Fuel 89 (2010) 611615

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Fuel
journal homepage: www.elsevier.com/locate/fuel

Fuel properties of hydroprocessed rapeseed oil

Pavel imcek a,*, David Kubicka b,1, Gustav ebor a, Milan Pospil a
a
b

Institute of Chemical Technology, Prague Department of Petroleum Technology and Alternative Fuels, Technick 5, 166 28 Prague 6, Czech Republic
Research Institute of Inorganic Chemistry, Department of Rening and Petrochemical Research, 436 70 Litvnov Zluz 1, Czech Republic

a r t i c l e

i n f o

Article history:
Received 2 March 2009
Received in revised form 16 September
2009
Accepted 17 September 2009
Available online 1 October 2009
Keywords:
Hydroprocessing
Rapeseed oil
Biodiesel
Hydrodeoxygenation

a b s t r a c t
This paper deals with the hydroprocessing of rapeseed oil as a source of hydrocarbon-based biodiesel.
Rapeseed oil was hydroprocessed in a laboratory ow reactor under four combinations of reaction conditions at temperatures 310 and 360 C and under hydrogen pressure of 7 and 15 MPa. A commercial
hydrotreating NiMo/alumina catalyst was used. Reaction products contained mostly n-heptadecane
and n-octadecane accompanied by low concentrations of other n-alkanes and i-alkanes. Reaction product
obtained at 360 C and 7 MPa was blended into mineral diesel fuel in several concentration levels ranging
from 5 to 30 wt.%. It was found, that most of the standard parameters were similar to or better than those
of pure mineral diesel. On the other hand, low-temperature properties were worse, even after addition of
high concentrations of ow improvers.
2009 Elsevier Ltd. All rights reserved.

1. Introduction
Hydroprocessing of vegetable oils allows easy transformation of
fatty acid triglycerides into hydrocarbons. Three most important
reactions take place during hydroprocessing of vegetable oil [1]:
(i) Hydrogenation of double bonds present in unsaturated
chains of bonded fatty acids.
(ii) Hydrodeoxygenation (HDO), which results in removal of
oxygen atoms from carboxylic group in the form of water.
(iii) Hydrodecarboxylation (HDC), which leads to elimination of
carboxylic group in the form of carbon dioxide.
It was found that hydrogenation of double bonds precedes HDO
and HDC reactions [1]. HDO and HDC of saturated triglycerides
proceed at different reaction rates, which depend on reaction conditions and type of catalyst used. The changes in the respective
reaction rates can be observed by the changing ratio of the principal products, i.e. n-octadecane in the case of HDO and n-heptadecane in the case of HDC. In general, the main reaction products of
vegetable oil hydroprocessing are thus n-alkanes having the same
carbon atom number as fatty acids present in the original vegetable oil (HDO) and n-alkanes with the carbon atom number lower
by one as compared to the carbon atom number of fatty acids in
the original vegetable oil (HDC). Hydroprocessing of common veg-

* Corresponding author. Tel.: +420 220 444 236; fax: +420 220 444 321.
E-mail addresses: pavel.simacek@vscht.cz (P. imcek), david.kubicka@
vuanch.cz (D. Kubicka).
1
Tel.: +420 476 163 735; fax: +420 476 768 476.
0016-2361/$ - see front matter 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2009.09.017

etable oils (rapeseed, sunower, soybean and palm oil) leads to

hydrocarbon mixtures, in which n-alkanes C15 to C18 are predominant [24].
Reaction conditions and type of catalyst also inuence the extent of side reactions leading to formation of i-alkanes, cycloalkanes and aromatics [2,4]. Cracking of the hydrocarbon chains is
usually negligible. The vegetable oil hydroprocessing [5] is sometimes referred to as hydrogenation [6] or hydrocracking [2,3].
However, the term hydrogenation can be misleading, because it
has a different meaning in food industry. During this process the
unsaturated chains of fatty acids are hydrogenated and become
saturated while the structure of triglycerides remains unchanged.
The term hydrocracking may also not be completely exact, because
cracking of carboncarbon bonds occurs only in some cases (HDC)
and generally at the carbon atom carrying oxygen-functional
group. Therefore, we will denote the set of reactions in this reaction system as hydroprocessing and the individual reactions will
be referred to as hydrodeoxygenation (HDO) and hydrodecarboxylation (HDC) throughout the article.
From the renery point of view, all hydrocarbons present in
hydroprocessed vegetable oil belong to middle distillates and are
thus suitable for production of diesel fuel. Hydroprocessed vegetable oil can be, hence, called hydrocarbon-based or oxygen-free biodiesel. Oxygen-free biodiesel eliminates some drawbacks of the
traditional FAME-type biodiesel relating mostly to fuel stability.
Car manufacturers would probably also prefer hydrocarbon-based
biodiesel to FAME as it offers full compatibility with current diesel
fuel for which the diesel engine systems are optimized. Moreover,
the content of such bio-component in diesel fuel could be much
higher than 5 vol.% permitted currently for FAME concentration

