ARTICLE IN PRESS

Biomass and Bioenergy 30 (2006) 76–81

www.elsevier.com/locate/biombioe

Biodiesel from Jojoba oil-wax: Transesterification with methanol and

properties as a fuel
Laureano Canoira, Ramón Alcántara, Ma% Jesús Garcı́a-Martı́nez, Jesús Carrasco
Department of Chemical Engineering and Fuels, School of Mines, Polytechnic University of Madrid, Rı´os Rosas 21, 28003-Madrid, Spain
Received 14 April 2005; accepted 27 July 2005
Available online 19 September 2005

Abstract

The Jojoba oil-wax is extracted from the seeds of the Jojoba (Simmondsia chinensis Link Schneider), a perennial shrub that grows in
semi desert areas in some parts of the world. The main uses of Jojoba oil-wax are in the cosmetics and pharmaceutical industry, but new
uses could arise related to the search of new energetic crops.
This paper summarizes a process to convert the Jojoba oil-wax to biodiesel by transesterification with methanol, catalysed with sodium
methoxide (1 wt% of the oil). The transesterification reaction has been carried out in an autoclave at 60 1C, with a molar ratio methanol/
oil 7.5:1, and vigorous stirring (600 rpm), reaching a quantitative conversion of the oil after 4 h. The separation of the fatty acid methyl
esters (the fraction rich in FAME, 79% FAME mixture; 21% fatty alcohols; 51% of methyl cis-11-eicosenoate) from the fatty alcohols
rich fraction (72% fatty alcohols; 28% FAME mixture; 26% of cis-11-eicosen-1-ol, 36% of cis-13-docosen-1-ol) has been accomplished
in a single crystallization step at low temperature (
18 1C) from low boiling point petroleum ether.
The fraction rich in FAME has a density (at 15 1C), a kinematic viscosity (at 40 1C), a cold filter plugging point and a high calorific
value in the range of the European standard for biodiesel (EN 14214).
r 2005 Elsevier Ltd. All rights reserved.

Keywords: Simmondsia chinensis Link Schneider; Cryogenic crystallization; European standard EN 14214

1. Introduction (see Scheme 1), and therefore is more properly referred to

Jojoba (Simmondsia chinensis Link Schneider) is a
perennial shrub that grows naturally in the Sonora desert
(Mexico) and in the South-West of USA. Jojoba is now
cultivated in some countries: Argentina (2.0 kt yr
1), Israel
(1.1 kt yr
1), USA (1.0 kt yr
1) and some Mediterranean
and African lands are the main seed producers (data are for
the campaign 2002–03). Actually, there are in the world
7930 ha planted of Jojoba [1].
The Jojoba seed has a nut shaped form and is around
1–2 cm long, with red-brown to dark-brown colour. This
seed contains between 45 and 55 wt% of Jojoba oil-wax, a
golden liquid that can be obtained by cool pressing or
solvent extraction [2]. Unlike vegetable oils and animal
fats, Jojoba oil is not a triglyceride but a mixture of long
chain esters (97–98 wt%) of fatty acids and fatty alcohols
Corresponding author. Tel.: +34 1 336 6949; fax: +34 1 336 6948.
E-mail address: laucan@qyc.upm.es (L. Canoira).
as a wax; however, Jojoba oil-wax is the term in general
use. Jojoba oil-wax contains minor amounts of free fatty
acids and alcohols, phytosterols, tocopherols, phospholi-
pids and trace amounts of a triacylglycerol which have
been carefully analysed [3]. These minor constituents have
also an economical interest and a pilot-scale plant for their
extraction has been built [4].
The Jojoba oil-wax has a low chemical reactivity and a
very high normal boiling point (398 1C) that gives this
product very important physico-chemical properties and
uses. One of the first uses of the Jojoba oil-wax in the 1970s
was the substitution of the sperm whale oil, when whale
hunting was banned worldwide, but it has many other uses
in cosmetics, pharmaceuticals, dietetic foods, animal
feeding, lubrication, polishing and gardening [5].
Biodiesel is defined as ‘‘a fuel comprised of mono-alkyl
esters of long chain fatty acids derived from vegetable oils
or animal fats’’ [6]. Transesterification (also called alcoho-
lysis) of triglycerides for biodiesel manufacture has been

