Fuel Processing Technology 90 (2009) 686691

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Fuel Processing Technology

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / f u p r o c

Hydroprocesssing of light gas oil rape oil mixtures

Jerzy Walendziewski , Marek Stolarski, Rafa uny, Bartomiej Klimek
Faculty of Chemistry, Wrocaw University of Technology, ul. Gdaska 7/9, 50-310 Wrocaw, Poland

a r t i c l e

i n f o

Article history:
Received 16 June 2008
Received in revised form 5 December 2008
Accepted 12 December 2008
Keywords:
Gas oil
Vegetable oils
Hydroprocessing
Diesel fuel
Properties
Catalyst

a b s t r a c t
Two series of experiments of hydroprocessing of light gas oil - rape oil mixtures were carried out. The reactor
feed was composed of raw material: rst series 10 wt.% rape oil and 90 wt.% of diesel oil; second series
20 wt.% rape oil and 80 wt.% of diesel oil.
Hydroprocessing of both mixtures was performed with the same parameter sets, temperature (320, 350 and
380 C), hydrogen pressure 3 and 5 MPa, LHSV = 2 h 1 and hydrogen feed ratio of 500 Nm3/m3. It was stated
that within limited range it is possible to control vegetable oil hydrogenolysis in the presence of light gas oil
fraction (diesel oil boiling range) through the proper selection of the process parameters. Hydrogenolysis of
ester bonds and hydrogenation of olenic bonds in vegetable oils are the main reactions in the process. Basic
physicochemical properties of the obtained hydroprocessed products are presented.
2008 Elsevier B.V. All rights reserved.

1. Introduction
Thermal or catalytic cracking of vegetable oils followed by
hydroprocessing can be an alternative method in renewable fuels
production. There are many advantages of such approach to the biofuels production in comparison to transesterication. We can
enumerate some examples like the possibility to produce hydrocarbon
fuels similar to diesel fuel of naphtha origin, the opportunity to avoid
by-product waste utilization and the lack of glycerol. This technology
can be considered as waste free and environmental friendly and it is a
very important advantage in the way of vegetable oil processing.
There is also possibility to submit vegetable oils directly to hydroprocessing resulting in partial or total hydrogenation of double and
ester bonds and splitting of linear carbon chain of fatty acids. There is
very limited information about vegetable oils hydroprocessing.
According to Djega-Mariadassou et al. (patent information) [1], the
hydrogenating process of vegetable oils should be carried out under
hydrogen partial pressure at least equal to 12 MPa in the presence of
hydrogenating catalyst and at the temperature higher than 350 C.
Stumborg et al. [2] informed that the main products of such
process are straight-chain parafn hydrocarbon fractions in diesel
boiling range with cetane number between 55 and 90. Due to the very
high cetane number they called that product super cetane. Some
hydroprocessing by-products were also obtained, such as C1C4 light
hydrocarbons, some quantity of water and carbon dioxide. Fatty acids
partial hydrogenation can lead to obtain certain quantity of alcohols or

Corresponding author. Tel.: +48 71 320 35 51; fax: +48 71 322 15 80.
E-mail address: jerzy.walendziewski@pwr.wroc.pl (J. Walendziewski).
0378-3820/$ see front matter 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.fuproc.2008.12.006

