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Author's Accepted Manuscript: Radiation Physics and Chemistry
Author's Accepted Manuscript: Radiation Physics and Chemistry
Author's Accepted Manuscript: Radiation Physics and Chemistry
www.elsevier.com/locate/radphyschem
PII: S0969-806X(17)30265-7
DOI: http://dx.doi.org/10.1016/j.radphyschem.2017.09.010
Reference: RPC7643
To appear in: Radiation Physics and Chemistry
Received date: 28 February 2017
Revised date: 21 July 2017
Accepted date: 11 September 2017
Cite this article as: Yuji Ueki, Seiichi Saiki, Hiroyuki Hoshina and Noriaki Seko,
Biodiesel fuel production from waste cooking oil using radiation-grafted fibrous
c a t a l y s t s , Radiation Physics and Chemistry,
http://dx.doi.org/10.1016/j.radphyschem.2017.09.010
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Biodiesel fuel production from waste cooking oil using radiation-grafted fibrous
catalysts
Research Institute, Quantum Beam Science Research Directorate, National Institutes for
Quantum and Radiological Science and Technology, 1233 Watanuki-machi, Takasaki, Gunma
370-1292, Japan
–1–
ABSTRACT
Waste cooking oil, which is raw material of a biodiesel fuel (BDF), contains two kinds of oil
components such as triglycerides (TGs) and free fatty acids (FFAs). Therefore, two kinds of
catalysts such as alkaline-type and acid-type are need in order to produce the BDF from waste
cooking oil. The alkaline-type grafted fibrous catalyst having hydroxide ion (OH-) was
and further treatment with NaOH. The acid-type catalyst having proton (H+) was synthesized
fabric, saponification with NaOH and protonation with HNO3. The OH- and H+ densities of
grafted fibrous catalyst were could be controlled by the grafting yield. The maximum OH- and
respectively. The catalytic performance of the each catalyst was evaluated by batchwise
transesterification of TGs and ethanol, and batchwise esterification of FFAs and ethanol. In
both cases, TGs and FFAs were gradually converted into BDF with the lapse of reaction time.
The mixed oil and four types of the actual waste cooking oils, which included both TGs and
FFAs, were completely converted into BDF by sequential catalytic reactions with acid-type
Keywords: Biodiesel fuel production, Triglyceride, Free fatty acid, Radiation-induced graft
–2–
1. Introduction
Primary energy sources are divided into non-renewable sources (fossil fuels, nuclear fuels)
and renewable sources (wind, solar, geothermal, tidal, hydroelectric, bioenergy). Today, most
of the world’s primary energy still comes from the burning of carbon-based fossil fuels [1]. So
many researches and developments aimed at harnessing renewable energy sources have been
carried out all around the world, from the point of view of global warming prevention
measures and diversification of energy sources. Especially, biodiesel fuel (BDF), which is one
of the bioenergy, has been attracting attention as an alternative petroleum diesel [2]. The BDF
is defined as the monoalkyl esters of long chain fatty acids (carbon chain length C12–C24),
and the BDF is generally produced by the chemical reaction of vegetable oils or animal fats
with alcohol in the presence of a catalyst. As compared with petroleum diesel fuel, the BDF
has the following characteristics. As derived from biomass resources, carbon dioxide to be
generated by the use of biodiesel fuel does not have any influence on the increase/decrease in
the amount of carbon dioxide in the global environment (carbon-neutral). As compared with
petroleum diesel fuel, the amount of noncombustible hydrocarbon, carbon monoxide and
suspended particulate matter (a leading cause of black smoke and smog) in the exhaust gas
can be reduced by less than 90%, 50% and 30%, respectively. Not containing sulfur
components, the sulfur oxide in the exhaust gas is nearly zero. The BDF is more easily and
faster biodegraded than petroleum diesel fuel, and the BDF can be handled with safety.
Additionally, the energy content of BDF is about 90% that of petroleum diesel fuel, and the
BDF can be used in compression-ignition engines instead of petroleum diesel with little or no
characteristics, the research and development to positively utilizing BDF is being gradually
activated. Recently, the BDF was vigorously produced in South America and Southeast Asia,
in addition to European Union and the United States which are the world's leading BDF
–3–
producer [3,4]. The world total BDF production amount reached nearly 25 billion liters in
2015 [5].