0961-9534/$ - see front matter r 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biombioe.2005.07.002
 ARTICLE IN PRESS
L. Canoira et al. / Biomass and Bioenergy 30 (2006) 76–81
CH3(CH2)7 (CH2)m
C C
H H
m = 7, 9, 11, 13
CH3(CH2)7 (CH2)m
C C
H H
H
Scheme 1. Transesterification reaction of Jojoba oil-wax with methanol, showing a general structure for methyl jojoboate (bottom left) and jojobyl
alcohol (bottom right).
extensively studied in the past few years [7] but the
transesterification of Jojoba oil-wax has received much
less attention [8]. Recently, Selim et al. [9] have published a
paper on the combustion of Jojoba methyl esters in an
indirect injection diesel engine.
Moreover, the feasibility of the commercial use of Jojoba
methyl ester as biodiesel is strongly dependant of the added
value (around 1.16 $ kg
1) [10] obtained for the fatty
alcohols produced as secondary products in the transester-
ification process, since the maximum price of the Jojoba
oil-wax for to make the process economically attractive
is 0.75 h kg
1 [11] far less than the actual market price
of the Jojoba oil-wax in USA (2.60 $ kg
1), although a
much lower price has been recently reported in Egypt of
0.80 h kg
1 [12].
The aim of this paper is to report the methods of
transesterification with methanol of Jojoba oil-wax with
acid and basic catalysis, and the procedure of separation of
methyl jojoboate (the fraction rich in FAME) from jojobyl
alcohol (the fatty alcohols rich fraction) by crystallization.
A preliminary evaluation of some properties of methyl
jojoboate as a diesel fuel (viscosity, density, cold filter
plugging point and high calorific value) is also reported.
2. Experimental
Methanol, toluene and petroleum ether (b.p. 40–70 1C)
all were commercial grade and used without drying or
purification.
2.1. Transesterification of jojoba oil-wax to methyl jojoboate
with acid catalysis
In a 1 L round bottomed flask, 0.4 L of methanol (316 g,
9.87 mol) were cooled in a ice-salt-water bath, and 23 mL of
77
O
C O (CH2)n (CH2)7CH3
C C
H H
n = 8, 10, 12, 14
CH3OH
O
C OCH3 + HO(CH2)n (CH2)7CH3
C C
H
acetyl chloride (25 g, 0.32 mol) added drop wise so that the
inside temperature was kept below 5 1C. The addition took
25 min. This solution was then added to 49.2 mL (42.4 g,
0.072 mol) of Jojoba oil-wax and 40 mL of toluene placed
in a 1 L cylindrical glass tank reactor, and the mixture was
refluxed at 62 1C for 4 h with vigorous stirring (600 rpm).
On cooling, it was poured into 0.6 L of distilled water. The
organic phase was decanted, and the aqueous phase was
extracted with petroleum ether (b.p. 30–70 1C). The organic
phases were combined, washed with 0.1 M sodium carbo-
nate solution, saturated sodium chloride solution (three
times) and dried over anhydrous sodium sulphate. Eva-
poration of the solvent in a rotary evaporator left 43.2 g
(97% isolated yield, 97% gas chromatography conversion)
of a mixture of methyl jojoboate and jojobyl alcohol in an
approximately 1:1 ratio. IR: 1745 cm
1 (CQO), 3649 cm
1
(O–H).
2.2. Transesterification of jojoba oil-wax to methyl jojoboate
with basic catalysis
Freshly cut sodium metal (0.736 g, 0.032 mol) was added
in small pieces to 50 mL of methanol (39.5 g, 1.23 mol)
placed in a glass flask in a hood over a period of about
30 min. The solution obtained was then poured over
200 mL of Jojoba oil-wax (172.4 g, 0.293 mol) and 100 mL
of methanol (78.7 g, 2.46 mol), placed in a 1 L autoclave
Burton-Coblin from Autoclave Engineers. The autoclave
was closed, and the mixture was heated at 65 1C with
stirring at 600 rpm for a 4 h period. On cooling at room
temperature, the autoclave was opened and the mixture
was neutralized adding concentrated hydrochloric acid
(2.8 mL, 0.032 mol) with vigorous stirring. The excess
methanol was evaporated under vacuum, and the crude
product was dried with anhydrous sodium sulphate and
 ARTICLE IN PRESS
78 L. Canoira et al. / Biomass and Bioenergy 30 (2006) 76–81

