead yeast cells
Acidification immobilized on chitosan
Neutralization
Adsorption
Neutralization 2020 80–90 n/a 4.82 0.74 4.27 2.62 n/a n/a Optimum dosage of 20 g/L [106]
Anti-solvent
treatment FFAs removed by
Neutralization physisorption and
Drying chemisorption by the reaction
with –OH attached on carbon
surface
Adsorption 2018 n/a n/a n/a n/a n/a n/a n/a n/a Use of Electrospun chitosan/ [114]
poly(ethylene oxide)
nanofibers as adsorbents
Adsorption 2019 n/a n/a 5.68 5.67 n/a n/a 13.48 n/a Kinetics and thermodynamics [123]
of glycerol adsorption
Membrane Distillation 2019 n/a n/a n/a n/a n/a n/a n/a n/a Rejection of glycerol: 99.9 % [13]
Ion-exchange 2019 18 40 n/a n/a n/a n/a n/a n/a Optimum condition: [105]

Bed height: 6 cm
Temperature: 40 ◦ C

13
T. Attarbachi et al. Fuel 340 (2023) 127485

membrane types and feed compositions. pharmaceutical-grade glycerol (purity of 99.7 %) with a by-product of
Vadthya et al. [137] used electrodialysis to desalinate a synthetic technical grade glycerol (purity of 85–90 %). Vacuum distillation is used
solution of crude glycerol containing a specific amount of sodium sulfate where the mixture is pre-heated to 175 ◦ C to separate the glycerol from
and water to desalinate it with commercial AMI-7001 and CMI-7000 ion organic components and salts. The residue is treated in a post-distillation
exchange membranes. Different water-glycerol and sodium sulfate salts still to increase glycerol yield, and the salt is decanted. Adsorption with
ratios were prepared. It was determined that a higher salt content at activated carbon in a fixed bed is used as a final step; the product is
constant water and glycerol ratios leads to longer operating times due to bleached to achieve a purity of 99.7 %. Air Liquide’s technology can
the increasing numbers of ions that migrate. Furthermore, the decrease process 10 tons per day to 600 tons per day with an operating expen­
in conductivity is much steeper when higher salt concentrations are diture of 35 USD/tonne.
used. An increase in water content led to a decrease in operating time. A more complex purification route that can also be found in
The results showed >95 % separation of the target salts. academia is proposed by KVT technology [142]. Their glycerol purifi­
A more fundamental study was conducted by Schepper et al. [138] cation technology is based on neutralization and drying, methanol
using various ion-exchange membranes to compare their performance rectification, distillation, rectification, and MONG desalination yielding
with respect to glycerol desalination. A synthetic crude glycerol solution a glycerol purity of 99.7 %, leading to pharmaceutical grade. Other
containing sodium chloride was prepared to study the salt, glycerol, and possible solutions are offered by GE with their electrodialysis module for
water transport and derive model coefficients to evaluate the transport. efficient salt removal [143] or Lanxess with their commercial LEWATIT
In this work, desalination of 92 % after 3.2 h and 9.5 h with Q380 (pilot resins which are available for different applications [144].
stack) and ED100 (small stack) stacks were reached respectively. Q380 The industry offers a broad range of solutions for the purification of
is therefore the preferable set up due to its higher membrane surface. crude glycerol for large-scale processes. Nevertheless, cost-competitive
Being a technology based on membranes, fouling could reduce technologies are not available for small and medium-sized biodiesel
dramatically the performance, therefore a pre-treatment step such as companies, especially for glycerol derived from 2nd generation bio­
with the other membrane-based processes is required. diesel plants which present high levels of impurities.
Schaffner et al. [107] used bipolar electrodialysis (BED) to desalinate
a 65 % glycerol solution from diester plants which contain 0.35 mol/L 5. Challenges in the glycerol industry and future research focus
sodium sulphates by 80 %. The purified glycerol contained 95 % glycerol
with less than 2 % mineral content. Lower mineral contents affected the Many problems and challenges remain in the crude glycerol purifi­
faradaic efficiency. During the process, approximately 2.5 % glycerol cation industry. As the amount of highly impure crude glycerol from
loss occurred of which half of it could be recovered via the acid recycling waste-based biodiesel is increasing, new and more cost-effective solu­
loop. The study concluded that an increase in the current density leads to tions are being considered also because many other oleochemical-based
a smaller membrane area but also an increase in the cost because the waste streams require similar purification. A lot of research has been
faradaic efficiency decreases. done on this topic, given the relevance, the growing market and appli­
The trend of composite membranes can be found in ED applications cations of glycerol for food, pharmaceutical and chemical industries.
as well. Rozhdestvenskaya et al. [139] investigated the NaCl removal However, as this crude glycerol is derived from waste, it cannot be used
from a highly concentrated glycerol-water and artificial impurities in the traditionally high-profit segments such as pharma and food but
mixture (90 % wt. glycerol and 10 % wt. water with 1000 mol/m3 NaCl only for technical applications such as raw chemicals from gasification
and 8 % wt. organic impurities) using composite membranes. Therefore, or biogas. The design of a purification process is relevant to reach
modification of heterogeneous polymer cation and anion-exchange accommodate the requirements of the downstream processes. Simulta­
membranes with nanoparticles of zirconium hydrophosphate (ZHP neously, the glycerol recovery has to be maintained high to avoid an
used as modifier for cation-exchange membrane CEM) and hydrated economic loss through the purification. Acidification and neutralization
zirconium dioxide (HZD used as modifier of anion-exchange membrane are proven processes at laboratory scale, but they require many steps,
AEM) were obtained. The results showed a decrease in salt concentra­ the addition and handling of hazardous chemicals, and the importance
tion by 90 %, a current efficiency of 95–98 % for 70 h and that the of corrosive-resistant material have hindered their implementation at
modified membranes showed improved stability against fouling industrial scale. A modular unit with membranes could be the answer to
compared to pristine membranes. Furthermore, it was detected that the existing challenge for small and medium scale glycerol purification
organic additives remained in the desalinated glycerol-water mixture. A technologies with limited energy consumption and without the addition
similar study was undertaken by the same research group by Dzyako of hazardous chemicals. The risk of fouling may be circumvented by
et al. [140] using the same membranes but focusing more on the char­ reducing the MONG content in the glycerol upstream by physio-
acterization of the membranes. chemical means. A list of the advantages and disadvantages of each
Electrodialysis remains an interesting option, especially to remove process can be found in Table 10.
ions which could otherwise harm a catalyst in a subsequent reaction Since crude glycerol is a by-product and, in many cases, a waste-
step. However, the same limitations as with pressure-driven processes stream, industry is often reluctant to invest on its purification. This
remain such as the problem with fouling. Potentially, this could be will change in the future as more existing and new producers of biodiesel
resolved by adding a pre-treatment step to reduce the MONG content in will shift towards the use of exclusively waste-based feedstocks. This
the crude glycerol. Whether such a process is economically and tech­ shift will not just yield an avalanche of highly impure crude glycerol but
nically feasible using real waste-based crude glycerol requires further also add costs to the final price of bio-diesel. The current gold standard
studies. for the purification of crude glycerol is vacuum distillation [52]. How­
ever, this will change as soon as the vacuum distillation becomes less
4. Industrial glycerol purification techniques profitable at higher impurity content such as in the case of short- and
long-chained organic molecules in the MONG content leading to high
Industrial glycerol purification technologies were developed by operating costs. Adsorption using biogenic materials will remain a
many different companies. Currently, plants with large outputs use finisher step in the future and should only be used to remove residual
vacuum distillation as the most common purification technique due to matter which has already been reduced significantly by prior treatment.
its reliability. The drawbacks of vacuum distillation are its high energy Io-exchange resins are useful for the reduction of ash contents but only
consumption responsible for about 50 % of plant operating costs, and for mixtures containing less than 10 wt% otherwise the regeneration
high investment costs. costs make the process not profitable. Ion-exchange resins and all
Air Liquide’s technology [141] offers the production of membrane-based processes share the same problem with the handling of