aldehydes in the reaction products. The products obtained in the

process are miscible with diesel fuel in all the proportions and linearly
improve cetane number. Other properties of vegetable diesel
fractions, such as viscosity and density, are similar to the commercial
diesel fuels.
As a result of heightened content of saturated parafn hydrocarbons,
a relatively high pour and cloud points (low temperature properties) is
the main disadvantage of the vegetable diesel fraction. Therefore, it
should rather be not used as a component of winter diesel fuels.
It is necessary to point out that the vegetable diesel fractions
produced by hydroprocessing can be used as cetane number improver.
The addition of 20 wt.% of cetane number improver increases cetane
number of highly aromatic (44.5 wt.%) fraction from 31.7 to 43.3.
Unfortunately, the spectacular cetane number increase is accompanied by heightening of cloud point from 38 to +8 C.
Similarly, addition of 8 wt.% of this cetane improver to renery
diesel fraction, can increase cetane number from 43.6 to 47.7 and
cloud point from 29 to +6 C. According to Stumborg et al. [2],
addition of the vegetable diesel fraction as cetane improver has a
vast impact on carbon monoxide and total hydrocarbon emission in
exhaust gases: a reduction of 69 and 63%, respectively, and relatively
small impact on NOx emission (4% emission reduction).
The common hydroprocessing of naphtha derived diesel fuel
fractions with 10 to 30% vegetable oil addition is the third possibility of
vegetable oil application in fuel production. In this case deep
hydrodesulphurization of diesel fuel should be accompanied by
hydrogenation of unsaturated fatty acid components and hydrogenolysis of ester bonds.
This paper presents the results of hydroprocessing of 10 and 20 wt.%
of rape oil and 90 and 80 wt.% of light gas oil fraction mixtures in

J. Walendziewski et al. / Fuel Processing Technology 90 (2009) 686691

Table 1
Hydroprocessing parameters.
Series/exp. no.

Temperature C

Hydrogen pressure,
MPa

LHSV, h 1

H2/feed
(Nm3/m3)

I/1
I/3
I/5
I/7
II/2
II/4
II/6
II/8

320
350
380
350
320
350
380
350

5
5
5
3
5
5
5
3

2
2
2
2
2
2
2
2

500
500
500
500
500
500
500
500

continuous ow pressure apparatus. Process parameters were changed in the following range: temperature 320380 C and hydrogen
pressure 35 MPa. In order to obtain hydrogenolysis of more than 95%
ester bonds and hydrogenation of double bonds with 10% of rape oil
content in the feed, very strong process parameters are necessary, such
as temperature at least 350 C and hydrogen pressure 5 MPa.
The hydroprocessing of such feeds presents two undesired
phenomena. Firstly, parafn hydrocarbons obtained in the result of
hydrogenation of fatty acids lead to the increase in product melting
temperature. This inuences further undesirable increase in cloud and
melting points as well as cold lter plugging point (CFPP) determined
for the hydrorened products. Secondly, some feed hydrocracking is
occurring and we observe lowering of obtained products ash point.
2. Experimental
Two series of hydrorening experiments were carried out. The rst
one used raw material 10 wt.% rape oil mixed with 90 wt.% of diesel

687

oil. The second one used raw material 20 wt.% rape oil mixed with
80 wt.% of diesel oil.
Each experiment series was composed of four tests at different
process parameters (Table 1). A commercial hydroreninghydrocraking (NiMo/Al2O3) catalyst was used in the studies.
50 cm3 of NiMo catalyst was packed to the reactor tube (total
reactor volume 300 cm3). The catalyst was sulded with diethyl
sulde, S(C2H5)2 solution in diesel fuel before hydrorening tests
were carried out. The experiments were realized in the laboratory
continuous ow apparatus presented in Fig. 1. A membrane pump (2)
supplied the oil feed mixture from the feed tank (3) to the catalytic
reactor (4) (100 cm3/h). Hydrogen, 50 dm3/h i.e. 500 dm3/1 dm3 of
the feed was fed to the reactor by the second inlet port. Catalyst bed
temperature was controlled and registered by three thermocouples.
Hydrogen pressure in the hydrorening apparatus was stabilized
using inletoutlet control gas valves and hydrogen manometers while
reactor and catalyst bed temperatures were controlled by temperature
controllers (5). The gasliquid reaction mixture was owing out from
the reactor to the water cooler (6) and then to the pressure gasliquid
separator (7) in order to separate gaseous fraction (hydrogen and
small quantity of light hydrocarbons) from hydrorened oil mixture.
Hydrogen containing gaseous products was released to atmosphere by
gasmeter (1) while liquid hydrorening product was drained to the
atmospheric separator (8) in order to remove the trace quantities of
gases. Afterwards it was submitted to the analysis.
The activity of the catalyst was stabilized in hydrodesulphurization
process of light gas oil (diesel fuel) for about 120 h before the
hydrorening studies. The single hydrorening experiment lasted 8 h
after stabilization of process parameters, i.e. reactor hydrogen
pressure and temperature as well as raw material and hydrogen
ows. Two product samples were taken from each experimental test.