Virgin edible oil, crude oil and waste cooking oil are used as raw oils for BDF production,
and these oils contains two kinds of oil components such as triglycerides (TGs) and free fatty
acids (FFAs). At present, homogeneous catalysts, which are easily soluble in a reaction
solution, are mainly used in the industrial BDF production process, because of their high
catalytic abilities and low costs [6,7]. In the homogeneous catalyst method, firstly, the only
FFAs contained in a raw oil was converted into BDF by acid-type homogeneous catalyst such
as H2SO4 and HNO3, and then the remaining TGs was converted into BDF by alkaline-type
homogeneous catalyst such as NaOH and KOH, as shown in the following equation:
H+
RCOOH + R’OH RCOOR’ + H2O
OH-
G(COOR)3 + R’OH 3RCOOR’ + G(OH)3
where RCOOH represents the FFAs, R’OH represents the alcohol, RCOOR’ represents the
BDF, G(COOR)3 represents the TGs, and G(OH)3 represents the byproduct glycerine,
respectively. However, the homogeneous catalysts have serious drawback: the removal and
the reuse of the dissolved catalyst in reaction solution are difficult, and furthermore the
complicated BDF production processes such as neutralization, washing with water and
dehydration are required. Additionally, the wastewater treating equipment is also required,
because a large amount of acidic and alkaline wastewater are generated in the washing
process. As described in the above, the homogeneous catalytic method involves a number of
risk factors of production cost increase and environmental burden increase. To solve these
problems, the various BDF production methods such as an enzymatic method using lipase, a
noncatalytic supercritical methanol method and heterogeneous catalytic methods using metal
oxides and ion-exchange resins are researched vigorously [8–13]. Among them, the use of
–4–
porous ion-exchange resin was proposed by N. Shibasaki-Kitakawa et al [11–13]. The
insoluble ion-exchange resin could be easily recovered from reaction solution, and those
could be repeatedly used without any significant loss of the catalytic activity, by treating the
regeneration process. The BDF production process could be simplified and streamlined,
because the neutralization and the washing processes were skipped. Additionally, the
ion-exchange resin could adsorb and remove the impurities such as pigment components in
the BDF, and therefore high purity BDF can readily be produced. However, the BDF
conversion speed using the ion-exchange resin was slow, because the diffusional
mass-transfer of reactants was the rate-determining factor for BDF production. Briefly, the
most of the catalytic sites of the porous ion-exchange resin were located within its micropores,
and hence the reactants were very slowly and gradually transported to the catalytic sites by
To overcome the slow diffusional mass-transfer, we proposed the use of grafted fibrous
polymer as a heterogeneous catalyst [14,15]. The grafted fibrous polymer (hereinafter referred
to as grafted fibrous catalyst) was synthesized by radiation-induced emulsion grafting and its
subsequent chemical modifications of graft chain. The OH- and H+, which functioned as true
catalytic sites, were immobilized with high density onto the graft chains, and the grafted
polymer functioned as a scaffolding for catalytic sites. In the case of the grafted fibrous
catalyst, the reactants were easily and immediately transported to the catalytic sites by
convective flow of the reaction solution. Therefore, the diffusional mass-transfer resistance of
the reactants to the catalytic sites could be neglected. The objective of this study is to
construct BDF production process from the waste cooking oils containing TGs and FFAs by
using the grafted fibrous catalyst. Firstly, two kinds of catalysts such as alkaline-type and
acid-type grafted fibrous catalysts were synthesized, and then the catalytic performances of
each grafted fibrous catalyst were evaluated through the batchwise reaction for a single oil
–5–
component system, respectively. Secondly, the BDF production from two oil component
system and actual waste cooking oils was attempted through the sequential use of the
–6–
2. Experimental
2.1. Materials
Textile Manufacturing Co., Ltd. (Osaka, Japan) and was used as a trunk polymer for BDF
catalysts. The average fiber diameter of the PE/PP nonwoven fabric was 13 μm.