14
T. Attarbachi et al. Fuel 340 (2023) 127485

the high MONG content which deactivates the resins or it generates handling of hazardous and corrosive chemicals, making the process
fouling. However, pressure-driven membranes have shown in lab trials comparably unsafe and expensive in terms of CAPEX and OPEX.
the ability to obtain high purity glycerol whether this can be converted Advanced purification technologies such as pressure-driven membrane
to industrial scale remains subject to research. Electrodialysis has also separation, ion-exchange, electrodialysis or membrane-distillation have
shown its efficiency in removing selectively ions from crude glycerol. proven to work although their technology development requires more
Whether ED can be used to remove ions for industrial waste-based crude effort to reduce inherent problems such as fouling or high cost of resin
glycerol has not been yet demonstrated. Membrane distillation could regeneration. Hence, finding a cost-competitive environmentally
replace vacuum distillation in the future making the permeate even friendly alternative to purifying highly impure crude glycerol remains a
purer through the selective membrane and reducing the CAPEX technical and commercial challenge which must be addressed in the
significantly. future considering the amount of crude glycerol provided to the market.
Coagulation can remove charged particles, making it possibly useful
for the removal of ashes and soaps. However, non-charged MONG CRediT authorship contribution statement
content will not be affected by this. In the future, the issue of high MONG
and ash content with simultaneously the requirement to achieve a high Taha Attarbachi: Conceptualization, Methodology, Investigation.
glycerol purity and recovery can potentially only be resolved by using a Martin D. Kingsley: Conceptualization, Methodology. Vincenzo
combination of conventional and advanced purification methods. Spallina: Supervision, Project administration, Conceptualization,
In the far future, other possible promising solutions which have been Methodology, Funding acquisition.
currently at the level of conceptualisation include advanced adsorbents
such as MOFs (Metal-Organic Frameworks) [150] as well as hybrid
processes such as MOF-aided membranes, graphene-based membranes Declaration of Competing Interest
[151] or nanomaterials [152] which are currently employed in water
desalination. The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
6. Conclusion the work reported in this paper.

From the market study, it is expected that by the year 2024, 6 million Data availability
tonnes of crude glycerol will be produced from which 4 million tonnes
are derived from the biodiesel industry (bio-glycerol). Furthermore, it Data will be made available on request.
can be expected that approximately 680,000 tonnes of this glycerol are
highly impure and not suitable for typical glycerol applications such as Acknowledgements
food and pharma products. Hence, waste-based crude glycerol purifi­
cation and valorisation remain important research area for the industry. This work is part of the GLAMOUR project which is supported by the
In terms of purification, vacuum distillation is still the most dominant European Union’s Horizon 2020 research and innovation programme
way of industrial crude glycerol purification given its use. The scale-up under grant agreement No 884197. The authors would like to thank Dr
of physio-chemical treatments is hampered by the application and Christopher De Leeuwe for his constructive criticism of the manuscript.

