JAEA-Review-2010-065.pdf:15.99MB - 日本原子力研究開発機構

2-01
Fibrous Catalyst for Biodiesel Production Synthesized
by Radiation-induced Graft Polymerization
Y. Ueki a) , N. H. Mohamed b, c) , N. Seko a) and M. Tamada a)
a) Environment and Industrial Materials Research Division, QuBS, JAEA,
b) Radiation Processing Technology Division, Malaysian Nuclear Agency,
c) Department of Chemistry and Chemical Biology, Graduate School of Engineering, Gunma University
1. Introduction
Fossil fuel resources are decreasing daily. Biodiesel,
which is produced from vegetable oils and animal fats, has
been attracting attention as an alternative to petroleum diesel
fuel, since it is a non-toxic, biodegradable, renewable and
carbon-neutral fuel. At present, the homogenous alkali-
catalyzed method using NaOH or KOH as a catalyst is the
mainstream for the industrial production of biodiesel.
Recently, novel synthesis techniques, such as acid-, ion-
exchange resin-, lipase-, and metal oxide-catalyzed method
and non-catalytic supercritical methanol method, have been
investigated and developed by numerous researchers. In
this study, fibrous catalyst for biodiesel production was
synthesized by using radiation-induced graft polymerization.
2. Experimental
The graft polymerization was carried out by contacting
the nonwoven fabric irradiated by 100 kGy electron beam
with 5 wt% aqueous emulsion, which consisted of 4-chloro-
methylstyrene, polysorbate 20 and deionized water, in a
deaerated glass ampoule for 4 h at 40 ºC. After grafting,
the grafted fabric was treated with 0.25 M trimethylamine
(TMA) at 50 ºC to introduce a quaternary ammonium group,
and then resulting fabric was further treated with 1 M NaOH
to replace Cl - with OH - , before use.
3. Results and Discussion
The catalytic performance of the grafted polymer was
evaluated through the transesterification of triolein (purity:
60%) and ethanol. The transesterification was performed
by adding grafted polymer (weight: 0.5 g, capacity: 3.5
mmol-TMA/g-polymer) in a homogenous reaction solution
(triolein: 2.8 g, ethanol: 7.2 g, decane (auxiliary solvent):
10.0 g) at 50 ºC. As seen in Fig. 1, the triglycerides were
consumed with the lapse of time, and on the other hand the
biodiesels were produced with time. These results confirm
that the grafted polymer functions as a catalyst for biodiesel
production. The conversion ratio of triglycerides in
different reaction times reached 23%, 48%, 70%, 82%, and
95% at 10 min, 30 min, 1 h, 2 h, and 4 h, respectively.
Triglycerides in Fig. 1 is specifically noted; and the
conversion ratio of triglycerides relative to the reaction time
is plotted as in Fig. 2. In Fig. 2, the data with a commercial
granular anion exchange resin (Diaion PA306S, particle
size: 150–425 m, capacity: 3.4 mmol-TMA/g- resin) are
also shown for comparison. The grafted polymer promoted
the transesterification at a reaction speed higher by at least 3
JAEA-Review 2010-065
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times than that with the granular resin, and it was found that
the grafted polymer produced biodiesel efficiently within a
shorter period of time. The conversion ratio of
triglycerides in a reaction time of 2 h was 82% with the
grafted polymer and 26% with the granular resin.
Biodiesels Triglycerides
(A) Before reaction
(B) After 10 min
(C) After 30 min
(D) After 1 h
(E) After 2 h
(F) After 4 h
0 5 10 15 20 25
Retention time [min]
Conversion ratio of
triglycerides [%]
100
80
60
40
Grafted polymer
Fig. 1 Biodiesel produ-
ction using grafted
polymer synthesized
by radiation-induced
graft polymerization.
Transesterification conditions
Reactant: triolein (2.8 g),
ethanol (7.2 g), decane (auxili-
ary solvent) (10.0 g); catalyst:
grafted polymer (weight: 0.5
g, capacity: 3.5 mmol-TMA/g-
polymer; reaction time: 0 ~ 4
h, reaction temperature: 50 ºC.
Measurement conditions
Sample: biodiesel solution (10
times dilution); injection
volume: 5.0 L; column:
octadecyl bonded column
(size: 2.1 mm i.d. × 150 mm
long, particle size: 5 m);
mobile phase: A: water, B:
acetonitrile, C: 2-propanol–
hexane (5:4, v/v); flow rate:
0.5 mL/min; linear gradient:
30%A + 70%B (0 min) →
100%B (10 min) → 50%B +
50%C (20 min) → 50%B +
50%C (25 min); column temp-
erature: 40ºC; detection: UV
absorption at 205 nm.
20
Granular resin
0
0 1 2 3 4
Retention time [h]
Fig. 2 Comparison of catalytic performance of grafted
polymer and granular resin for biodiesel production.