filtered, yielding 163.4 g (90% isolated yield, 100% gas
chromatography conversion) of a mixture of methyl
jojoboate and jojobyl alcohol in an approximately 1:1
ratio. IR: 1745 cm
1 (CQO), 3690 cm
1 (O–H).
2.3. Analysis
IR spectra were registered with a FT-IR Bruker Vector
22 in 1,1,2-trichlorotrifluoro ethane solution using a cell for
liquids with potassium bromide windows and a 0.1 mm
Teflon spacer, or in film between potassium bromide disks.
The gas chromatography-mass spectrometry analyses were
determined in a GC-MS HP-6890/MSD-5973 system. The
sample was dissolved in dichloromethane and 4 mL of this
solution were injected in the splitless mode at 275 1C in the
injection port using an automatic injector. The column was
a 5% diphenylpolydimethylsiloxane AT-5 from Alltech
(25 m  0.25 mm  0.20 mm), and helium was used as the
carrier gas at a constant column head pressure of 4.0 psi.
The gradients used were as follows: 60 1C (1 min), heating
at 6.00 1C min
1 to 300 1C, 10 min at 300 1C, and leaving
15 min between runs. The mass selective detector MSD-
5973 was set at 70 eV of accelerating voltage in the ion
source. Mass spectra were matched against the Wiley 275
mass spectral library for the identification of compounds,
using the software Chemstations from Hewlett-Packard.
The Fig. 1 shows a chromatogram of the crude transester-
ification product obtained in the GC-MS instrument,
corresponding to the composition of the Table 1, 3rd
column.
2.4. Separation of methyl jojoboate from jojobyl alcohol
The mixture of methyl jojoboate and jojobyl alcohol
(43 g, 50 mL) was dissolved in petroleum ether (b.p.
30–70 1C, 100 mL), and the solution was left overnight
in the freezer (
18 1C). An abundant white solid crystal-
lized that was quickly filtered at vacuum while cool using a
water pump. The mother liquors were concentrated in a
rotary evaporator yielding 23.8 g of oil (55.3% yield), the
FAME mixture methyl jojoboate, whose composition was
determined by GC-MS (Table 1, 4th column). The solids
filtered in the Büchner funnel were left at room tempera-
ture and they melted slowly (20 h) to yield after vacuum
concentration in a rotary evaporator 17.9 g of an oily
product (41.6% yield), the fatty alcohols rich fraction
jojobyl alcohol, whose composition was also determined by
GC-MS (Table 1, 5th column). A small amount of oily
solids (0.638 g, 1.6% yield) did not melt at room
temperature, and this oily white solid was also analysed
by GC-MS (Table 1, 6th column).
2.5. Determination of the physicochemical properties
of the biodiesel of jojoba oil-wax
Some physicochemical properties of the raw Jojoba oil-
wax, the transesterification crude product and the methyl
jojoboate separated by crystallization were determined in a
preliminary study of the feasibility of use these products as
a fuel in diesel engines. The ASTM, EN or ISO testing
methods used as well as the values obtained for the samples

TIC: 364A2.D
28.64

5e+07 28.57
4.8e+07
4.6e+07
4.4e+07
4.2e+07
4e+07
3.8e+07
3.6e+07
3.4e+07
3.2e+07 27.61
3e+07
Abundance

24.29
2.8e+07
2.6e+07 33.14
2.4e+07
2.2e+07 34.40
2e+07
1.8e+07
1.6e+07
1.4e+07
1.2e+07
1e+07
8000000
6000000
4000000 20.83 34.50 42.07 44.24
2000000 23.54 35.11
0
10.00 15.00 20.00 25.00 30.00 35.00 40.00
Time -->

Fig. 1. Gas chromatogram of the crude product of the transesterification of Jojoba oil-wax. Retention times of the products marked in the peaks
correspond approximately to those in Table 1.
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L. Canoira et al. / Biomass and Bioenergy 30 (2006) 76–81 79

Table 1
Composition of the products of the transesterification and separation of Jojoba oil-wax analysed by GC/MS

Compound RT (min) Crude product (%) Methyl jojoboate (%) Jojobyl alcohol (%) Residual solids (%)