15
T. Attarbachi et al. Fuel 340 (2023) 127485

Appendix A

Appendix B

Table B1

References [11] Pitt FD, Domingos AM, Barros AAC. Purification of residual glycerol recovered
from biodiesel production. South African J Chem Eng 2019;29:42–51. https://
doi.org/10.1016/j.sajce.2019.06.001.
[1] Clean VP. Clean coal technologies. Sustain Util Nat Resour 2017:19–53. https://
[12] Tan HW, Abdul Aziz AR, Aroua MK. Glycerol production and its applications as a
doi.org/10.1201/9781315153292-2.
raw material: A review. Renew Sustain Energy Rev 2013;27:118–27. https://doi.
[2] Schöpe M. Renewable energy directive. Eur Wind Energy Conf Exhib 2008;2008
org/10.1016/j.rser.2013.06.035.
(1):32–8.
[13] Pal P, Chaurasia SP, Upadhyaya S, Agarwal M, Sridhar S. Glycerol Purification
[3] Parliament E. Directive (EU) 2018/2001 of the European Parliament and of the
Using Membrane Technology. 2019.
Council on the promotion of the use of energy from renewable sources. Off J Eur
[14] Seidensticker T, Behr A. Einführung in die Chemie nachwachsender Rohstoffe.
Union 2018;2018:82–209.
vol. 4. 2016.
[4] Bhuiya MMK, Rasul MG, Khan MMK, Ashwath N, Azad AK. Prospects of 2nd
[15] Ciriminna R, Pina C Della, Rossi M, Pagliaro M. Special Feature Understanding
generation biodiesel as a sustainable fuel – Part: 1 selection of feedstocks, oil
the glycerol market 2014:1432–9. doi: 10.1002/ejlt.201400229.
extraction techniques and conversion technologies. Renew Sustain Energy Rev
[16] Nda-Umar UI, Ramli I, Taufiq-Yap YH, Muhamad EN. An overview of recent
2016;55:1109–28. https://doi.org/10.1016/j.rser.2015.04.163.
research in the conversion of glycerol into biofuels, fuel additives and other bio-
[5] Nabgan W, Jalil AA, Nabgan B, Jadhav AH, Ikram M, Ul-Hamid A, et al.
based chemicals. Catalysts 2019:9. https://doi.org/10.3390/catal9010015.
Sustainable biodiesel generation through catalytic transesterification of waste
[17] Santibáñez C, Teresa Varnero M, Bustamante M. Residual glycerol from biodiesel
sources: A literature review and bibliometric survey. RSC Adv 2022;12:1604–27.
manufacturing, waste or potential source of bioenergy: a review. vol. 71. n.d.
https://doi.org/10.1039/d1ra07338a.
[18] Chozhavendhan S, Karthiga Devi G, Bharathiraja B, Praveen Kumar R,
[6] Anand P, Saxena RK. A comparative study of solvent-assisted pretreatment of
Elavazhagan S. Assessment of crude glycerol utilization for sustainable
biodiesel derived crude glycerol on growth and 1,3-propanediol production from
development of biorefineries. Elsevier Inc.; 2019. doi: 10.1016/B978-0-12-
Citrobacter freundii. N Biotechnol 2012:29. https://doi.org/10.1016/j.
818996-2.00009-0.
nbt.2011.05.010.
[19] Pott RWM, Howe CJ, Dennis JS. The purification of crude glycerol derived from
[7] Fávaro VR, Ezequiel JMB, D’Aurea AP, Van Cleef EHCB, Sancanari JBD,
biodiesel manufacture and its use as a substrate by Rhodopseudomonas palustris
Santos VC, et al. Glicerina na alimentação de bovinos de corte: Consumo,
to produce hydrogen. Bioresour Technol 2014;152:464–70. https://doi.org/
digestibilidade, parâmetros ruminais e sanguíneos. Semin Agrar 2015;36:
10.1016/j.biortech.2013.10.094.
1495–505. https://doi.org/10.5433/1679-0359.2015v36n3p1495.
[20] Lopes AP, Souza PR, Bonafé EG, Visentainer JV, Martins AF, Canesin EA. Purified
[8] E L, Gopi M, Kumar RD, Patel B, PS B, Deginal R, et al. Crude glycerol: by-product
glycerol is produced from the frying oil transesteri fication by combining a pre-
of biodiesel industries as an alternative energy source for livestock feeding. J Exp
purification strategy performed with condensed tannin polymer derivative
Biol Agric Sci 2017;5:755–66. doi: 10.18006/2017.5(6).755.766.
followed by ionic exchange. Fuel Process Technol 2019;187:73–83. https://doi.
[9] Siles López JÁ, Martín Santos M de los Á, Chica Pérez AF, Martín Martín A.
org/10.1016/j.fuproc.2019.01.014.
Anaerobic digestion of glycerol derived from biodiesel manufacturing. Bioresour
[21] Kreutzer UR. Control plant based on natural fats and oils. J Am Oil Chem Soc
Technol 2009;100:5609–15. doi: 10.1016/j.biortech.2009.06.017.
1984;61:343–8.
[10] He Q (Sophia), McNutt J, Yang J. Utilization of the residual glycerol from
[22] Chol CG, Dhabhai R, Dalai AK, Reaney M. Purification of crude glycerol derived
biodiesel production for renewable energy generation. Renew Sustain Energy Rev
from biodiesel production process: experimental studies and techno-economic
2017;71:63–76. doi: 10.1016/j.rser.2016.12.110.
analyses. Fuel Process Technol 2018;178:78–87. https://doi.org/10.1016/j.
fuproc.2018.05.023.

