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Abstract
Three principal variables, molar ratio of methanol to oil, amount of catalyst, and reaction temperature, affecting the yield of
acid-catalyzed production of methyl ester (biodiesel) from crude palm oil were investigated. The biodiesel was then used as an
extractant in batch and continuous acetone–butanol–ethanol fermentation, and its fuel properties and that of the biodiesel–ABE
product mix extracted from the batch culture analyzed. The optimized variables, 40:1 methanol/oil (mol/mol) with 5% H2S04
(vol/wt) reacted at 95°C for 9 h, gave a maximum ester yield of 97%. Biodiesel preferentially extracted butanol, and enhanced its
production in the batch culture from 10 to 12 g l − 1. The fuel properties of biodiesel and the biodiesel– ABE mix were comparable
to that of No.2 diesel, but their cetane numbers and the boiling points of the 90% fractions were higher. Therefore, they could
serve as efficient No. 2 diesel substitutes. The biodiesel– ABE mixture had the highest cetane number. © 2001 Elsevier Science
Ltd. All rights reserved.
0032-9592/01/$ - see front matter © 2001 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 3 2 - 9 5 9 2 ( 0 1 ) 0 0 1 7 8 - 9
66 E. Crabbe et al. / Process Biochemistry 37 (2001) 65–71
Studies to date based on biodiesel produced from In a preceding investigation we reported that CPO–
rapeseed or canola [8], sunflower [9], safflower [10] and FAME or crude palm oil methyl ester (CPOE) is bio-
soybean oils [11], have shown that biodiesel is environ- compatible with the process organism, selectively
mentally friendly because there is substantial reduction extracted butanol and in so doing increased both bu-
of unburned hydrocarbons, CO and particulate matter tanol productivity and production in ABE fermentation
emission when it is used in conventional diesel engine [15]. Therefore, the objective of this study was to
[12]. Moreover, biodiesel contains no sulphur, so the optimize the parameters that affect transesterification
sulphate fraction in the fuel is eliminated; and since the of CPO to its corresponding methyl ester (CPOE) and
oil originates from vegetable matter, the CO2 produced to evaluate its solvent extraction and fuel properties. In
is sequestered and the net CO2 released into the atmo- addition, we report on the performance of CPOE as an
sphere would be greatly reduced. Biodiesel blends effi- online butanol extractant in continuous ABE
ciently with petroleum diesel, and this results in less fermentation.
offensive exhaust odours which is a real benefit when
machinery or vehicles are used in confined environ-
ments. Additionally, it operates in modern combustion 2. Methods and materials
engines just like petroleum diesel; therefore, no engine
modifications are required. Biodiesel is less flammable 2.1. Chemicals
than No. 2 diesel fuel, which makes it useful in mining
operations where the risk of fire outbreak in under- Crude palm oil (CPO) was obtained from the Palm
ground shafts must be reduced to the minimum. Since it Oil Research Institute of Malaysia (PORIM, Serdang,
can be produced domestically it would boost many Malaysia) and stored at 4°C. Its quality characteristics
domestic economies and conserve foreign expenditure were determined according to the official methods of
fats and oils published by the Association of Oil
on crude oil imports by providing an impetus for the
Chemists. The fatty acid composition was determined
production of high yielding oil-seed crop varieties to
by gas chromatography (GC) as described later.
sustain a domestic biodiesel industry.
Methanol, hexane, petroleum ether and sulphuric acid,
In addition to their fuel properties, FAMEs of veg-
all of commercial grade quality, were purchased from
etable oil origin are known to extract butanol [13,15],
Nacalai Tesque Inc. (Kyoto, Japan). Fatty acid methyl
an excellent fuel extender, which efficiently blends with
esters, methyl laurate, methyl myristate, methyl palmi-
petroleum diesel to form diesohol [14]. Butanol is pre-
tate, methyl palmitoleate, methyl oleate, methyl
ferred to ethanol in diesohol formulation because un-
linoleate, methyl linoleneate and methyl arachidate ob-
like the latter it has a lower vapour pressure and mixes
tained from Sigma Chemical Co. (St. Louis, MO) and
with petroleum diesel at all temperatures. Diesohol
methyl stearate purchased from Wako Chemical Co.
production can also be achieved using FAME of veg- (Osaka, Japan) were used as the reference standards for
etable oil origin as butanol extractant in the acetone– GC analyses while methyl heptadecanoate purchased
butanol –ethanol (ABE) fermentation since the from Sigma Chemical Co. was used as the internal
composite product (FAME – butanol mix) would have standard.