P. imcek et al. / Fuel 89 (2010) 611615

612

in diesel in Europe without negative impacts on engine operation.

Thanks to its high content of n-alkanes, oxygen-free biodiesel has
an excellent cetane number ranging from 55 to 90 [5] depending
on degree of branching. The worsened low-temperature properties
seem to be the only disadvantage in comparison with FAME-type
biodiesel. Low-temperature properties can be improved either by
choice of proper catalyst and reaction conditions or by isomerisation [7,8] following the hydroprocessing. It is also possible to use
existing renery technologies for co-processing of vegetable oil
and petroleum feedstock. The most promising way is perhaps the
addition of vegetable oil into feedstock for hydrocracking or hydrotreating [9,10].
Commercial production of hydrocarbon-based biodiesel from
vegetable oil has been recently incorporated in petroleum renery.
Finnish company Neste Oil operates two vegetable oil hydroprocessing units with capacity 170 kt/y each in its renery in Porvoo.
Two world-scale plants, in Singapore and Rotterdam, with capacity
800 kt/y each are under construction [8,11,12]. The production of
biodiesel takes place in two stages. Product of vegetable oil hydroprocessing (stage 1) proceeds to an isomerisation unit (stage 2)
where its low-temperature properties are improved. The nal
product called NExBTL is used as renewable component for production of diesel fuel. Neste Oil guarantees that its Neste Green
diesel, which suits all diesel engines, contains at least 10% of
NExBTL.
The paper summarizes some fuel properties of hydroprocessed
rapeseed oil obtained at various reaction conditions using commercial NiMo catalyst. Furthermore, fuel properties of mixed
fuels containing the selected hydroprocessed rapeseed oil (5
30 wt.%) and mineral diesel are reported and discussed. This work
is a logical continuation of the recent experiments aimed at reaction mechanism description and determination of detailed composition of reaction products [4,13].

2. Experimental
2.1. Hydroprocessing
Hydroprocessing of rapeseed oil was performed in a bench scale
ow reactor equipped with a salt bath heating system. The experimental set-up is schematically depicted in Fig. 1. All the feed and
product lines were heated to prevent feed and product solidication in the lines. The liquid products were stripped with hydrogen

prior to sample collection (not shown in Fig. 1). The dimensions of

the reactor were 900 mm (length) and 40 mm (inner diameter).
The total amount of the catalyst used was 100 g. The composition
of the commercial hydrotreating NiMo/alumina catalyst was as
follows: NiO 3.8 wt.%, MoO3 17.3 wt.% and P2O5 6.7 wt.%. Rapeseed oil used as raw material had food quality (S: 3 mg kg 1; P:
<0.5 mg kg 1; Na: 5 mg kg 1; K: 2 mg kg 1; Ca: 4 mg kg 1; Mg:
<0.5 mg kg 1). The liquid feed ow and hydrogen ow was
100 g h 1 and 0.1 Nm3 h 1, respectively. The WHSV and gas-tooil ratio were thus 1 h 1 and 920 Nm3/Nm3, respectively. The reaction products were collected during the hydroprocessing of rapeseed oil at two temperature levels, 310 and 360 C, and at two
hydrogen pressure levels, 7 and 15 MPa.

2.2. Analysis of products

After separation of aqueous and organic phases, the reaction
products were analyzed by gas chromatography. A gas chromatograph, model HP-6890 (Agilent), was used for all chromatographic measurements. Gaseous products and all organic liquid
products were analyzed by gas-chromatographic methods proposed in recent work [4]. Physiochemical properties of the organic liquid products and mixed fuels were determined using
standard test procedures designated for diesel fuel or petroleum
products.