Fig. 1. Schematic view of hydrorening apparatus.

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J. Walendziewski et al. / Fuel Processing Technology 90 (2009) 686691

2.1. Product analysis

Table 3
Properties of the hydrorening products of the second experimental series.

Hydrorening products contained small quantities of water and

suspended white products, waxy parafns. Water was removed by
ltration using anhydrous sodium sulfate and parafn crystals by
decantation.
The following analyses of the obtained product were carried out
according to the suitable standards:
Product density (15 C) was determined using aerometer, according
to EN ISO 3675, EN ISO 12185,
Kinematical viscosity (40 C) was determined using Ubbelohde
viscosimeter, according to EN ISO 3104,
Fractional composition, according to EN ISO 3405 method,
Flash point was determined in PenskyMartens-closed cup, according to EN ISO 2719,
Cold lter plugging point (CFPP), according to EN 116,
Bromine number was determined by potentiometer titration
according to PN-68/C-04520,
Total acid number (TAN) was determined by titration of the sample
with KOH solution, according to PN 85/C-04066,
Contents of ester bonds, aromatic compounds and carboxylic groups
in hydrorened products were determined by FTIR method.
3. Results and discussion
Results of the rst series of hydroprocessing products are presented
in Table 2 while the results of the second series in Table 3. Table 4
presents comparison among physicochemical properties of diesel oil,
rape oil and fatty acid methyl ester produced from rape oil.

Feed, 20 wt.% Sample no., parameters

rape oil
No. 2
No. 4
No. 6

No. 8

350 C,
380 C,
350 C
320 C,
5 MPa, H2 5 MPa, H2 5 MPa, H2 3 MPa, H2
Liquid product yield,
wt.%
Viscosity at 40 C,
[mm2/s]
Density 15 C
[kg/m3]
Distillation
Initial boiling
point [C]
10% [C]
50% [C]
90% [C]
250 C [vol.%]
350 C [vol.%]
End boiling point [C]
% distilled fraction
Flash point [C]
CFPP [C]
Bromine number
[g Br2/100 g]
Acid number,
[mg KOH/g]

96

95

94

95

4.38

3.74

3.06

2.86

3.24

854.5

842.4

832.9

830.5

836.0

187

180

165

155

184

220
287
287
28
87
353
91
70
24
15

218
286
286
28
95
360
98
38
+ 4.3
8.43

213
279
279
31
97
358
98
37
0
3.8

208
277
277
33
98
363
100
37
+ 1.8
2.05

217
288
288
31
98
348
98
38
2.3
4.9

0.96

1.74

1.33

1.24

2.21

products yields should be achieved. As a result of hydrocracking

reactions, the purge gas fraction owing from the plant condensation/
separator system contained about 5 wt.% of gaseous light hydrocarbons.

3.1. Product yields

The preparation of the correct material balance for the laboratory
studies is a very difcult assignment. Tables 2 and 3 present the data of
the obtained product yields after receiving them directly from the
separator. It is visible that ca 95 wt.% yield of hydrorened products can
be obtained. In larger process scale, i.e. industrial plant, higher liquid
Table 2
Properties of the hydrorening products of the rst experimental series.
Reactor feed 10
wt.% rape oil

Sample no., parameters

No. 1

No. 3

No. 5

No. 7

350 C,
380 C,
350 C
320 C,
5 MPa, H2 5 MPa, H2 5 MPa, H2 3 MPa, H2
Liquid product
yield, wt.%
Viscosity at 40 C
[mm2/s]
Density at 15 C
[kg/m3]
Distillation
Initial boiling
point [C]
10% [C]
50% [C]
90% [C]
250 C [vol.%]
350 C [vol.%]
End boiling point
[C]
% distilled fraction
Flash point [C]
(CFPP) [C]
Bromine number
[g Br2/100 g]
Acid number,
[mg KOH/g]