16
T. Attarbachi et al. Fuel 340 (2023) 127485

[23] Yildiz G, Ronsse F, Venderbosch R, van Duren R, Kersten SRA, Prins W. Effect of [64] Carmines EL, Gaworski CL. Toxicological evaluation of glycerin as a cigarette
biomass ash in catalytic fast pyrolysis of pine wood. Appl Catal B Environ 2015; ingredient. Food Chem Toxicol 2005;43:1521–39. https://doi.org/10.1016/j.
168–169:203–11. https://doi.org/10.1016/j.apcatb.2014.12.044. fct.2005.04.010.
[24] Di Fraia A, Miliotti E, Rizzo AM, Zoppi G, Pipitone G, Pirone R, et al. Coupling [65] Viana MB, Freitas AV, Leitão RC, Pinto GAS, Santaella ST. Environmental
hydrothermal liquefaction and aqueous phase reforming for integrated technology reviews anaerobic digestion of crude glycerol: a review anaerobic
production of biocrude and renewable H 2. AIChE J 2022. https://doi.org/ digestion of crude glycerol: a review. Environ Technol Rev 2012;1:81–92.
10.1002/aic.17652. https://doi.org/10.1080/09593330.2012.692723.
[25] Tabatabaei M, Aghbashlo M. Biodiesel. From Production to Combustion; 2019. [66] Pagliaro M. C3-Monomers. Glycerol 2017:23–57. https://doi.org/10.1016/B978-
[26] Elgharbawy AS, Sadik WA, Sadek OM, Kasaby MA. A review on biodiesel 0-12-812205-1.00002-3.
feedstocks and production technologies. J Chil Chem Soc 2021;65:5098–109. [67] Propylene Glycol (PG) Production and Manufacturing Process | ICIS n.d.
https://doi.org/10.4067/S0717-97072021000105098. [68] van Bennekom JG, Venderbosch RH, Heeres HJ. Biomethanol from glycerol.
[27] Thompson JC, He BB. Characterization of crude glycerol from biodiesel Biodiesel - Feed Prod Appl 2012. https://doi.org/10.5772/53691.
production from multiple feedstocks. Appl Eng Agric 2006. [69] University of Manchester. Sustainable Production of ACrylic acId from reNewable
[28] Global COM, Market G. Global glycerol market 2019-2023. 2019. waste Glycerol n.d.
[29] Eryilmaz T, Yesilyurt MK, Cesur C, Gokdogan O. Biodiesel production potential [70] Kumar LR, Kaur R, Tyagi RD, Drogui P. Identifying economical route for crude
from oil seeds in Turkey. Renew Sustain Energy Rev 2016;58:842–51. https://doi. glycerol valorization: Biodiesel versus polyhydroxy-butyrate (PHB). Bioresour
org/10.1016/J.RSER.2015.12.172. Technol 2021;323:124565. https://doi.org/10.1016/j.biortech.2020.124565.
[30] United States Department of Agriculture. EU-28 Biofuel Mandates in the EU by [71] Vandi L-J, Chan CM, Werker A, Richardson D, Laycock B, Pratt S. Wood-PHA
Member State 2015. Composites: Mapping Opportunities n.d. doi: 10.3390/polym10070751.
[31] Indonesia adds biodiesel capacity ahead of B40 mandate n.d. [72] Hassan EA, Abd-Alla MH, Zohri ANA, Ragaey MM, Ali SM. Production of butanol
[32] Malaysia postpones biodiesel mandate rollout to 2022 - state media | Successful and polyhydroxyalkanoate from industrial waste by Clostridium beijerinckii
Farming n.d. ASU10. Int J Energy Res 2019;43:3640–52. https://doi.org/10.1002/er.4514.
[33] Brazil to cut biodiesel blend mandate to 10pc: Update n.d. [73] The cost of hydrogen: Platts launches Hydrogen Price Assessment - Ammonia
[34] Produktion von Biodiesel weltweit und in Deutschland bis 2018 | Statista n.d. Energy Association n.d.
[35] Kent R. Renewables. Plast Eng 2018;74:56–7. https://doi.org/10.1002/ [74] N-Butanol (NBA) Pricing, Prices, Price, Demand & Supply | ChemAnalyst n.d.
peng.20026. [75] Crutchik D, Franchi O, Caminos L, Jeison D, Belmonte M, Pedrouso A, et al.
[36] Mizik T, Gyarmati G. Economic and sustainability of biodiesel production—a Polyhydroxyalkanoates (PHAs) Production: A Feasible Economic Option for the
systematic literature review. Clean Technol 2021;3:19–36. https://doi.org/ Treatment of Sewage Sludge in Municipal Wastewater Treatment Plants? n.d. doi:
10.3390/cleantechnol3010002. 10.3390/w12041118.
[37] Aro EM. From first generation biofuels to advanced solar biofuels. Ambio 2016; [76] Almuharef I, Rahman MS, Qin W. Enzymatic conversion of glycerol to 2,3-buta­
45:24–31. https://doi.org/10.1007/s13280-015-0730-0. nediol and acetoin by serratia proteamaculans SRWQ1. Waste Biomass Valoriz
[38] Bhuiya MMK, Rasul MG, Khan MMK, Ashwath N, Azad AK, Hazrat MA. Second 2019;10:1833–44. https://doi.org/10.1007/s12649-018-0221-1.
generation biodiesel: potential alternative to-edible oil-derived biodiesel. Energy [77] Zhang L, Singh R, Guo Z, Li J, Chen F, He Y, et al. An artificial synthetic pathway
Procedia 2014;61:1969–72. https://doi.org/10.1016/j.egypro.2014.12.054. for acetoin, 2,3-butanediol, and 2-butanol production from ethanol using cell free
[39] Water Waste FOGs | Argent Energy n.d. multi-enzyme catalysis. Green Chem 2017;20:230. https://doi.org/10.1039/
[40] Alam F, Mobin S, Chowdhury H. Third generation biofuel from Algae. Procedia c7gc02898a.
Eng 2015;105:763–8. https://doi.org/10.1016/j.proeng.2015.05.068. [78] Veiga S, Faccio R, Romero M, Bussi J. Utilization of waste crude glycerol for
[41] Shokravi H, Shokravi Z, Heidarrezaei M, Ong HC, Rahimian Koloor SS, Petrů M, hydrogen production via steam reforming over Ni–La–Zr catalysts. Biomass
et al. Fourth generation biofuel from genetically modified algal biomass: Bioenergy 2020;135:105508. https://doi.org/10.1016/j.biombioe.2020.105508.
challenges and future directions. Chemosphere 2021:285. https://doi.org/ [79] Biotechnol Biofuels A, Rosales-Calderon O, Arantes V. A review on commercial-
10.1016/j.chemosphere.2021.131535. scale high-value products that can be produced alongside cellulosic ethanol 2019.
[42] Singh SP, Singh D. Biodiesel production through the use of different sources and doi: 10.1186/s13068-019-1529-1.
