Fuel 88 (2009) 2238–2240

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Fuel
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Hydrogenated monoterpenes as diesel fuel additives

Noah I. Tracy, Daichuan Chen, Daniel W. Crunkleton, Geoffrey L. Price *
Department of Chemical Engineering, University of Tulsa, 800 S. Tucker Drive, Tulsa, OK 74104, USA

a r t i c l e i n f o a b s t r a c t

Article history: Myrcene and limonene were hydrogenated to their fully saturated forms, 2,6-dimethyloctane and 1-iso-
Received 27 August 2008 propyl-4-methylcyclohexane, respectively. Mixtures of diesel fuel and up to 10% of each saturated hydro-
Received in revised form 4 February 2009 carbon were tested by ASTM D975 to evaluate the 2,6-dimethyloctane and 1-isopropyl-4-
Accepted 6 February 2009
methylcyclohexane as diesel fuel additives. The results showed that all tested mixtures were within
Available online 26 February 2009
the acceptable ranges specified by ASTM for diesel fuel and that the additives lowered the measured
cloud point, compared to the base diesel fuel. Saturated limonene had positive effects on viscosity, as
Keywords:
well. As myrcene and limonene are produced naturally in plants, these species represent a renewable
Myrcene
Limonene
route to fuel additives.
Renewable fuel Ó 2009 Elsevier Ltd. All rights reserved.
Diesel
Fuel additive

1. Introduction tively unselective for the paraffinic product, with production

Terpenes are unsaturated hydrocarbons found in various plant
extracts and used in metabolic processes in many plants. Naturally
occurring terpenes are important building blocks for fine chemi-
cals, flavorings, fragrances, and pharmaceuticals [1,2], and many
studies have considered the hydrogenation of terpenes for those
purposes. Two such terpenes are considered in this work, namely
myrcene (7-methyl-3-methylene-1,6-octadiene) and limonene
(1-methyl-4-prop-1-en-2-yl-cyclohexene). As seen in Fig. 1a, myr-
cene is a branched polyolefinic monoterpene found in tree oils [3].
Myrcene is also readily produced industrially by the pyrolysis of b-
pinene, which is a major constituent of pine turpentine [2,4]. Lim-
onene, shown in Fig. 1b, is a cyclic terpene extracted from orange
oil [5] and is used as both a fragrance molecule and a precursor
for other fragrances [1,6].
Catalytic hydrogenation of both myrcene and limonene have
been reported in the literature [1,2,6–8]; however, these studies
are not necessarily interested in the completely hydrogenated spe-
cies that would be useful as fuel additives. Instead, the partially
hydrogenated olefinic products of myrcene and limonene are stud-
ied for use as precursor molecules for scents, flavorings [2,6,7,9] or
other chemical precursors [10]. For example, Speziali et al. [2] used
various palladium, ruthenium, chromium, iridium, and rhodium
catalysts, with the goal of selecting the mono-olefinic species. They
found the reaction to be highly selective, with the rhodium cata-
lysts being the most selective. Such a catalyst, however, was rela-
* Corresponding author. Tel.: +1 918 631 2575; fax: +1 918 631 3268.
E-mail address: price@utulsa.edu (G.L. Price).
ranging from a trace to 4%. In our case, we chose palladium and
platinum because they promote complete hydrogenation.
From a fuel perspective, the multiple, highly reactive, unsatu-
rated bonds present in terpenes would be problematic if these spe-
cies were added directly to a diesel fuel. As a result, these species
need to be fully hydrogenated to eliminate double-bond reactivity.
With this in mind, this study considers the total hydrogenation of
myrcene and limonene to 2,6-dimethyloctane and 1-isopropyl-4-
methylcyclohexane (commonly known as p-menthane), respec-
tively, and use of these molecules as possible additives to diesel
fuels. These terpene-based fuel additives would be totally renew-
able because they come from plant tissues. Also, if renewable spe-
cies such as these are useful as additives to diesel fuels, other
investigators may be inspired to create such molecules by novel
pathways.
2. Materials and methods
Two monoterpenes, myrcene and limonene, were purchased
from Sigma–Aldrich. Ultra high purity hydrogen was obtained from
Best Welder’s Supply, Inc. (Tulsa, OK), and two US gallons (7.6 L)
of retail No. 2 diesel fuel were purchased in March 2008 in Tulsa,
OK. An Agilent 5975C GC–MS was used for the analysis of the myr-
cene and limonene precursors. GC–MS analysis indicated the myr-
cene was contaminated with a small amount of limonene and that
the limonene contaminants were pinene and 3-carene, both of
which are polysubstituted bicyclic monoolefins.
Two noble metal catalysts were used. The first was an activated
charcoal containing 1% palladium from Alfa Aesar. This catalyst

0016-2361/$ - see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2009.02.002
 N.I. Tracy et al. / Fuel 88 (2009) 2238–2240 2239