Methyl palmitoleate C 16:1 20.34 0.21

CAS No: 1120-25-8
Methyl palmitate C 16: 0 20.83 1.08 1.27 0.43
CAS No: 112-39-0
Methyl 8,11-octadecadienate 24.09 0.04
C 18:2, CAS No: 56599-58-7
Methyl oleate C 18:1 24.29 7.22 9.51 3.39
CAS No: 112-62-9
Methyl cis-11-eicosenoate 28.60 37.55 51.46 18.33 25.96
C 20:1, CAS No: 3946-08-5
Methyl eicosanoate C 20:0 28.87 0.23
CAS No: 1120-28-1
Methyl cis-13-docosenoate 34.45 11.15 14.49 5.02 5.30
C 22:1, CAS No: 1120-34-9
Methyl docosanoate C 22:0 35.11 0.29
CAS No: 929-77-1
Methyl 15-tetracosenoate 44.24 1.07 1.96 0.62
C 24:1, CAS No: 56554-33-7
Cis-9-octadecen-1-ol 23.54 0.66 0.82 0.53
CAS No: 143-28-2
Cis-11-eicosen-1-ol 27.61 19.30 11.58 26.10 27.26
CAS No: 629-96-9
Cis-13-docosen-1-ol 33.14 19.00 7.21 35.75 41.48
CAS No: 629-98-1
Trans-13-docosen-1-ol 33.82 0.88 1.36
CAS No: 23519-83-7
15-Tetracosen-1-ol 42.00 1.34 1.70 7.99
CAS No: cis-50995-29-4
CAS No: trans-69521-46-6
FAME ¼ 79 FAME ¼ 28
Alcoh. ¼ 21 Alcoh. ¼ 78

Table 2
Properties of the biodiesel from Jojoba oil-wax

Sample Density at 15 1C (kg m
3) Kinematic viscosity at 40 1C Cold filter plugging point High calorific value (kJ g
1)
ASTM D 4052 (mm2 s
1) ASTM D 445 (CFPP, 1C) EN 116 ASTM D 2382

Jojoba oil-wax 868.6 24.89 +14

43.47
Crude producta 866.0 11.82 +4
42.17
Methyl jojoboateb 863.5 9.04
14
41.52
Methyl jojoboatec 871.6 10.44
10
42.82
Reference values Min. Max. Min. Max. Winter Summer
EN 14214 860 900 3.50 5.00
10 0
a
Crude transesterification product.
b
Methyl jojoboate obtained by crystallization of the crude product.
c
Methyl jojoboate obtained by elimination of the volatile compounds by distillation followed by crystallization.

and the reference values for biodiesel after EN 14214 are
summarized in Table 2.
3. Results and discussion
The transesterification of Jojoba oil-wax with methanol
has been carried out by two alternative methods: (a) acid
catalysis, with acetyl chloride and methanol to yield
anhydrous hydrogen chloride [8]. The conversion of the
oil (measured by GC/MS) was 97% and the yield of crude
isolated product was also 97%. However, the main
drawbacks of this method are the work-up of the reaction
product, that is time consuming and requires the use of
a great amount of petroleum ether to extract the aqueous
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80 L. Canoira et al. / Biomass and Bioenergy 30 (2006) 76–81

phase, and the formation of emulsions due to the free soaps
formed in the neutralization step, that difficult the phase
separation.
(b) With this precedent, we tried a basic catalyst, sodium
methoxide (1 wt% of the oil), freshly prepared from
sodium metal and methanol, that has proven very
successful in the transesterification reaction of triglyceride
oils [7]. In this method, the laborious steps of extraction
were avoided but, although the GC/MS conversion was
quantitative, only 90% of the crude mixture could be
isolated, probably due to the adsorption of some polar
components in the sodium sulphate used to dry the mixture
after neutralization.
The crude product, mixture of methyl jojoboate and
jojobyl alcohol, was analysed by GC-MS and FT-IR,
showing good agreement with its molecular structure
(Table 1, 3rd column). However, although its density and
high calorific value were adequate (866 kg m
3 and
42.17 kJ g
1, respectively), its fluidity properties were not:
kinematic viscosity (11.82 mm2 s
1) and cold filter plugging
point (CFPP, +4 1C). These fluidity properties were much
better than that of the raw Jojoba oil-wax (Table 2), due to
the breaking of the long molecular chains of the original
wax into shorter chains of methyl jojoboate and jojobyl
alcohol, but still they did not meet the specifications
of biodiesel as defined in the European standard EN 14214.
In the work of Selim [9], the low molar ratio of methanol
to raw oil used for the transesterification reaction (0.1)
implied that a significant amount of the product was
unreacted Jojoba oil-wax; as a proof of the above assertion,
the kinematic viscosity at 40 1C of the biodiesel used
(24.6 mm2 s
1) is very close to that of the raw Jojoba oil-
wax (24.8 mm2 s
1, Table 2) and very far from the limits
marked by the European standard for biodiesel
(3.5–5.0 mm2 s
1).
On the light of these preliminary results, a separation
step was devised, since the poor fluidity properties are due
mainly to the fatty alcohols that present strong inter-
molecular hydrogen bonds. The mixture of methyl
jojoboate and jojobyl alcohol (50 mL) was dissolved in
low boiling point petroleum ether (100 mL) in a volumetric
ratio 1:2, and the solution was left in the freezer overnight
at
18 1C. An abundant white solid crystallized, that was
quickly filtered at vacuum while cool. The mother liquors
were concentrated at vacuum, yielding 23.8 g (55%) of an
oil, the FAME mixture methyl jojoboate, whose GC-MS
analysis showed a composition of 79% FAME mixture
(51.5% of methyl-cis-11-eicosenoate, C 20:1, and 14.5% of
methyl-cis-13-docosenoate, C 22:1), and 21% fatty alco-
hols (11.6% of cis-11-eicosen-1-ol).
The solids filtered in the Büchner funnel were left at
room temperature and they melted slowly (20 h) to yield
after vacuum concentration in a rotary evaporator 17.9 g
(41.6% yield) of an oily product, the fatty alcohols rich