characterization of oils and their esters as the substitute of diesel: A review n.d. [80] Zahid I, Ayoub M, Bin AB, Nazir MH, Zulqarnain KMA, et al. Activation of nano
doi: 10.1016/j.rser.2009.07.017. kaolin clay for bio-glycerol conversion to a valuable fuel additive. Sustain 2021;
[43] Anuar MR, Abdullah AZ. Challenges in biodiesel industry with regards to 13:1–17. https://doi.org/10.3390/su13052631.
feedstock, environmental, social and sustainability issues: A critical review 2016. [81] Kheireddine Aroua M, Shya Lee C, Sh Al-Saadi L, Eze VC, Harvey AP. Techno-
doi: 10.1016/j.rser.2015.12.296. economic analysis of glycerol valorization via catalytic applications of sulphonic
[44] Lim S, Keat Teong L. Recent trends, opportunities and challenges of biodiesel in acid-functionalized copolymer beads. Front Chem 2020;1:882. https://doi.org/
Malaysia: An overview n.d. doi: 10.1016/j.rser.2009.10.027. 10.3389/fchem.2019.00882.
[45] Orugba HO, Oghenejoboh KM, Oghenejoboh UM, Ohimor OE. Production of [82] Sittijunda S, Reungsang A. Valorization of crude glycerol into hydrogen, 1,3-
biodiesel from a novel combination of raphia africana kernel oil and turtle shell propanediol, and ethanol in an up-flow anaerobic sludge blanket (UASB) reactor
(centrochelys sulcata) heterogenous catalyst. J Human, Earth, Futur 2021;2: under thermophilic conditions. Renew Energy 2020;161:361–72. https://doi.org/
258–68. https://doi.org/10.28991/hef-2021-02-03-07. 10.1016/j.renene.2020.07.053.
[46] Oleoline_Glycerine_Quarterly_December_2020 n.d. [83] Ethanol Price Market Analysis - Echemi n.d.
[47] Glycerol Market Trends Analysis 2018-2024 World Industry Report n.d. [84] Ethanol Prices, Price, Pricing, Market Analysis | ChemAnalyst n.d.
[48] Is HVO the Holy Grail of the world biodiesel market? - Greenea n.d. [85] Genieva S, Mollova E. Utilization of the glycerol phase from biodiesel production
[49] REFINERY NEWS ROUNDUP: European plants ramping up renewables projects | for the preparation of alkyd paints. J Coatings Technol Res 2020;17:1207–16.
S&P Global Platts n.d. https://doi.org/10.1007/s11998-020-00339-y.
[50] Synthetic glycerine is back (but never really went away)! n.d. [86] Yao P, You S, Qi W, Su R, He Z. Investigation of fermentation conditions of
[51] Ufop. Report on global market supply 2017/2018. Union Promot Oil Protein biodiesel by-products for high production of β-farnesene by an engineered
Plants 2017::51. Escherichia coli. Environ Sci Pollut Res 2020;27:22758–69. https://doi.org/
[52] Ardi MS, Aroua MK, Hashim NA. Progress, prospect and challenges in glycerol 10.1007/s11356-020-08893-z.
purification process: a review. Renew Sustain Energy Rev 2015;42:1164–73. [87] 18794-84-8 (E)-β-Farnesene 062-03001 068-03003[Detail Information] |
https://doi.org/10.1016/j.rser.2014.10.091. Laboratory Chemicals-FUJIFILM Wako Chemicals U.S.A. Corporation n.d.
[53] Greenea. Glycerine market: lack of interdependence between supply and demand [88] Wang Y, Furukawa S, Song S, He Q, Asakura H, Yan N. Catalytic production of
- Greenea. 2015. alanine from waste glycerol. Angew Chem. – Int Ed 2020;59:2289–93. https://
[54] Albarelli JQ, Santos DT, Holanda MR. Energetic and economic evaluation of doi.org/10.1002/anie.201912580.
waste glycerol cogeneration in Brazil. Brazilian J Chem Eng 2011;28:691–8. [89] Tian M, Wang ZY, Fu JY, Li HW, Zhang J, Zhang XF, et al. Crude glycerol
https://doi.org/10.1590/S0104-66322011000400014. impurities improve Rhizomucor miehei lipase production by Pichia pastoris. Prep
[55] Animal by-product categories, site approval, hygiene and disposal – GOV.UK n.d. Biochem Biotechnol 2020. https://doi.org/10.1080/10826068.2020.1870135.
[56] Market T, To I, Your S. Glycerine Market Report; 2020. [90] Shahrin NAM, Chin PW, Serri NA. Crude glycerol utilisation in monolaurin
[57] Reymermier F. Glycerine Market Report. Oleoline 2020:1–4. production using immobilised Rhizomucor miehei lipase: optimisation and
[58] Glycerine Market Is Estimated To Reach USD 4506.6 Million By 2028 n.d. thermodynamics study. J Oil Palm Res 2019;31:615–23. https://doi.org/
[59] Oleoline. Crude glycerine market report. 2020. 10.21894/jopr.2019.0054.
[60] Samul D, Leja K, Grajek W. Impurities of crude glycerol and their effect on [91] Abd Rahim MH, Hasan H, Lim EJ, Samrani PK, Abbas A. Pretreatment strategies
metabolite production. Ann Microbiol 2014;64:891–8. https://doi.org/10.1007/ to improve crude glycerol utilisation and metabolite production by Aspergillus
S13213-013-0767-X/TABLES/2. terreus. Int J Chem Eng 2019;2019. https://doi.org/10.1155/2019/2504540.
[61] Vs S, Nl E, et al. Short- and long-term bacterial inhibiting effect of high [92] Lovastatin (MK-803) | ≥99%(HPLC) | Selleck | HMG-CoA Reductase inhibitor
concentrations of glycerol used in the preservation of skin allografts. Burns 2008; QCFile n.d.
34:205–11. https://doi.org/10.1016/J.BURNS.2007.02.009. [93] Geodin | Plasminogen PAI-1 activator | Hello Bio n.d.
[62] Soucek MD, Salata RR. Alkyd resin synthesis. Encycl Polym Nanomater 2015: [94] SULOCHRIN price,buy SULOCHRIN - chemicalbook n.d.
12–7. https://doi.org/10.1007/978-3-642-29648-2_278. [95] Wu Y, Jiang L, Lin Y, Qian L, Xu F, Lang X, et al. Novel crude glycerol
[63] Sh P, Od A, Ma O. Curr trends biomedical eng & biosci production and pretreatment for selective saccharification of sugarcane bagasse via fast pyrolysis.
characterization of soymilk using locally prepared date paste (phoenix Bioresour Technol 2019;294:122094. https://doi.org/10.1016/j.
dactylifera). White Sugar and Glycerol as Sweeteners 2017:7. https://doi.org/ biortech.2019.122094.
10.19080/CTBEB.2017.07.555709. [96] 1,6-Anhydro-beta-D-glucopyranose | 498-07-7 | Carbosynth Product n.d.