Mixtures of the hydrogenated monoterpenes and diesel fuel

were prepared by adding the products in desired quantities to re-
tail diesel samples. We chose 2, 5, and 10 wt.% levels for hydro-
genated myrcene which are similar to additive levels which find
commercial application in other fuels such as the ethanol in
Fig. 1. Monoterpenes investigated in this work: (a) Myrcene, and (b) Limonene.
gasoline. A fuel containing diesel at 90 wt.% and hydrogenated
limonene at 10 wt.% was also prepared. The mixtures were then
was a very fine powder that rapidly clogged filtration paper and
tested by ASTM standard methods to measure how these hydro-
took hours to spin down in a centrifuge. Preparing a second cata-
genated monoterpenes affect fuel properties. An independent lab-
lyst on alumina pellets for use in subsequent studies simplified
oratory (Intertek, Memphis, TN) was chosen for ASTM D975
separating the catalyst from the hydrogenation product. This cata-
analysis. As a control, a sample of the pure retail diesel fuel
lyst, comprising 1% platinum on alumina, was prepared in the lab-
was also tested.
oratory by incipient wetness addition of aqueous Pt(NH4)4NO3 to
Mixing 2–10% hydrogenated myrcene or 10% hydrogenated lim-
gamma alumina. The hydrogenation catalysts were activated un-
onene into diesel fuel modified its properties. Table 3 shows the
der hydrogen at 25 °C for 1 h prior to use. Batches of 400 mL
subset of relevant ASTM test results affected by the addition of
hydrocarbon were hydrogenated in a 600 mL, stirred, pressure ves-
hydrogenated monoterpenes. Adding 5% 2,6-dimethyloctane or
sel with approximately 20 g of catalyst. The reactor was kept at
10% 1-isopropyl-4-methylcyclohexane to diesel fuel was sufficient
200 °C and H2 pressure was held to 1100 kPa (160 psi). The reac-
to decrease the cloud point by 1 °C. Decreasing the cloud point of
tion was considered complete when a sample drawn from the reac-
the fuel enhances cold-weather performance by lowering the tem-
tor showed about 95% conversion as analyzed by GC–MS. This took
perature at which wax crystals form in the fuel and plug the fuel
approximately 2.5 days. The product was then centrifuged to re-
filter [14]. This result suggests that either of these species may
move the catalyst particles. Three batches of myrcene and one
be useful in blending operations to reduce cloud points.
batch of limonene were processed. A third-party laboratory tested
Other properties of the diesel fuel were also modified. The vis-
the fuel mixtures for compliance with ASTM D975 diesel fuel
cosity increased as the level of hydrogenated myrcene increased in
requirements.
the diesel fuel, but decreased with the addition of the hydroge-
nated limonene. Adding 10% hydrogenated myrcene produced
3. Results and discussion
the greatest viscosity, 3.899 mm2/s, which was near the ASTM
D975 limit of 4.1 mm2/s. However, the viscosity decreased to
Tables 1 and 2 give the composition of the final hydrogenated
2.3 mm2/s by adding 10% hydrogenated limonene. Too great a vis-
products as given by GC–MS. The preponderance of the products,
cosity causes the fuel to atomize poorly, resulting in a loss of power
in both cases, is the species expected by full hydrogenation of
in the engine [15]. Work by Zannis et al. shows that the amount of
the parent monoterpene. From Table 1, the vast majority of the
soot emitted from diesel engines increases with viscosity and ce-
reaction products were the completely hydrogenated form of myr-
tane number [16]. This suggests that a 10% hydrogenated limonene
cene, 2,6-dimethyloctane, with a small amount of the partially
blend would be preferable to 5 or 10% 2,6-dimethyloctane mixture
hydrogenated component. The substituted cyclical compounds re-
because the limonene blend would produce less soot due to its
sult from hydrogenation of the limonene contaminant which was
lower viscosity.
in the bulk myrcene. The bicyclic products likely result from the
All fuel mixtures met the ASTM D975 lubricity requirements;
thermal degradation of the partially hydrogenated limonene [11].
however the addition of 5–10% hydrogenated myrcene actually in-
Fully hydrogenated limonene constitutes the majority of the
creased the lubricity of the fuel mixture by 25–30%. Olefinic com-
limonene reaction product. The detected cymene came from the
pounds are known to increase the lubricity of diesel [17], therefore,
aromatization of the C6-ring in limonene and is a known byprod-
this behavior for the 2,6-dimethyloctane may be explained by the
uct of limonene hydrogenation [12,13]. Its presence in the sample
incomplete hydrogenation products which are present in the
may be advantageous from a fuel perspective. The bicyclic com-
hydrogenated myrcene sample.
pound results from the thermal degradation of limonene discussed
Adding hydrogenated myrcene or hydrogenated limonene also
above and the 2,6-dimethyloctane is a contaminant from previous
altered the flashpoint and distillation profile temperatures. In par-
myrcene experiments.
ticular, the initial boiling point decreased by about 5–7 °C due to
the hydrogenated additives. The ASTM D975 requirements specify
Table 1 that 90% of the fuel should boil between 282 °C and 338 °C. This
Composition of hydrogenated myrcene as measured by GC–MS. requirement is met by all four mixtures and helps to minimize
Component Composition (wt.%) the formation of soot and the percent of unburned hydrocarbons
in the exhaust [15]. The small downward shift in the distillation
2,6-Dimethyloctane 84.5
Other dimethyloctanes 1.7
profile of the blended fuels should also slightly decrease soot for-
C8 mono-olefins and di-olefins 3.6 mation during combustion [16]. The flashpoint increased by an
1-Isopropyl-4-methylcyclohexane and similar 8.7 average of 2.8 °C with the addition of the hydrogenated monoter-
Cymene and other aromatics 1.0 penes, staying well above the minimum value of 52 °C.
Bicyclics 0.2
In contrast to the viscosity, the cetane number decreased by
Other and unknown 0.3
including the hydrogenated additives. We expected the cetane
number for each blend to decrease with increasing hydrogenated
additive concentration, similar to results shown by Aoyama et al.
Table 2
Composition of hydrogenated limonene as measured by GC–MS.
[18] with other low cetane number molecules. The relationship be-
tween the amount of additive and the cetane number of the blend
Component Composition (wt.%) may be linear, or non-linear, according to Murphy et al. [19]. Deter-
1-Isopropyl-4-methylcyclohexane (cis- + trans-) 72.4 mining the exact relationship between the additive concentration
m-Cymene 25.3 and the cetane number of the blend will require several more data
2,6,6-Trimethyl-bicyclo [3.1.1] heptane 0.3
2,6-Dimethyloctane 2.0
points than were necessary to assess the effects of the additives on
the fuel’s cold-weather properties.
2240 N.I. Tracy et al. / Fuel 88 (2009) 2238–2240