4-Chloromethylstyrene (CMS, purity: >95%) was purchased from AGC Seimi Chemical Co.,
Ltd. (Kanagawa, Japan) and the received yellow CMS was purified through a column of
activated basic alumina (MP EcoChrom™ Alumina B - Super I; MP Biomedicals, LLC., CA,
USA) to remove the tert-butylcatechol inhibitor. The purified transparent CMS was stored at
4°C. Ethyl p-styrenesulfonate (EtSS) was purchased from Tosoh Organic Chemical Co., Ltd.
(Tokyo, Japan) and was used as received. Polyoxyethylene (20) sorbitan monolaurate (Tween
20), which was used as a nonionic surfactant for preparing the monomer emulsion, was
obtained from Kanto Chemical Co., Inc. (Tokyo, Japan). The chemical reagents such as
(purity: >60%) and oleic acid (purity: >80%) were also obtained from Kanto Chemical and
were used without further purification. The water used for monomer emulsions was purified
Alkaline-type grafted fibrous catalyst, which had OH- and effectively functioned against
previously [14]. The synthesis scheme of alkaline-type grafted fibrous catalyst is shown in
Figure 1. PE/PP nonwoven fabric was irradiated with electron beam at the dose of 100 kGy.
–7–
Then, the irradiated PE/PP nonwoven fabric reacted with a deaerated monomer emulsion,
which was composed of 3 wt% CMS, 0.3 wt% Tween 20 and 96.7 wt% water, in a glass
ampoule and was kept in water bath at 40°C for 3 h. After grafting, the CMS-grafted
nonwoven fabric was aminated with 0.25 M TMA aqueous solution at 60°C for 2 h to
introduce quaternary ammonium groups into the CMS-graft chains, and then the aminated
CMS-grafted nonwoven fabric was further treated with 1 M NaOH at 25°C for 24 h, to
replace Cl- with OH-. The degree of grafting (Dg [%]) of the alkaline-type grafted fibrous
where W0 and W1 are the weights of the PE/PP nonwoven fabrics before and after grafting,
respectively. On the other hand, the OH- density of the alkaline-type grafted fibrous catalyst
was indirectly estimated from the quaternary amine-group density, because the OH- density
was equivalent to the quaternary amine-group density. The OH- density was defined by the
following equation:
where N is the nitrogen content (quaternary amine-group density) [N, %] of the alkaline-type
grafted fibrous catalyst, and the nitrogen content was measured using elemental analyzer
(model: 2400 Series II CHNS/O elemental analyzer, PerkinElmer, Inc., MA, USA).
Acid-type grafted fibrous catalyst, which had H+ and effectively functioned against FFAs,
was synthesized by radiation-induced emulsion grafting technique, and the synthesis scheme
is shown in Figure 1. After irradiating a PE/PP nonwoven fabric with 100 kGy, the irradiated
PE/PP nonwoven fabric reacted with a deaerated monomer emulsion, which was composed of
3 wt% EtSS, 0.3 wt% Tween 20, 92.7 wt% water and 4 wt% n-butanol, at 40°C for 4 h. After
–8–
grafting, the EtSS-grafted nonwoven fabric was treated with 1 M NaOH solution containing
50 vol% ethanol and 50 vol% water at 80°C for 2 h, to saponify the ester groups of the
EtSS-graft chains. Furthermore, the saponified EtSS-grafted nonwoven fabric was treated
with 0.5 M HNO3 aqueous solution at 25°C for 24 h, to immobilize the H+ onto the EtSS-graft
chains. The H+ density was indirectly estimated by the equilibrium adsorption capacity for
Cu2+ through a batchwise adsorption test, in a similar manner to that described previously
[16].
2.4. BDF production from TGs using alkaline-type grafted fibrous catalyst
The catalytic performance of the alkaline-type grafted fibrous catalyst was evaluated
through the batchwise transesterification of triolein, which was one of TGs, and ethanol,
referring to previous paper [14,15]. The reactor was initially filled with 1.4 g of triolein and
obtain a homogeneous phase. After stirring for 10 min, 0.2 g of the alkaline-type grafted
reaction solution, and the resultant mixture was heated up to 50˚C while stirring at 600 rpm.