Fig. 2. Block diagram of the batch transesterification process of Jojoba oil-wax with methanol, catalyzed with sodium methoxide. From left to right:
M1 ¼ fresh methanol feed; M2 ¼ recycled methanol; M ¼ methanol feed to the reactor; CAT ¼ catalyst feed; OIL ¼ Jojoba oil-wax feed; Pn ¼ Products
of the different unit operations; TKNEUTRL ¼ neutralization tank; HCL ¼ hydrochloric acid 35 wt%; TKSECADO ¼ drying tank; NA2-
SO4 ¼ anhydrous sodium sulphate; FILT1 ¼ filter 1; R ¼ residual solids (NaCl and Na2SO4  nH2O); DEST-ATM ¼ distillation column for the
recovery of methanol; E1 ¼ fresh petroleum ether; E2 ¼ recycled petroleum ether from the fatty alcohols mixture; E3 ¼ recycled petroleum ether from the
FAME mixture; CRISTALZ ¼ crystallizator; E ¼ petroleum ether feed to the crystallizator; FILT2 ¼ filter for FAME and fatty alcohols separation;
DEST-1 and DEST-2 ¼ distillation columns for the recovery of petroleum ether; P8 ¼ fatty alcohols mixture (42% yield); P9 ¼ FAME mixture
(55% yield).
 ARTICLE IN PRESS
L. Canoira et al. / Biomass and Bioenergy 30 (2006) 76–81
fraction or jojobyl alcohol, whose GC-MS analysis showed
a composition of 28% FAME mixture (18.33% of methyl-
cis-11-eicosenoate, C 20:1) and 72% fatty alcohols (26.1%
of cis-11-ecosen-1-ol, 35.75% of cis-13-docosen-1-ol, and
8.0% of 15-tetracosen-1-ol).
Only a minor amount of residual solids remained in the
filter (0.64 g, 1.6% yield) after the 20 h fusion period, whose
composition is showed in the Table 1.
After this relative success in the separation by a single
crystallization step of the FAME mixture from the fatty
alcohols, the physicochemical properties of the FAME
mixture sought as biodiesel were analysed: density
(863.5 kg m
3), high calorific value (41.52 kJ g
1) and cold
filter plugging point (
14 1C) were now in good agreement
with the European standard, although kinematic viscosity
(9.0 mm2 s
1) was still above the maximum allowed
(5.0 mm2 s
1). Fig. 2 shows a block diagram of the process
of transesterification of Jojoba oil-wax with basic catalysis,
including the steps of methanol recovery from the reaction
and of petroleum ether recovery from the cryogenic
crystallization.
A different separation method based in the vacuum
distillation of the crude transesterification product was
totally unsuccessful, since only a very small amount of light
cracked products could be distilled. The bottom product
was then separated by the single crystallization step and the
properties of the FAME mixture fraction analysed,
resulting poorer values of the CFPP (
10 1C) and the
kinematic viscosity (10.4 mm2 s
1) due to the evaporation
of the lighter products in the distillation.
This work demonstrated the successful production of a
Jojoba-based FAME biodiesel which is close to meet the
biodiesel standard EN 14214. This was achieved through
the use of sodium methoxide as a catalyst and a cryogenic
separation of the products. While FAME from Jojoba can
be produced in 55% yield, its use as a fuel will be
dependant on the co-production of value added products
from the fatty alcohols to make it economical. Jojoba as an
81
energetic crop for South Europe and North Africa has a
high potential.
Acknowledgements
We wish to thank to the CEPSA research centre in
Torrejón de Ardoz (Madrid) for the analysis of the density,
viscosity and cold filter plugging point of the samples, and
EIEC Complex SL for the gift of Jojoba oil-wax.
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