Table 3
Effect of 2–10% 2,6-dimethyloctane and 1-isopropyl-4-methylcyclohexane in diesel fuel on ATSM D975 test results.

Propertya Hydrogenated myrcene Hydrogenated limonene

wt.% of additive wt.% of additive
0% 2% 5% 10% 10%

Flash point 58.3 63.9 61.7 60 58.9 °C

Viscosity at 40 °C 2.606 2.854 3.178 3.899 2.311 mm2/s
Lubricity, HFFR 470 470 325 350 476 lm
Cloud point 10 10 11 11 11 °C
Cetane number 45.6 44.9 44.3 44.7 42.8
Distillation
Initial BP 175.4 168.8 170.3 168.0 169.5 °C
10% 206.1 202.4 195.4 191.2 190.7 °C
30% 237.1 235.1 233.1 229.8 219.3 °C
50% 263.2 261.7 261.5 261.6 254.3 °C
70% 289.7 288.9 290.6 290.6 284.5 °C
90% 330.0 328.6 330.9 331.7 327.3 °C
End point 363.7 358.3 355.0 353.2 359.8 °C
a
Test results unaffected by additives are not shown.

Adding 10% hydrogenated limonene decreased the cetane num-
ber of the fuel mixture by 2.8, whereas the hydrogenated myrcene
only decreased the cetane number by one. Higher cetane numbers
also raise the soot emissions, but to lesser extent than viscosity
[16]. The small change in cetane number caused by the hydroge-
nated myrcene will probably have little effect on the performance
of the fuel. The drop in cetane number due to the addition of 10%
hydrogenated limonene decreases the cetane number to 42.8, near
the ASTM minimum of 40, but still within acceptable ranges. Once
more, the hydrogenated limonene blend is probably preferable to
the hydrogenated myrcene blends because lower cetane number
blends should produce less soot.
4. Conclusions
The monoterpenes myrcene and limonene were fully hydroge-
nated to 2,6-dimethyloctane and 1-isopropyl-4-methylcyclohex-
ane, respectively, by hydrogenation over platinum and palladium
catalysts. The hydrogenated products decreased the cloud point
of consumer grade diesel fuel by 1 °C when mixed into the fuel
at 5–10%. All fuel mixtures met ASTM D975 minimum standards.
The hydrogenated limonene blend should produce less soot during
combustion, compared to the unblended retail diesel. However, the
2,6-dimethyloctane will likely increase soot emissions due to the
increased viscosity of the blends compared to the retail diesel used
in this study. Therefore, hydrogenated forms of myrcene, and pref-
erentially limonene, can be used as blending agents in diesel fuels
without significant detrimental effects on the properties of the
fuels. This represents a potential usefulness of terpenes (bio-de-
rived hydrocarbons) as renewable fuel supplements.
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