At pertinent intervals, 0.1 mL aliquots were withdrawn from the reaction solution, and then
TGs and BDF concentration in the reaction solution were measured by using high
The conversion ratio of TGs to BDF was calculated from the change rate of total HPLC peak
2.5. BDF production from FFAs using acid-type grafted fibrous catalyst
The catalytic performance of the acid-type grafted fibrous catalyst was evaluated through
the batchwise esterification of oleic acid, which was one of FFAs, and ethanol. Reaction
–9–
solution was composed of 0.3 g of oleic acid, 9.2 g of ethanol and 5.0 g of n-decane. After
stirring the reaction solution for 10 min, 0.6 g of the acid-type grafted fibrous catalyst
(capacity: 3.4 mmol-H+/g-catalyst) was immersed in the reaction solution, and the resultant
mixture was heated at desired temperature while stirring at 600 rpm. At pertinent intervals,
0.1 mL aliquots were withdrawn from the reaction solution, and then FFAs and BDF
– 10 –
3. Results and discussion
In typical tendency of grafted polymer, the functional group density could be controlled by
the Dg. To enable use of the grafted polymer as the catalyst, the Dg of over 200% was
necessary. Especially, the emulsion grafting technique was more effective graft
polymerization technique, and the Dg of emulsion grafting was 10 times or more higher than
that of non-emulsion grafting [17]. As shown in Figure 2, in the case of alkaline-type grafted
fibrous catalyst, the emulsion grafting of CMS proceeded effectively, and the Dg of CMS
reached 300% after 3 h of grafting at 40°C. In this study, the Dg of CMS-emulsion grafting
enhanced 23 times higher compared with that of CMS-non-emulsion grafting using methanol
(Dg: CMS non-emulsion using methanol: 13%). After amination and alkaline treatment, the
OH- density of alkaline-type grafted fibrous catalyst with 300% Dg was equivalent to 3.6
mmol-OH-/g-catalyst.
On the other hand, in the case of acid-type grafted fibrous catalyst, the Dg of EtSS without
adding alcohol was 120%, because of low affinity between the EtSS micelle and the PE/PP
nonwoven fabric. That is, the hydrophilic groups on the EtSS micelle surface and the
hydrophobic groups on the PE/PP nonwoven fabric surface repelled each other. In order to
reduce the repulsive force of the EtSS micelle and the PE/PP nonwoven fabric, an alcohol was
added into the EtSS emulsion. As shown in Figure 3, it was found that the Dg was improved
by the addition of alcohol with higher hydrophobicity such as n-propanol and n-butanol.
However, in the case of n-pentanol and n-hexanol having excessive hydrophobicity, the EtSS
micelles were disintegrated, and they were dissolved into the water phase. As a result, the Dg
with adding n-hexanol was decreased than that without adding alcohol. In this study, it was
concluded that the optimal alcohol for the EtSS emulsion was n-butanol, and the Dg with
– 11 –
adding n-butanol was about 2 times higher than that without adding alcohol (Dg: EtSS
emulsion with adding n-butanol: 270%). After saponification and protonation, the H+ density
of acid-type grafted fibrous catalyst with 270% Dg was equivalent to 3.4 mmol-H+/g-catalyst.
