Author’s Accepted Manuscript

Biodiesel fuel production from waste cooking oil

using radiation-grafted fibrous catalysts

Yuji Ueki, Seiichi Saiki, Hiroyuki Hoshina,

Noriaki Seko

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

Yuji Ueki*, Seiichi Saiki, Hiroyuki Hoshina, Noriaki Seko

Department of Advanced Functional Materials Research, Takasaki Advanced Radiation

Research Institute, Quantum Beam Science Research Directorate, National Institutes for

Quantum and Radiological Science and Technology, 1233 Watanuki-machi, Takasaki, Gunma

370-1292, Japan

* Corresponding author. Tel.: +81-27-346-9202

E-mail address: ueki.yuji@qst.go.jp (Y. Ueki).

–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

synthesized by radiation-induced emulsion grafting of 4-chloromethylstyrene onto a

polyethylene-coated polypropylene (PE/PP) nonwoven fabric, amination with trimethylamine

and further treatment with NaOH. The acid-type catalyst having proton (H+) was synthesized

by radiation-induced emulsion grafting of ethyl p-styrenesulfonate onto a PE/PP nonwoven

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

H+ densities of each catalyst were 3.6 mmol-OH-/g-catalyst and 3.4 mmol-H+/g-catalyst,

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

grafted fibrous catalyst and then alkaline-type grafted fibrous catalyst.

Keywords: Biodiesel fuel production, Triglyceride, Free fatty acid, Radiation-induced graft

polymerization, Fibrous catalyst.

–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

modifications to the engine components. Based on above excellent environmental-friendly

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

diffusion (i.e., concentration gradient).

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

acid-type and alkaline-type grafted fibrous catalysts.

–6–
2. Experimental

2.1. Materials

A polyethylene-coated polypropylene (PE/PP) nonwoven fabric was supplied by Kurashiki

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

trimethylamine (TMA), sodium hydroxide, nitric acid, methanol, ethanol, n-propanol,

2-propanol, n-butanol, n-pentanol, n-hexanol, acetonitrile, n-hexane, n-decane, triolein

(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

with a Milli-Q deionization system (Nihon Millipore K.K., Tokyo).

2.2. Synthesis of alkaline-type grafted fibrous catalyst

Alkaline-type grafted fibrous catalyst, which had OH- and effectively functioned against

TGs, was synthesized by radiation-induced emulsion grafting technique, as published

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

catalyst was calculated by the following equation:

Dg [%] = 100 × (W1 – W0)/W0,

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:

OH- density [mmol-OH-/g-catalyst] = (N/100)/14 × 1000

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).

2.3. Synthesis of acid-type grafted fibrous catalyst

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

3.6 g of ethanol, followed by the addition of 5.0 g of n-decane as a cosolvent in order to

obtain a homogeneous phase. After stirring for 10 min, 0.2 g of the alkaline-type grafted

fibrous catalyst (capacity: 3.6 mmol-OH-/g-catalyst) was immersed in the homogenous

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

performance liquid chromatography (HPLC) system, as mentioned in previous paper [15].

The conversion ratio of TGs to BDF was calculated from the change rate of total HPLC peak

areas of TGs before and after transesterification.

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

concentration in the reaction solution were measured by using HPLC system.

– 10 –
3. Results and discussion

3.1. Synthesis of alkaline-type and acid-type grafted fibrous catalysts

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

the difference of diffusional mass-transfer resistance, as described above.

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

having H+ functioned as an acid-type catalyst for BDF production from FFAs.

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

the grafted fibrous catalysts.

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

carried out at 70°C.

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:

RCOOH + S+(OH-) → S+(RCOO-) + H2O

where S is the grafted fibrous polymer. The FFAs-adsorbed alkaline-type grafted fibrous

catalyst was inactivated, because of consumption of OH-. Additionally, as a result of trying

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

grafted fibrous catalyst was present in the reaction solution.

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

acid-type and alkaline-type grafted fibrous catalysts.

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

production could adapt to any kind of actual waste cooking oils.

– 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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16. Ueki, Y., Seko, N., Hoshina ,H., Tamada, M., 2007. Preparation of polylactic acid

nonwoven fabric-based metal adsorbent by radiation-induced graft polymerization. J. Ion

Exchange 18, 214–219.

17. Seko, N., Ninh, N.T.Y., Tamada, M., 2010. Emulsion grafting of glycidyl methacrylate

onto polyethylene fiber. Radiat. Phys. Chem. 79, 22–26.

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Figure captions

Fig. 1 Synthesis schemes of (A) alkaline-type grafted fibrous catalyst and (B) acid-type

grafted fibrous catalyst.

Fig. 2 Effect of grafting condition on Dg. ‫ ۑ‬: CMS-emulsion grafting, ‫ ە‬:

CMS-non-emulsion grafting.

Fig. 3 Effect of addition of alcohol in EtSS emulsion on Dg.

Fig. 4 Comparison of catalytic activity of (‫ )ۑ‬alkaline-type grafted fibrous catalyst and

(‫ڹ‬porous-type anion exchange resin for BDF production.

Fig. 5 Effect of esterification temperature on conversion ratio of FFAs. ‫ۂ‬: 50°C, ‫ڧ‬:

60°C, ‫ڸ‬: 70°C, ‫ۑ‬: 80°C.

Fig. 6 BDF production from mixed oil through sequential (A) esterification using

acid-type grafted fibrous catalyst and (B) transesterification using alkaline-type

grafted fibrous catalyst. ‫ۑ‬: TGs, ‫ڹ‬: FFAs, ‫ڧ‬: BDF.

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 Alkali
(A) Grafting Cl Amination N+ Cl- treatment N+ OH-
+ -
Cl N Cl N+ OH-
N(CH3)3 NaOH
Electron Radical Cl
beam CMS

Trunk polymer Saponifi-

PE/PP non- + Protonation
Grafting SO3C2H5 cation SO3 Na SO3 H+
woven fabric
SO3C2H5 SO3 Na+ SO3 H+
SO3C2H5 NaOH HNO3
(B) EtSS

Figure 1. Y. Ueki et al.

– 20 –
Degree of grafting [%] 23 times

Grafting time [h]

Figure 2. Y. Ueki et al.

– 21 –
 Degree of grafting [%]

Without alcohol

Methanol

Ethanol

Figure 3.

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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

Transesterification time [h]

Figure 4. Y. Ueki et al.

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Conversion ratio of FFAs [%]
Co

Esterification time [h]

Figure 5. Y. Ueki et al.

– 24 –
(A)

Amount of BDF [mmol]

Amount of oils [mmol]
TGs

FFAs
BDF

Esterification time [h]

(B)

Amount of BDF [mmol]

Amount of oils [mmol]

BDF

TGs
FFAs
A

Transesterification time [min]

n]

Figure 6. Y. Ueki et al.

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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

catalyst converted free fatty acid into BDF.

z Waste cooking oil could be converted into BDF by sequential catalytic reactions using

acid-type and alkaline-type grafted catalysts.

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