2.3. Mixing of product with mineral diesel fuel

Organic liquid product (OLP) obtained by hydroprocessing of rapeseed oil at 360 C and 7 MPa was chosen for preparation of
blends with mineral diesel fuel. The mineral diesel fuel was obtained from a renery and it had low sulfur content (10 mg kg 1).
Furthermore, it did not contain FAME or any additives. All monitored physiochemical properties of this basic mineral diesel corresponded to the properties of a commercial diesel fuel before nal
additivation. Four diesel blends containing 5, 10, 20 and 30 wt.%
of OLP, respectively, were prepared and evaluated as commercial
diesel fuel according to the European standard EN 590. These
mixed fuels were then separately treated with ow improvers Keroux 3566 (BASF) and Inneum R 288 (Inneum) in concentration ranges of 10500 mg kg 1 to evaluate their impact on lowtemperature properties of the blends.

FIRC

PIC

High-pressure
gas line H2

TIRC

TIR1-3
FIR

Off-gas
collection system

WIR

1 - analytical scales
2 - heated feed container

PIRC

3 - fixed-bed reactor
Liquid product
collection

4 - mixed salt bath

5 - gas/liquid separator
Fig. 1. A schematic gure of the bench scale reactor.

P. imcek et al. / Fuel 89 (2010) 611615

613

400

3. Results and discussion

3.1. Composition of reaction products
Temperature (C)

350

Hydroprocessing of rapeseed oil yielded water, gaseous hydrocarbons and organic liquid product (OLP). The conversion of rapeseed oil was >99% at 310 C and complete conversion was achieved
at 360 C. The yields of the main products were as follows: OLP
83 wt.%, water 11 wt.% and gaseous hydrocarbons 6 wt.%. Beside
hydrogen, the reaction gas contained mainly propane (0.8
2.5 vol.%) and small amounts of carbon dioxide (0.050.3 vol.%),
carbon monoxide (up to 0.5 vol.%) and methane.
All OLPs were colourless or slightly yellowish liquids with density around 770 kg m 3 at 40 C. However, in the temperature
range of 2030 C they became solids. The composition of OLPs is
presented in Table 1. It is evident, that OLP is a mixture of saturated, in particular non-branched, hydrocarbons. Two hydrocarbons n-heptadecane and n-octadecane represent more than
75 wt.% of OLP in all cases. Besides other n-alkanes, the OLPs contained also i-alkanes and smaller amounts of cycloalkanes. Formation of i-alkanes was observed to increase with increasing reaction
temperature and pressure. Aromatics were found in OLPs only in
trace amounts (<0.1 wt.%) in some cases. The OLPs obtained at
310 C contained small amounts (up to 2 wt.%) of reaction intermediates (mainly stearic acid) and reactants. Traces of n-octadecanol,
another reaction intermediate, was also observed, but only in one
of the products. On contrary, the OLPs obtained at 360 C contained
no oxygenated compounds and they can be, thus, denoted as oxygen-free hydrocarbon mixtures.

300

310 C, 7 Mpa
310 C, 15 MPa
360 C, 7 MPa
360 C, 15 MPa

250

200
0

20

40
60
Recovery (vol.%)

80

100

Fig. 2. Distillation curves of organic liquid products obtained under various

reaction conditions.

Products obtained at 310 C showed increased acid number, probably due to carboxylic acid content (see Table 1 and 2).
The main disadvantage of OLPs as a potential component of diesel fuel consists in their poor low-temperature properties. All lowtemperature parameters (cloud point, pour point and cold lter
plugging point) fell into the range of +20 to +30 C (Table 2). Utilization of such a kind of diesel fuel in the pure form would be very
problematic even in countries with hot climate.
3.3. Mixed diesel fuels

3.2. Physiochemical properties

The composition of OLPs determines their boiling point range.
Narrow range of carbon atom numbers of dominant hydrocarbons
causes the at shape of distillation curve. Approximately 80% of
each product distilled at a boiling point of about 300310 C (see
Fig. 2), which is the boiling point falling into the diesel fuel distillation range. Density and kinematic viscosity of OLPs showed also
values acceptable for diesel fuel although the density of OLPs was a
little lower than that of diesel (see Table 2). However, this issue can
be easily solved by blending with a suitable heavier fraction. Typical composition of hydroprocessed rapeseed oil leads to high calculated cetane index of all prepared OLPs. It is expected that cetane
number can reach or even exceed the value of 100, as the calculated cetane index does. Other monitored parameters (sulfur,
water and ash point) also satised the demands for diesel fuel.