97

95

95

95

3.48

2.97

2.94

2.86

2.93

846,4

836.5

834.7

834.6

835.8

169

161

167

140

158

212
279
309
33
92
341

213
275
329
32
97
345

212
280
329
31
98.5
348

211
277
327
31
98.5
353

212
276
327
32
98.5
340

93
70
25
8.9

96.5
58
9
1.7

98.5
64
17
0.79

99
53
14
0.96

98
62
13.5
1.8

0.51

0.60

0.48

0.58

0.89

3.2. Fractional compositions and ash points

Due to the high boiling temperature of rape oil, its addition to
diesel fuels results mainly in some changes in end boiling point, i.e.
lowering of the volume percent of distilled fuel fractions at
temperature 350 C (Tables 2 and 3). The application of the relatively
severe process parameters brings as the outcome hydrogenation of
unsaturated and esters bonds. One can detect also products of partial
and total glycerol hydrogenation (propane) as well as products of
hydrocracking of long chain hydrocarbons in the feed. Small quantity
of light hydrocarbons in hydrorened products resulted in lowering of
initial boiling points and temperatures of distillation of 10, 50 and
90 vol.%.
In case of the hydrorened products, almost the whole product
volume (9998%) was distilled at the end boiling point although only
9193 vol.% of the used feeds distilled at this point. It means that almost
all the amount of vegetable oils in the reactor feed was transformed

Table 4
The selected quality requirements for diesel fuel, vegetable oil and methyl ester of rape
oil.

Density at 15 C [kg/m3]
Kinematics viscosity, 40 C mm2/s]
Heating value [MJ/kg]
Ignition point [C]
Cetane number
CFPP [C]
Sulfur content [mg/kg]
Water content [mg/kg]
Fractional distillation
Initial boiling point, IBP [C]
Temp. of 50 vol.% distillation

Vegetable oil

FAME

Min.

Max.

Min.

830
80
37.4
285
~ 39
+ 15

930

~ 885
4.3
37
~ 200
~ 55
~ 10

~ 210
~ 340

1000

~ 320
~ 350

Diesel fuel
Max.
5,3
39

~ 10
500

Min.

Max.

820
2
42.8
65
51
20

845
4.5

+5
50
200

176
290

J. Walendziewski et al. / Fuel Processing Technology 90 (2009) 686691

689

(hydrocracked) to lower temperature boiling hydrocarbons. It is

necessary to point out that distillation volumes and temperature
range data of both the obtained hydrorened products and the
commercial diesel fuels are very close.
The lowering of ash points of the hydrocracked products was
caused by the light hydrocarbon molecules contained in the obtained
samples, which resulted from partial hydrocracking. It is especially
noticeable for the feed containing hydrorening products of 20-wt.%
rape oil. Improvement of the product properties, heightening of the
ash point, is possible by product stabilization through the separation
of low boiling hydrocarbons from the product by distillation.
3.3. Density
The density of the used rape oil (890 kg/m3) is higher than density of
diesel oil (835 kg/m3) due to the fatty linear acids and oxygen content.
Therefore densities of the obtained feeds are: the 10% rape oil of 847 kg/
m3, while the 20% rape oil achieved value of 854 kg/m3 (Fig. 2).
As the result of the hydrocracking process, densities of the
obtained products distinctly decreased. The simple dependence was
stated: the more severe the process parameters and higher rape oil
conversion levels, the lower densities of the obtained products. It is a
result of vegetable oil hydrocracking presumably followed by
isomerization of the obtained hydrocarbons. Densities of all the fuel
samples, including feeds were conformed to the standardized
requirements specied for diesel fuels, i.e. standard density range
820860 kg/m3 Table 4.
3.4. Kinematics viscosity
Kinematical viscosity of rape oil (78 mm2/s) is much higher than of
diesel oil (2.9 mm2/s, max. 4.5 mm2/s, Table 4) and 10 or 20% addition
of rape oil to diesel oil resulted in viscosity increase (Fig. 3). However,
hydrorening of both feeds at process parameters, temperature 350 C
and 5 MPa or 350 C and 3 MPa made possible to lower viscosity to ca
3 mm2/s. That phenomenon is explained by hydrocracking of
triglycerides molecules and lowering of average molecule weight in
the reaction mixtures in comparison to the processed feeds. Large
vegetable oil molecules were converted to considerable smaller
molecules of gasoline and gas oil. Similarly, as in the case of density,

Fig. 2. Inuence of process parameters on density of the hydroprocessed products.