17
T. Attarbachi et al. Fuel 340 (2023) 127485

[97] Wang Z, Ning T, Gao K, He X, Zhang H. Utilization of glycerol and crude glycerol of Crotalaria juncea oil. Energy Convers Manag 2016;118:450–8. https://doi.org/
for polysaccharide production by an endophytic fungus Chaetomium globosum 10.1016/j.enconman.2016.03.088.
CGMCC 6882. Prep Biochem Biotechnol 2019;49:807–12. https://doi.org/ [123] Silveira N, Frantz TS, Lütke SF, Arabidian VC, Cadaval TRS, Pinto LAA. Treatment
10.1080/10826068.2019.1621895. of industrial glycerol from biodiesel production by adsorption operation: kinetics
[98] Rodrigues CV, Rios Alcaraz FA, Nespeca MG, Rodrigues AV, Motteran F, Tallarico and thermodynamics analyses. Chem Eng Commun 2019;206:1399–409. https://
Adorno MA, et al. Biohydrogen production in an integrated biosystem using crude doi.org/10.1080/00986445.2018.1537267.
glycerol from waste cooking oils. Renew Energy 2020;162:701–11. https://doi. [124] Chiu CW, Dasari MA, Sutterlin WR, Suppes GJ. Removal of residual catalyst from
org/10.1016/j.renene.2020.08.061. simulated biodiesel’s crude glycerol for glycerol hydrogenolysis to propylene
[99] Boga DA, Liu F, Bruijnincx PCA, Weckhuysen BM. Aqueous-phase reforming of glycol. Ind Eng Chem Res 2006;45:791–5. https://doi.org/10.1021/ie050915s.
crude glycerol: effect of impurities on hydrogen production. Catal Sci Technol [125] Cognet P, Antonaroli S, Pontalier P-Y, Aziz A, Raman A, Tan HW, et al. Two-step
2016;6:134–43. https://doi.org/10.1039/c4cy01711k. purification of glycerol as a value added by product from the biodiesel production
[100] Ahmad Farid MA, Hassan MA, Roslan AM, Ariffin H, Norrrahim MNF, process. Front Chem | WwwFrontiersinOrg 2019;7:774. https://doi.org/10.3389/
Othman MR, et al. Improving the decolorization of glycerol by adsorption using fchem.2019.00774.
activated carbon derived from oil palm biomass. Environ Sci Pollut Res 2021. [126] Isahak WNRW, Jahim JM, Ismail M, Nasir NF, Ba-Abbad MM, Yarmo MA.
https://doi.org/10.1007/s11356-021-12585-7. Purification of crude glycerol from industrial waste: Experimental and simulation
[101] Kongjao S, Damronglerd S. Purification of crude glycerol derived from waste studies. J Eng Sci Technol 2016;11:1056–72.
used-oil methyl ester plant 2010;27:944–9. doi: 10.1007/s11814-010-0148-0. [127] Espacenet – Suchergebnisse n.d.
[102] Manosak R, Limpattayanate S, Hunsom M. Sequential-refining of crude glycerol [128] Carmona M, Lech A, de Lucas A, Pérez A, Rodriguez JF. Purification of glycerol/
derived from waste used-oil methyl ester plant via a combined process of water solutions from biodiesel synthesis by ion exchange: sodium and chloride
chemical and adsorption. Fuel Process Technol 2011;92:92–9. https://doi.org/ removal. Part II J Chem Technol Biotechnol 2009;84:1130–5. https://doi.org/
10.1016/j.fuproc.2010.09.002. 10.1002/jctb.2144.
[103] Hájek M, Skopal F. Treatment of glycerol phase formed by biodiesel production. [129] Sdrula N. A study using classical or membrane separation in the biodiesel process.
Bioresour Technol 2010;101:3242–5. https://doi.org/10.1016/j. Desalination 2010;250:1070–2. https://doi.org/10.1016/j.desal.2009.09.110.
biortech.2009.12.094. [130] Rohm, Haas. Ion Exchange for Dummies. n.d.
[104] Yong K, Ooi TL, Dzulkefly K, Wan Yunus WMZ, Hazimah A. Refining of crude [131] Ion Exchange Resins for Cane Sugar Decolorization AmberLite TM FP Ion
glycerine recovered from glycerol residue by simple vacuum distillation refining Exchange Resins. n.d.
of crude glycerine recovered from glycerol residue by simple vacuum distillation. [132] Biodiesel Magazine – The Latest News and Data About Biodiesel Production n.d.
J Oil Palm Res 2001;13:39–44. [133] Shaari NZK, Rahman NA. Performance of thin film composite in the purification
[105] Priya S, Desai SM. Studies on purification of crude glycerol using ion exchange of crude glycerol. BEIAC 2013 – 2013 IEEE Bus Eng Ind Appl Colloq 2013:565–70.
resin 2019;8:671–4. doi: 10.1109/BEIAC.2013.6560192.
[106] Khok YT, Ooi CH, Matsumoto A, Yeoh FY. Reactivation of spent activated carbon [134] Mah SK, Chang CCH, Wu TY, Chai SP. The study of reverse osmosis on glycerin
for glycerine purification. Adsorption 2020;26:1015–25. https://doi.org/ solution filtration: dead-end and crossflow filtrations, transport mechanism,
10.1007/s10450-020-00210-x. rejection and permeability investigations. Desalination 2014;352:66–81. https://
[107] Schaffner F, Pontalier PY, Sanchez V, Lutin F. Bipolar electrodialysis for glycerin doi.org/10.1016/j.desal.2014.08.008.
production from diester wastes. Filtr 2003;40:35–9. https://doi.org/10.1016/ [135] Govindaraju R, Chen SS, Wang LP, Chang HM, Pasawan M. Significance of
S0015-1882(03)00037-5. membrane applications for high-quality biodiesel and byproduct (glycerol) in
[108] Shirazi MMA, Kargari A, Tabatabaei M, Ismail AF, Matsuura T. Concentration of biofuel industries—review. Curr Pollut Reports 2021;7:128–45. https://doi.org/
glycerol from dilute glycerol wastewater using sweeping gas membrane 10.1007/s40726-021-00182-8.
distillation. Chem Eng Process Process Intensif 2014;78:58–66. https://doi.org/ [136] Zhang K, Qin Y, He F, Liu J, Zhang Y, Liu L. Concentration of aqueous glycerol
10.1016/j.cep.2014.02.002. solution by using continuous-effect membrane distillation. Sep Purif Technol
[109] Nanda M, Yuan Z, Qin W. Purification of crude glycerol using acidification: effects 2015;144:186–96. https://doi.org/10.1016/j.seppur.2015.02.034.
of acid types and product characterization. Austin J Chem Eng 2014;1:1–7. [137] Vadthya P, Kumari A, Sumana C, Sridhar S. Electrodialysis aided desalination of