fuel properties comparable to diesohol obtained by
blending petroleum diesel and commercial butanol. 2.2. Transesterification 6ariables (biodiesel preparation)
This process eliminates the need for further recovery of
butanol and would reduce the running cost of an ABE Methylation was carried out in ordinary 250-ml
fermentation industry. screw-capped bottles. Approximately 25 g of the melted
However, unlike fossil reserves, different regions of oil (at 400°C) was used in each experiment. All molar
the world have their own vegetable oil resources that ratios (mol/mol) are by convention written as methanol
could be exploited for biodiesel production. Biodiesel to CPO. The reaction catalyst used was concentrated
has been produced from a variety of sources including H2SO4 which was added as volume by weight of the oil
refined and crude vegetable oils, residues from veg- (vol/wt%). The fatty acid composition of the oil was
etable oil extraction, used cooking oils, and animal determined using a large excess of methanol (167:1
grease or tallow. In Southeast Asia, Malaysia has a rich mol/mol), in 3% H2SO4 and reacted at 95°C for 24 h.
oil palm industry that generates excess crude palm oil This product was then used as the standard of compari-
(CPO), in vast quantities for consumption. CPO is one son for subsequent ester yield. The effect of molar ratio
of the four leading vegetable oils traded on the world of methanol to oil was determined as 3:1 to 40:1
market. It is also cheaper than canola, rapeseed or mol/mol in 3% H2SO4; and the effect of the amount of
soybean oil and would reduce the overhead cost of acid was determined as 1 to 5% H2SO4 (vol/wt%) using
biodiesel production and generate a ready supply of 23:1. methanol to oil (mol/mol). Both reactions were
diesel fuel substitute or blend. carried out at 95°C for 24 h. The effect of the reaction
E. Crabbe et al. / Process Biochemistry 37 (2001) 65–71 67
2.6. Analysis
Fig. 1. Experimental setup of the continuous extractive fermentation 2.6.1. Fatty acid composition and ester yield
with cell recycle. The components are designated as follows: A, feed A mixture of the fatty acids (10 g l − 1 each in hexane)
reservoir; B, acid pump; C, acid reservoir; D, alkali reservoir; E,
served as the standard for gas chromatographic analysis
alkali pump; F, pH controller; G, feed pump; H, fermentor; I, pH
electrode; J, hollow fibre pump; K, hollow fibre module; L, permeate with methyl heptadecanoate as the internal standard.
pump; M, sparger; N, extractant; 0, filtrate; P, filtrate pump; Q, The fatty acids were quantified by injecting 2 ml of each
product reservoir; and R, stirrer. sample into the Shimadzu GC 8A chromatograph (Shi-
68 E. Crabbe et al. / Process Biochemistry 37 (2001) 65–71
ABE
Butanol Acetone Ethanol (g l−1)
Fig. 3. Effect of acid concentration on methyl ester yield. Initial glucose 40 g l−1.
70 E. Crabbe et al. / Process Biochemistry 37 (2001) 65–71
Table 3
Performance of CPOE as an online extractant
a
Permeate values reported are product concentrations after solvent extraction.
this microorganism. Furthermore, CPOE remained produced while enhancing its production (Table 2).
thermally and chemically stable even after autoclave Therefore, to further enhance solvent extraction during
sterilization at high temperature (121°C) and pressure continuous fermentation, a 3:2 (vol/vol) ratio of CPOE/
and as an extractant during in situ batch fermentation. cell-free permeate was used. Fig. 5 shows the profile of
In the present batch culture experiment, CPOE selec- ABE products in the fermentor and in the two phases
tively extracted about 40–50% of the total butanol of the extraction unit at steady state. Butanol was
preferentially extracted into the CPOE layer. About
10.5 g l − 1 of butanol and 18 g l − 1 of total ABE
solvents accumulated in the extractant, which also in-
cluded a high concentration of acetone (Table 3).
a
From batch extractive ABE fermentationusing 40 g l−1 sago
glucose in TYA medium. CPOE contained 5.74 g l−1 butanol ex-
Fig. 5. Concentration of ABE solvents, at the various stages of the tracted from the broth during cultivation.
continuous extractive fermentation with cell recycle experiment. The b
Annual Book of ASTM Standards, American Society for Testing
graphs are (A) butanol; (B) total ABE solvent. Key to symbols: and Materials Philadelphia, 2000.
Product concentration in the first fermentor,
; in permeate after c
From ASTM 1994.
solvent extraction, ; in CPOE, . d
IBP, FBP — Initial and final boiling point, respectively.
E. Crabbe et al. / Process Biochemistry 37 (2001) 65–71 71