3.2. BDF production from TGs and FFAs using grafted fibrous catalysts
In the case of the grafted fibrous catalysts, the OH- and H+, which were electrostatically
immobilized on the graft chains, functioned as true catalytic sites for TGs and FFAs,
respectively. In this section, the catalytic performances of each grafted fibrous catalyst were
evaluated through the batchwise reaction for a single oil component system. Figure 4 shows
the results of BDF production from TGs using the alkaline-type grafted fibrous catalyst,
where the result of the commercially available porous-type anion exchange resin (DIAION
PA306S, Mitsubishi Chemical Co., Ltd., Tokyo, Japan) with OH- are also indicated for
comparison. As shown in Figure 4, in the case of both alkaline-type catalysts, the TGs was
gradually converted into BDF with the lapse of transesterification time. Although, these
results demonstrated that both alkaline-type catalysts exhibited good catalytic activities, it was
found that the alkaline-type grafted fibrous catalyst could produce BDF with faster and higher
efficiency. The conversion speed of TGs using the grafted fibrous catalyst was 2.5 times faster
than that of the commercial resin. This difference of the conversion speeds was attributed to
Next, the catalytic performance of acid-type grafted fibrous catalyst was evaluated through
the batchwise esterification of FFAs and ethanol, and Figure 5 shows the relationship between
esterification temperature and conversion ratio of FFAs. As expected, the FFAs was gradually
converted into BDF with the lapse of esterification time, and the BDF was produced
efficiently in a short time at the higher esterification temperature. The esterification times
required to convert 90% of the initial FFAs into BDF were 27, 12, 8 and 4 h at 50, 60, 70 and
– 12 –
80°C, respectively. Based on these results, it was confirmed that the fibrous grafted polymer
3.3. BDF production from mixed oil consisting of TGs and FFAs
In the world’s BDF production process, the virgin and crude vegetable oils are used as raw
oils; rapeseed oil is used in European Union, soybean oil is used in United States, Brazil and
Argentina, palm oil is used in Indonesia, Thailand, Malaysia and Colombia. On the other hand,
Japan depends greatly on imports for almost all raw materials, and the self-sufficiency ratios
of overall oils/fats and edible vegetable oils are 13% and only 2%. Because of the low
self-sufficiency rate of oils/fats as well as the traditional Japanese spirit of “Mottainai”, the
research and development of BDF from waste cooking oils as raw oils has been engaged
mainly, instead of virgin oils. The composition ratio of TGs and FFAs in the waste cooking
oils are typically 95% or more and 5% or below, respectively. As in the above results of
Section 3.2, it was elucidated that the alkaline-type and acid-type grafted fibrous catalysts
show good activities for BDF production from TGs and FFA, respectively. In this section, the
BDF production from two oil component system included TGs and FFAs was attempted by
using the alkaline-type and the acid-type grafted fibrous catalysts, to enable practical use of
In this test, the reaction solution was composed of 0.9 g of triolein (TGs), 0.3 g of oleic
acid (FFAs), 9.2 g of ethanol and 5.0 g of n-decane, and the 0.3 g each of the alkaline-type
and the acid-type grafted fibrous catalysts was used, respectively. The all molar quantities of
TGs, FFAs, OH- of alkaline-type grafted fibrous catalyst and H+ of the acid-type grafted
fibrous catalyst in this reaction system were fixed at 1 mmol. The BDF production was
When the alkaline-type grafted fibrous catalyst was used as the primary catalyst for BDF
– 13 –
production from a mixed oil consisting of TGs and FFA, the transesterification of TGs was
stopped in just 30 minutes before reaching complete conversion of TGs, although a part of the
TGs was converted into BDF. Over 80% of the initial TGs still remained. The reason for this
incomplete transesterification of TGs that the alkaline-type grafted fibrous catalyst not only
functioned as a catalyst for BDF production from TGs but also functioned as an adsorbent for
FFAs, during the transesterification process. In this case, the electrostatically immobilized
OH- on the graft chain was reacted with FFAs (RCOOH) in the reaction solution, and then the
OH- was consumed in the production of water, as shown in the following equation:
where S is the grafted fibrous polymer. The FFAs-adsorbed alkaline-type grafted fibrous
BDF production from mixed oil by using together with alkaline-type and acid-type grafted
fibrous catalysts, the TGs and the FFAs were incompletely converted into BDF, similarly as
the above. The reason for this incomplete conversion was as follows: the FFAs conversion
speed using the acid-type grafted fibrous catalyst was very slow, and, on the other hand, the
FFAs adsorption speed with respect to the alkaline-type grafted fibrous catalyst was very fast.
