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Transcript of No21-Kyoto-Univ
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8/2/2019 No21-Kyoto-Univ
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NEDO High-efficiency Bioenergy Conversion Project
- R & D for Biodiesel Fuel (BDF) by Two-step Supercritical Methanol Method -
Shiro Saka, Eiji Minami and Dadan Kusdiana
Graduate School of Energy Science, Kyoto University
Yoshida-honmachi, Sakyo-ku, Kyoto 606-8501
Biodiesel fuel (BDF) is one of the most promising bioenergies, which can be produced from oils/fats
through transesterification. A current commercial process for BDF production involves the use of alkali
catalyst, followed by the removal of the catalyst and saponified products from free fatty acids (FFA). Inaddition, water-containing waste oils/fats depress the catalyst activity. These cannot allow the low-quality
feedstocks, such as waste cooking oil and waste industrial oil, available for their efficient utilization.
For solving these problems, our research group has been working to develop non-catalytic biodiesel
production by supercritical methanol treatment (>239oC, >8.09MPa) since 1998. Variables affecting the
reaction were investigated followed by proposing the optimum conditions to be 350oC, 20MPa and 9 min.
Compared with the alkali-catalyzed method, the supercritical methanol method has superiorities in terms of
reaction time and purification step. In addition, the yield of BDF is higher than that of alkali-catalyzed
method due to a simultaneous conversion of FFA to its methyl esters through esterification. These findings
indicate that the supercritical methanol treatment has a great availability to perform transesterification of
triglycerides (TG) and methyl esterification of FFA, and that would provide a clue as to establishment of
the efficient biodiesel production process.
Although the catalyst-free supercritical methanol method (Saka process) has been proven to produce
BDF in high yield, it requires a restrictive reaction condition compared to the conventional alkali- and
acid-catalyzed methods. Therefore, further effort was made to develop an alternative method through the
two-step preparation; hydrolysis of TG in subcritical water and subsequent methyl esterification of the fatty
acids in supercritical methanol as shown in Figure 1. In this two-step method (Saka-Dadan process),
therefore, esterification is the main reaction for BDF production, while in the conventional supercritical
method, transesterification is the most major one. The proposed reaction conditions were 270oC, 7MPa and
20 min for hydrolysis and methyl esterification, respectively. For such conditions, the common stainless
steel can be applicable and resist enough for reaction vessel. Furthermore, the BDF product was found to be
low in total glycerol content which satisfies the biodiesel specification standards in EU, US and Kyoto City.
Fortunately, this research project has been selected as one of the NEDO High-efficiency Bioenergy
Conversion Projects in FY2003 for coming 3 years with a budget of about 840 million. Figure 2 shows
the framework of this industry-university joint research team. In this project, Asahi KASEI Corp. is
responsible for establishment of the commercial process to produce high quality BDF (total glycerol
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8/2/2019 No21-Kyoto-Univ
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content < 0.24wt% through a high energy efficiency, > 80%), while Kyoto University is for fundamental
study on the reactions and BDF evaluation, Asahi Engineering Co., Ltd. is for development of the
pre-/post-treatment and automatic control systems, Asahi Research Center Co., Ltd. is for establishment of
the business model on BDF and Toyota Tsusyo Corp. is for market research on the oil/fat feedstocks and
BDF, respectively.
In FY2003, two flow-type systems have been designed and developed based on scientific and
technical knowledge at Kyoto University; one is the laboratory-scale equipment for the fundamental study
on the reactions, while the other is the bench-scale plant in Fuji City, as shown in Figure 3, which is used to
discuss a mass production technology. In addition, pre- and post-treatment steps for oil/fat feedstocks and
waste water were, respectively, examined to establish the total process of the system. On the other hand, a
trend survey on BDF including its production, utilization and policy was made in Japan as well as foreign
countries. A market research on oil/fat feedstocks was also carried out to assure the feedstock suppliers.
Oils/fats
Water
Subc ritic al Wate r
(270oC/7MPa)
Glycerol
MeOH
Biodiesel fuel
BDF
Wate r phase
Oil pha se
Supercritica l MeO H
(270oC/7MPa)
Waste wa ter
MeOH reco very
Purification
Figure 1. Scheme of the two-step supercritical methanol method (Saka-Dadan Process)
NEDO
Consignation
Asahi Engine ering Co ., Ltd .
Kyoto University
Asahi Research Cen ter Co ., Ltd.
Toy ota Tsusho Co rp.
Asahi KASEI Corp.
Re-consignation
Ta rgets
1. Estab lishment of c omm ercialprocess
2. Esta blishme nt o f b usiness mod el
3. Tota l glyce rol con tent < 0.24wt%4. Energy efficiency > 80%
Figure 2. Framework of the NEDO project Figure 3. Bench-scale plant in Fuji City for the
two-step supercritical methanol method