Table 1
Composition (wt.%) of organic liquid products obtained under various reaction
conditions (temperature and pressure).
Component

n-alkanes 6 n-C16
n-heptadecane
n-octadecane
n-alkanes > n-C18
Other hydrocarbonsa
Palmitic acid (C16:0)
Stearic acid (C18:0)
n-octadecanol
Monoglycerides
Diglycerides
Triglycerides

Reaction conditions
310 C,
7 MPa

310 C,
15 MPa

360 C,
7 MPa

360 C,
15 MPa

5.0
18.4
70.6
3.3
1.1

0.6

0.1
0.1
0.8

4.9
10.5
78.2
3.2
2.3

0.6
0.1
0.1

0.1

5.8
24.9
58.1
4.5
6.7

6.3
24.9
51.8
3.6
13.4

a
This group includes all hydrocarbons except n-alkanes (contains more than 90%
i-alkanes C16C18).

The product obtained by hydroprocessing of rapeseed oil at

360 C and 7 MPa was chosen for mixing with mineral diesel fuel.
Neither reactants nor intermediates were detected in OLPs

Table 2
Physiochemical properties of organic liquid products obtained under various reaction
conditions.
Parameter

Reaction conditions
310 C,
7 MPa

772
Density at 40 C
(788b)
(kg m 3)a
4.15
Kin. viscosity at 40 C
(mm2 s 1)
Distillation
At 250 C recovered
<5
(vol.%)
At 350 C recovered
>95
(vol.%)
95 vol.% recovered at
339
(C)
Flash point in closed
>128
cup (C)
c
Cetane index
103
9
Sulfur (mg kg 1)
Nitrogen (mg kg 1)
11
95
Water (mg kg 1)
0.54
Acid number
(mg KOH g 1)
Low-temperature properties
Cloud point (C)
2628
CFPP (C)
>20
Pour point (C)
28

310 C,
15 MPa

360 C,
7 MPa

360 C,
15 MPa

771 (787b)

770 (786b)

4.11

771
(787b)
3.92

<5

<5

<5

>95

>95

>95

330

344

323

>128

125

120

105
9
11
95
0.65

103
10
11
66
0.06

103
10
11
42
0.05

2830
>20
29

2527
>20
25

2325
>20
23

3.82

a
Solid nature of the sample did not allow to measure its standard density at
15 C.
b
Approximate values (density at 15 C was calculated from density at 40 C
taking the sample as homogenous liquid).
c
Cetane index calculated with the estimated density at 15 C.

P. imcek et al. / Fuel 89 (2010) 611615

614

400

0%

5%

10%

20%

30%

-5
300
250

CFPP (C)

Temperature (C)

350

0%
10%
20%
30%

200

-10
-15
-20
-25
-30

150
0

20

40

60

80

100

-35

Recovery (vol.%)

100

200

300

400

500

Content of flow improver (mg kg-1)

Fig. 3. Distillation curves of mixed fuels containing various amount of organic

liquid product (hydroprocessed rapeseed oil processed at 360 C and 7 MPa).

Fig. 4. Cold lter plugging point (CFPP) of diesel fuels containing various amount of
organic liquid product (hydroprocessed rapeseed oil processed at 360 C and 7 MPa)
treated with ow improver Keroux 3566 (BASF).

processed at 360 C. While the low-temperature properties of the

products processed at 7 and 15 MPa were comparable, hydroprocessing at the lower pressure would be the preferable technological solution. Addition of OLP into mineral diesel results in a shift of
the distillation curve toward to higher boiling points (see Fig. 3).
The shift is in the middle part of the curve and therefore it does
not inuence negatively the key points of distillation curve. All
measured physiochemical properties of mixed fuels containing
various amount of hydroprocessed rapeseed oil are presented in
Table 3. Viscosity and density of mixed fuels corresponded to EN
590 standard requirements with one exception of a little deviation
in density (for the mixed fuel containing 30 wt.% of OLP). Flash
points of mixed fuels were comparable or slightly higher than that
of basic mineral diesel. Mixed fuels had, however, signicant benet in the calculated cetane index, which linearly increased from
52 (pure basic mineral diesel) up to 66 units (mixed fuel containing
30 wt.% of OLP). Similar increase of cetane number can be
expected.
As expected, the addition of OLP worsened the low-temperature
properties of the mixed fuels in comparison with the basic mineral
diesel. The increase of cloud point and CFPP seems to be negligible
(not more than 2 C) for fuels containing up to 10 wt.% of OLP.
However, higher concentration of OLP in the mixed fuel caused a
more signicant increase (512 C) of all key low-temperature
parameters. After evaluation of the fuels without additives, the
performance of two different ow improvers (Keroux 3566 by
BASF and Inneum R 288 by Inneum) was investigated. The results of CFPP measurements of the mixed fuels treated with vari-