[110] Velez AR, Mufari JR, Rovetto LJ. Sodium salts solubility in ternary glycerol+ crude glycerol in the production of biodiesel from oil feed stock. Desalination
water+alcohol mixtures present in purification process of crude glycerol from the 2015;362:133–40. https://doi.org/10.1016/j.desal.2015.02.001.
biodiesel industry. Fluid Phase Equilib 2019;497:55–63. https://doi.org/ [138] De SW, Moraru MD, Jacobs B, Oudshoorn M, Helsen J. Separation and
10.1016/j.fluid.2019.05.023. purification technology electrodialysis of aqueous NaCl-glycerol solutions: a
[111] Dhabhai R, Ahmadifeijani E, Dalai AK, Reaney M. Purification of crude glycerol phenomenological comparison of various ion exchange membranes. Sep Purif
using a sequential physico-chemical treatment, membrane filtration, and Technol 2019;217:274–83. https://doi.org/10.1016/j.seppur.2019.02.030.
activated charcoal adsorption 2016. doi: 10.1016/j.seppur.2016.05.030. [139] Rozhdestvenskaya LM, Dzyazko YS, Kudelko EO, Vasilyuk SL, Belyakov VN.
[112] Hunsom M, Autthanit C. Adsorptive purification of crude glycerol by sewage Desalination of glycerol-water solutions by electrodyalysis using the organo-
sludge-derived activated carbon prepared by chemical activation with H3PO4, inorganic membranes. J Water Chem Technol 2017;39:26–32. https://doi.org/
K2CO3 and KOH. Chem Eng J 2013;229:334–43. https://doi.org/10.1016/j. 10.3103/S1063455X17010052.
cej.2013.05.120. [140] Dzyazko YS, Rozhdestvenska LM, Vasilyuk SL, Kudelko KO, Belyakov VN.
[113] Hunsom M, Autthanit C. Preparation of sludge-derived KOH-activated carbon for Composite membranes containing nanoparticles of inorganic ion exchangers for
crude glycerol purification. J Mater Cycles Waste Manag 2017;19:213–25. electrodialytic desalination of glycerol. Nanoscale Res Lett 2017:12. https://doi.
https://doi.org/10.1007/s10163-015-0402-y. org/10.1186/s11671-017-2208-4.
[114] de Farias BS, Vidal ÉM, Ribeiro NT, da Silveira N, da Silva VB, Kuntzler SG, et al. [141] Glycerin Distillation and Bleaching | Air Liquide n.d.
Electrospun chitosan/poly(ethylene oxide) nanofibers applied for the removal of [142] Glycerin Purification: Biocerin - KVT Process Technology n.d.
glycerol impurities from biodiesel production by biosorption. J Mol Liq 2018;268: [143] Ed E, Bped BE. Electromat 2010.
365–70. https://doi.org/10.1016/j.molliq.2018.07.081. [144] LEWATIT® MDS 1269 K / 290 n.d.
[115] Anzar E, Yusi S, Bow Y. Purification of crude glycerol from biodiesel by-product [145] Hazimah AH, Ooi TL, Salmiah A. Recovery of glycerol and diglycerol from
by adsorption using bentonite. Indones J Fundam Appl Chem 2018;3:83–8. glycerol pitch recovery of glycerol and diglycerol from glycerol pitch. J Oil Palm
https://doi.org/10.24845/ijfac.v3.i3.83. Res 2003;15:1–5.
[116] Aziz I, Sulistina RC, Hendrawati AL. Purification of crude glycerol from [146] Muniru O, Ezeanyanaso C, Fagbemigun T, Akubueze E, Oyewole A, Okunola O,
acidification using Tea waste. IOP Conf Ser Earth Environ Sci 2018:175. https:// et al. Valorization of biodiesel production: focus on crude glycerine refining/
doi.org/10.1088/1755-1315/175/1/012010. purification. J Sci Res Reports 2016;11:1–8. https://doi.org/10.9734/jsrr/2016/
[117] Kocak B, Yapar S. Bleaching of crude glycerol by organobentonite. Gazi Univ J Sci 27982.
2011;24:867–76. [147] Electrodialysis Systems and Ion Exchange Membranes - PCCell GmbH n.d.
[118] Yuliana M, Trisna L, Sari F, Lunardi VB. Glycerol purification using reactivated [148] Xu T, Huang C. Electrodialysis-based separation technologies: a critical review.
spent bleaching earth from palm oil refineries: Zero-waste approach. J Environ Am Inst Chem Eng AIChE J 2008;54:3147–59. https://doi.org/10.1002/
Chem Eng 2021;9:105239. https://doi.org/10.1016/j.jece.2021.105239. aic.11643.
[119] Saifuddin N, Refal H, Kumaran P. Rapid purification of glycerol by-product from [149] Coagulation and Flocculation | EMIS n.d.
biodiesel production through combined process of microwave assisted [150] Lee SJ, Hann T, Park SH. Seawater desalination using MOF-incorporated Cu-
acidification and adsorption via chitosan immobilized with yeast. Res J Appl Sci based alginate beads without energy consumption. ACS Appl Mater Interfaces
Eng Technol 2014;7:593–602. https://doi.org/10.19026/rjaset.7.295. 2020;12:16319–26. https://doi.org/10.1021/ACSAMI.9B22843.
[120] Barbosa SL, de Freitas MS, dos Santos WTP, Nelson DL, de Freitas Marques MB, [151] Homaeigohar S, Elbahri M. Graphene membranes for water desalination. NPG
Klein SI, et al. Preparation of activated charcoal from Acrocomia aculeata for Asia Mater 2017;2017(98):9. https://doi.org/10.1038/am.2017.135. e427.
purification of pretreated crude glycerol. Biomass Convers Biorefinery 2020. [152] Teow YH, Mohammad AW. New generation nanomaterials for water desalination:
https://doi.org/10.1007/s13399-020-00745-7. a review. Desalination 2019;451:2–17. https://doi.org/10.1016/J.
[121] Ahmad Farid MA, Hassan MA, Roslan AM, Ariffin H, Norrrahim MNF, DESAL.2017.11.041.
Othman MR, et al. Improving the decolorization of glycerol by adsorption using [153] Sinaga MS, Ramadhan MR, Rico G, Sitompul WGT. Effect of Acidification Mole
activated carbon derived from oil palm biomass. Environ Sci Pollut Res 2021;28: Ratio and Solvent Volume Ratio of Glycerol Purification. IOP Conf Ser Mater Sci
27976–87. https://doi.org/10.1007/s11356-021-12585-7. Eng 2019;505. doi: 10.1088/1757-899X/505/1/012116.
[122] Sadhukhan S, Sarkar U. Production of purified glycerol using sequential [154] Dewajani H, Hakim AR, Iswara MAI, Susanti T, Pratiwi D. The effect of
desalination and extraction of crude glycerol obtained during trans-esterification concentration and acid types on the acidification process for improving the