Consequently, the FFAs adsorption onto alkaline-type grafted fibrous catalyst was
preferentially progressed as compared with the FFAs conversion, even though the acid-type
So next, we attempted to produce BDF from mixed oil by sequentially using the acid-type
and alkaline-type grafted fibrous catalysts, in the same manner as the conventional
homogeneous catalyst method. As shown in Figure 6 (A), when the acid-type grafted fibrous
catalyst was used as the primary catalyst for BDF production from a mixed oil consisting of
TGs and FFA, the FFAs in the reaction solution was completely converted into BDF for about
15 h, and the unreacted TGs remained as it is in the reaction solution. After reaching complete
– 14 –
esterification of FFAs, the acid-type grafted fibrous catalyst in the reaction solution was
replaced with the alkaline-type grafted fibrous catalyst functioned as the secondary catalyst,
by only pulling up with a forceps. In the subsequent transesterification, the all remaining TGs
was completely converted into BDF by the alkaline-type grafted fibrous catalyst, without
remaining any kind of oil components, as shown in Figure 6 (B). Based on above results, it
was found that the optimal procedure of the BDF production from mixed oil containing TGs
and FFAs using the grafted fibrous catalysts was the sequential catalytic treatment using
Finally, the BDF production from actual waste cooking oils was attempted. In this test, four
types of waste cooking oil were used. Their waste cooking oils derived from author’s house A,
author’s house B, oil bath in our laboratory and cafeteria of our institute, and the composition
ratio of TGs and FFAs of house A, house B, oil bath and cafeteria were 99.9%/0.1%,
99.8%/0.2%, 99.4%/0.6% and 97.9%/2.1%, respectively. The reaction mixture was composed
of 1.4 g of waste cooking oil, 14.4 g of EtOH, and 5.0 g of n-decane, and the 0.3 g each of the
alkaline-type and the acid-type grafted fibrous catalysts was used, respectively. The BDF
production for each waste cooking oil was carried out at 50°C, and the primary esterification
time and the sequential transesterification time were fixed at 24 h and 3 h, respectively.
Consequently, all oil components were completely converted into BDF by sequential catalytic
reactions with acid-type and then alkaline-type grafted fibrous catalyst, in any types of waste
cooking oils. Based on this result, it was found that the grafted fibrous catalysts for BDF
– 15 –
4. Conclusion
Two kinds of heterogeneous BDF catalysts such as alkaline-type and acid-type grafted
fibrous polymers were developed by radiation-induced emulsion grafting and their subsequent
chemical modifications. The emulsion grafting of EtSS was improved by adding alcohol to
EtSS emulsion, and the Dg of EtSS-emulsion grafting with adding 4 wt% n-butanol was about
2 times higher than that without adding alcohol. The TGs could be converted into BDF by
transesterification using the alkaline-type grafted fibrous catalyst, and the FFAs could be
converted into BDF by esterification using the acid-type grafted fibrous catalyst, respectively.
Additionally, a simple production process of BDF from any kind of oils including both TGs
and FFAs was constructed by using sequential catalytic reactions with acid-type and then
alkaline-type grafted fibrous catalysts. Therefore, by using the grafted fibrous catalysts, the
BDF production will probably become more simple and rational than the conventional BDF
production that require some complicated processes such as neutralization, washing with
water and dehydration. We are convinced that the results of this study indicated the versatility
and convenience of the radiation processing. And furthermore, we hope that our grafted
fibrous catalysts will help to create and promote new possibility and application for radiation
research.
– 16 –
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Production of high quality biodiesel from waste acid oil obtained during edible oil
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Figure captions
Fig. 1 Synthesis schemes of (A) alkaline-type grafted fibrous catalyst and (B) acid-type
CMS-non-emulsion grafting.
Fig. 5 Effect of esterification temperature on conversion ratio of FFAs. ۂ: 50°C, ڧ:
Fig. 6 BDF production from mixed oil through sequential (A) esterification using
– 19 –
Alkali
(A) Grafting Cl Amination N+ Cl- treatment N+ OH-
+ -
Cl N Cl N+ OH-
N(CH3)3 NaOH
Electron Radical Cl
beam CMS
– 20 –
Degree of grafting [%] 23 times
– 21 –
Degree of grafting [%]
Without alcohol
Methanol
Ethanol
Figure 3.
– 22 –
270%
70%
n-Propanol
Y. Ueki et al.
n-Butanol
n-Pentanol
n-Hexanol
of micelles
Disintegration
Conversion ratio of TGs [%]
1
100
75
Rate: 2.5 times
50
25
0
0 2 4 6
C
– 23 –
Conversion ratio of FFAs [%]
Co
– 24 –
(A)
FFAs
BDF
(B)
BDF
TGs
FFAs
A
– 25 –
Highlights
z 2-types of grafted fibrous catalysts for BDF production was synthesized by emulsion
grafting.
z Alkaline-type grafted catalyst converted triglyceride into BDF, and acid-type grafted
z Waste cooking oil could be converted into BDF by sequential catalytic reactions using
– 26 –