Fig. 3. Inuence of process parameters on viscosity of the hydroprocessed products.

viscosities of all the fuel samples, including feeds, were conformed to

standardized requirements, i.e. standard viscosity range 24.5 m2/s
Table 4. One can observe only small inuence of rape oil content in the
feed on the viscosity of the hydrorened products.
3.5. CFPP (cold lter plugging point)
CFPP (cold lter plugging point) is a direct content function of high
melting point parafn hydrocarbons in the studied hydrorening
products. The higher the parafn content in oil fraction, the higher is
the melting point (as well as crystallization and pour points) of the
fuel. The addition of rape oil, with relatively low melting point, to
diesel oil fraction does not inuence distinctly its CFPP (Fig. 4).
CFPP increase from lower than 20 C up to 4 C was due to the
partial hydrogenation of ester bonds and unsaturated bonds in fatty acid
chains without hydrocracking. The results were obtained in hydrorening process of 20-wt.% rape oil containing feed at 320 C and pressure
5 MPa. Such distinct increase in CFPP is an outcome of relatively rapid
hydrogenation rate of olen bonds and hydrogenation of double bonds
in fatty acids in oil triglycerides in the low hydroprocessing temperature.
The application of higher process temperature (350 C) and pressure (3
and 5 MPa) led also to partial hydrocracking of oil molecules of high
crystallization point and enabled to obtain products with CFFP lower
than 10 C for the 10 wt.% rape oil containing feed.
All hydrorening products acquired by the use of 20 wt.% rape oil
containing feed were characterized by higher quantity of saturated
linear hydrocarbons (parafns) and therefore their CFPP was higher
than 0 C but lower than 5 C. It means that all the products from both

Fig. 4. Inuence of process parameters on CFPP of the hydroprocessed products.

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J. Walendziewski et al. / Fuel Processing Technology 90 (2009) 686691

Table 5
Inuence of process parameters on the selected feed and hydrorened product
properties: ester content, acid number and carbon atoms content in aromatic structures.
Sample, no.

Ester content, Acid number, Acid number Carbon atoms

vol.%
mg KOH/g
(IR method) content in aromatic
structures, wt.%

Feed 1
10.0
Sample 1 (320, 5)
0.89
Sample 3 (350, 5)
0.26
Sample 5 (380, 5)
0.12
Sample 7 (350, 3)
0.57
Feed 2
20.0
Sample 2 (320, 5)
9.66
Sample 4 (350, 5)
2.65
Sample 6 (380, 5)
0.31
Sample 8 (350, 3)
4.12

0.48
0.60
0.63
0.46
0.88
0.49
1.92
1.34
1.16
2.07

0.46
0.55
0.61
0.51
0.72
0.48
1.69
1.38
1.12
2.01

14.69
15.71
16.01
16.79
15.41
11.66
13.88
14.55
16.06
14.97

Fig. 5. Inuence of process parameters on bromine number of the hydroprocessed

products.

FTIR analysis was used to compare fatty acids and esters content in
the used feeds and the obtained hydrorening products. Fig. 6

presents FTIR patterns obtained for the feeds and product samples
from the rst hydroprocessing series.
The absorption band caused by carbonyl bond CfO suitable for
ester content determination is placed at the frequency 1750 cm 1.
Ester content in the hydrorened samples was determined on the
basis of FTIR patterns and absorption peak areas as well as calibration
curves (ester content versus 1750 cm 1 band area).
The calculation results for the rst and second series of feeds and
rening products are presented in Table 5. Table 5 demonstrates very
clearly that the feed before processing contains the highest esters
content. After that, the content was strongly reduced, the lowest value
was found in samples 5 and 6, hydrorened at the most severe process
parameters (380 C and 5 MPa). One can state that at these parameters
ester bond content was small, almost negligible. In order to obtain
relatively high level of ester bonds hydrogenation and to lower ester
content below 0.5 wt.% for the rst feed, it is necessary to apply at least
moderate hydrorening process parameters, i.e. process temperature
at least 350 C and hydrogen pressure 5 MPa (Fig. 6).
In case of 20 wt.% vegetable oil content in the feed it is compulsory
to use higher process temperature i.e. 380 C. There is a simple
dependence: the higher the vegetable oil content, the higher the
process temperature and/or the higher hydrogen pressure should be
applied in order to obtain high level of ester bond conversion and to
lower ester content below 0.5%.
It is worth noticing that hydrogenolysis of some part of ester bonds
gives fatty acids that contain carboxyl group (COOH) created from
vegetable oil ester group. Therefore, acid numbers of the hydrorening
products were higher than the feeds. It is especially well visible in case of