18
T. Attarbachi et al. Fuel 340 (2023) 127485

glycerol concentration and its application as a bio additive. IOP Conf Ser Mater [158] Cai T, Li H, Zhao H, Liao K. Purification of crude glycerol from waste cooking oil
Sci Eng 2020;732. doi: 10.1088/1757-899X/732/1/012009. based biodiesel production by orthogonal test method. China Pet Process
[155] Contreras-andrade I, Avella-moreno E, Sierra-cantor JF, Guerrero-fajardo CA, Petrochemical Technol 2013;15:48–53.
Ricardo J. Purification of glycerol from biodiesel production by sequential [159] Yatish KV, Lalithamba HS, Suresh R, Dayananda GN. Sodium phosphate synthesis
extraction monitored by 1 H NMR. Fuel Process Technol 2015;132:99–104. through glycerol purification and its utilization for biodiesel production from
https://doi.org/10.1016/j.fuproc.2014.12.016. dairy scum oil to economize production cost. Sustain Energy Fuels 2018;2:
[156] Elisa C, Oro D, Bonato M, Oliveira JV, Vinícius M, Luis M, et al. A new approach 1299–304. https://doi.org/10.1039/c8se00034d.
for salts removal from crude glycerin coming from industrial biodiesel production [160] Rakkitkanphun C, Teeka J, Kaewpa D, Areesirisuk A. Purification of biodiesel-
unit. J Environ Chem Eng 2019;7:102883. https://doi.org/10.1016/j. derived crude glycerol by acidification to be used as a carbon source for microbial
jece.2019.102883. oil production by oleaginous yeast Pseudozyma parantarctica CHC28. Biomass
[157] Mena-Cervantes VY, Hernández-Altamirano R, Tiscareño-Ferrer A. Development Convers Biorefinery 2021. https://doi.org/10.1007/s13399-021-01600-z.
of a green one-step neutralization process for valorization of crude glycerol [161] Mousavi HS, Rahimi M, Mohadesi M. Purification of glycerol using organic
obtained from biodiesel. Environ Sci Pollut Res 2020;27:28500–9. https://doi. solvent extraction in a microreactor. Biomass Convers Biorefinery 2020. https://
org/10.1007/s11356-019-07287-0. doi.org/10.1007/s13399-020-00750-w.
[162] Chethan SG, Khan MHM, L.K.Sreepathi. A novel method for refining crude
glycerol a byproduct from biodiesel industries 2018;7:138–43.

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