5
0%

5%

10%

20%

30%

CFPP (C)

-5
-10
-15
-20
-25
-30
-35
0

100

200

300

400

500

Content of flow improver (mg kg-1)

Fig. 5. Cold lter plugging point (CFPP) of diesel fuels containing various amount of
organic liquid product (hydroprocessed rapeseed oil processed at 360 C and under
the pressure of 7 MPa) treated with ow improver Inneum R 288.

ous concentrations of additive Keroux 3566 (BASF) are

presented in Fig. 4. While CFPP of pure basic mineral diesel
dropped according to expectations, the additive showed negligible
efciency in mixed fuels. While CFPP of the basic mineral diesel
dropped from original 12 to 27 C for additive concentration

Table 3
Physiochemical properties of mixed fuels containing various amount of organic liquid product (hydroprocessed rapeseed oil processed at 360 C and 7 MPa).
Parameter

Density at 15 C (kg m 3)
Kin. viscosity at 40 C (mm2 s
Distillation
At 250 C recovered (vol.%)
At 350 C recovered (vol.%)
95 vol.% recovered at (C)
Flash point in closed cup (C)
Cetane index
Sulfur (mg kg 1)
Nitrogen (mg kg 1)
Water (mg kg 1)
Low-temperature properties
Cloud point (C)
CFPP (C)
Pour point (C)
a
b

Content of the product (wt.%)

EN 590 (temperate climate)

10

20

30

829
2.35

826
2.44

824
2.50

820
2.63

816
2.76

820845
2.004.50

48
95
351
72
52.1
10
37
40

45
95
350
72
54.3
10
36
41

42
95
352
73
56.7
10
34
43

36
95
350
74
60.6
10
32
45

27
95
352
76
65.7
10
29
48

<65
>85
<360
>55
>46
<10

<200

9
12
12

8
12
12

7
10
9

+3
3
3

< 8a
<(+5 to

Grade F diesel.
Maximum values for grades A, B, C, D, E and F is +5, 0,

5,

10,

15 and

20 C, respectively.

1
7
9

20)

P. imcek et al. / Fuel 89 (2010) 611615

200 mg kg 1, the same concentration of additive in mixed fuels did

not improve CFPP more than by 5 C. Although CFPP of untreated
mineral diesel and mixed fuel containing 5 wt.% of OLP were the
same, basic mineral diesel became F-grade diesel after addition
of 100 mg kg 1 of ow improver. On the other hand, not even
500 mg kg 1 changed the grade of mixed fuels. Mixed fuels containing from 5 to 30 wt.% of OLP could be labeled only as E-grade
to B-grade diesel. Hence, there is no benet in treating the mixed
fuels with ordinary commercial ow improvers, as similar results
were obtained when using additive Inneum R 288 (see Fig. 5).
Nevertheless, it is possible that some kind of tailored ow improver could be more effective.

4. Conclusions
Hydroprocessing of rapeseed oil at 360 C and 7 and 15 MPa
yielded oxygen-free hydrocarbon mixtures. Only trace amounts
of reactants and intermediates were observed in products obtained
at 310 C. The organic liquid products (OLPs) contained acyclic saturated hydrocarbons having carbon atom number ranging from
about 14 to 20, where n-alkanes C17 and C18 formed more than
75 wt.% of the product. The composition and physiochemical properties of hydroprocessed rapeseed oil predetermine this product as
a high cetane diesel fuel, but its poor low-temperature properties
(pour point higher than +20 C) prevents its utilization in the pure
form.
Mixed diesel fuels containing from 5 to 30 wt.% of OLP (obtained at 360 C and 7 MPa) met the European diesel fuel specication EN 590. The greatest benet of the mixed fuels is probably the
increase of the cetane index (by 214 units). On the other hand, the
ow improvers used were shown to be ineffective in lowering
CFPP. The mixed fuels thus met only diesel grade specications
B, C, D and E, respectively, while the basic mineral diesel treated
with ow improvers met F-grade specication (EN 590) easily.

615

Acknowledgement
This work was supported by the Ministry of Industry and Trade
of the Czech Republic (project FT-TA3/074) and by the Ministry of
Education, Youth and Sports of the Czech Republic (agreement No.
MSM 6046137304).

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