Fig. 6. FTIR spectroscopy patterns made for the I series feed and the obtained
hydroprocessed products (sulded catalyst).

Fig. 7. FTIR spectroscopy patterns made for the II series feed and hydrorening products,
the frequency range 17101750 cm 1, (sulded catalyst).

experimental series cannot be applied to diesel fuels blending in

winter season in most of the European countries Table 4.
3.6. Bromine number
Rape oil addition to diesel oil fraction almost linearly increased
bromine number of both the feeds and products as the result of the
molecules presence with olen bonds in vegetable oils. Therefore,
considerably higher bromine number was stated for the second series
feed and products (20 wt.% rape oil content, Fig. 5). Increasing of the
process temperature and/or hydrogen pressure resulted in hydrogenation of double bonds and lowering bromine number of the obtained
product samples. It is visible that both process parameters, temperature
and hydrogen pressure, are inuencing double bonds hydrogenation.
Even in the case of the most severe process conditions (380 C and 5 MPa
hydrogen pressure) some olen compounds in hydrorened products
were determined. Due to the heightened reactivity, olens containing
fuels are more susceptible to oxygenation and thus having lowered
stability.
It is necessary to admit, however, that some content of olen
compounds both in gasoline and diesel fuel, similarly as in the case of
biodiesel, is admissible and, from fuel quality point of view, doesn't
present any tangible danger.
3.7. Ester content reduction

J. Walendziewski et al. / Fuel Processing Technology 90 (2009) 686691

products of the second experimental series, where the feed with 20 wt.%
rape oil content was applied. Those observations were conrmed by
FTIR studies. The band at 1710 cm 1, characteristic for carbonyl bond
CfO in carboxyl COOH group (Fig. 7), is suitable for the determination.
Acid numbers for the products samples were calculated by the
comparison between the surface areas of those bands and calibration
curve data. The calculation results are presented and compared to the
values determined by the titration method in the Table 5. It is visible that
both acid content determination (acid number in mg KOH/g and acid
content from FTIR analysis) attained similar values. It means that both
analytic methods give similar analytical results.
It also conrms that part of ester bonds was hydrogenolized giving
carboxylic group (COOH), presumably in fatty acids. At lower
vegetable oil content in the feed, 10 wt.%, there is no clear correlation
between ester content and acid numbers. At 20% rape oil content in
the feed there is a simple dependency: the higher the rape oil
conversion, the lower the ester content in hydrorening and the lower
acids content (lower acid number). Process temperature strongly
inuences hydrogenolysis of ester bonds in rape oil. The highest
hydrogenolysis level was determined for sample 6, hydrorened at the
highest process temperature. Similarly, as in the case of the 1st series
products, one can see that acid number determinations by classic and
spectroscopic give comparable results.
Absorption bands placed at wave length close to 1601 cm 1 and
810 cm 1 are characteristic for absorption by aromatic hydrocarbon
compounds. Atom percentage content in aromatic structures was
calculated on the basis of the surface area of these bands. The results
of the calculation are also presented in Table 5. They indicate that the
lowest carbon atom content was stated for both feeds while all the
hydrorened samples showed distinctly higher carbon atoms content
in aromatic structures. It does not mean that in the course of
hydrorening some dehydrocyclization takes place, but that the part
of parafn hydrocarbons and non aromatic fatty oils were hydrogenolysed in the course of hydrorening process. Some part of the
feed was simply removed from the hydrorening products in the form
of water and light hydrocarbons, mainly propane. The most distinct
lowering of carbon atoms in aromatic structures was determined for
the samples produced at the highest process temperature (380 C)
and at the largest ester hydrogenolysis levels.
The obtained hydrorening results of rape oil containing feeds
clearly indicate that hydrogenolysis of ester bonds gives partially
carboxylic compounds, COOH bonds, presumably as fatty acids. That
observation was conrmed in quite different series of our rape oil
hydrorening studies in the presence of reduced and sulded NiMo
Al2O3 catalyst forms. Fig. 8 presents selected results from those studies.

691

Results in Fig. 8 show that application of both catalyst forms enables

similar hydrogenolysis level of ester bonds at moderate process
parameters (samples 320/3 and 320/5 for reduced form as well as
320/5 and 350/5 for sulded form). Higher levels of ester bonds
hydrogenolysis in the presence of the both catalyst forms were attained
in the more sever process parameters, 350/5 for the reduced and 380/5
for the sulded catalyst form. Analysis of the absorption bands at
1710 cm 1 indicates that instead of hydrogenation to hydrocarbons, part
of ester bonds in rape oil is transformed to carboxyl bonds containing
acids. It is especially well visible in IR patterns obtained for the samples
from hydroprocessing process in the presence of the reduced catalyst
form (acid number from 3.84 to 7.22 mg KOH/g).
Application of the sulded catalyst resulted in considerable higher
hydrogenation level of ester bonds and relatively low acid number (1.11
to 1.30 mg KOH/g). It means that sulded NiMo catalyst, at similar
process parameters as the reduced NiMo catalyst, presents higher
hydrogenation activity. Mass spectroscopy analysis of the hydroprocessing products showed that some quantity of alcohols compounds as
partial products of carboxylic acid hydrogenation is produced in the
presence of the sulded catalyst form. However, despite relatively severe
process parameters, the hydroprocessing products contained always
higher quantity of fatty acids than the feed, acid number 0.49 mg KOH/g.
4. Conclusions
1. Rape oil hydrorening as additive (10 or 20 vol.%) to light gas oil
(diesel fuel fraction) can be realized in the temperature range 350
380 C at hydrogen pressure 5 MPa with good efciency. In the result
of the process one can observe over 95% yield of hydrogenolysis and
hydrogenation of ester and carboxyl acid bonds as well as hydrogenation of double bonds.
2. Hydrogenation of unsaturated hydrocarbons and hydrogenolysis
reactions of fatty acids results in higher melting temperatures
parafn hydrocarbons and alcohols. It leads to undesirable increase
in cloud and melting points as well as CFPP determined for the
hydrorened products. Some part of higher melting compounds
crystallizes in the hydrorened products.
3. Partial hydrocracking of parafn hydrocarbons causes production
of light hydrocarbons that lowers ash point of the hydrorened
samples. If the nal process product is used as a component of
diesel fuel, it will be necessary to remove light hydrocarbons in
order to increase its ignition temperature up to 56 C (according to
Polish standards).
4. Application of hydrogenation catalysts with mild hydrocracking
and isomerization activities is necessary for the deep hydrorening
process as a method of the utilization of rape oil in the mixture with
diesel fraction. The catalyst application task is to support hydrogenolysis of rape oil esters bonds, hydrogenation of unsaturated
bonds and isomerization of long parafn chains. The basic goal is to
obtain limited extent of hydrocracking of triglyceride molecules in
this process accompanied by possible low yield of gaseous products
and therefore low hydrogen consumption.
References
[1] G. Djega-Mariadassou, D. Brodzki, P. Nunes, J. Silva, D. Gusmao, Process for pressure
hydrocracking of vegetable oils or of fatty acids derived from the said oils, French
Patent, FR 2607803 (1988).
[2] M. Stumborg, A. Wong, E. Hogan, Hydroprocessed vegetable oils for diesel fuel
improvements, Bioresource Technology 56 (1996) 13.

Fig. 8. Comparison of the FTIR spectroscopy patterns made for the II series feed and
hydrorening products over sulded and reduced catalysts, the frequency range 1710
1750 cm 1.