Fuel Processing Technology 87 (2006) 759 767

www.elsevier.com/locate/fuproc

Diesel upgrading into a low emissions fuel

Roberto Galiasso Tailleur
Department of Thermodynamics, Simon Bolvar University, Sartenejas, Baruta, Caracas, Venezuela
Received 11 April 2005; received in revised form 14 April 2005; accepted 14 December 2005

Abstract

The revamp of existing diesel hydrotreating units using SHP technology was studied to improve the emission of the diesel engine. Gas and
liquid-phase reactors were sequentially added to the actual trickle bed reactor. A special catalyst was employed. Micro-plant kinetic studies were
performed and the results compared with those obtained with conventional trickle bed reactor operation. It was shown that using the gas and
liquid-phase reactor, the hydrogenation, hydrogenolysis, and ring-opening reactions can be enhanced, so can be the sulfur and cetane number
properties. The new scheme decreased the mono-aromatic content in the lighter part of the diesel that improve the NOx and particulate emissions in
exhaust gases of a diesel engine. A simplified kinetic model for gas and liquid-phase reactors was developed to optimize SHP reactors and to
minimize investment.
2006 Published by Elsevier B.V.

Keywords: Hydrotreating; Gas and liquid-phase reactors; WNiPd/TiO2Al2O3 catalyst; NOx and PM Diesel emissions

1. Introduction poor. Another possibility is to treat LCO in conventional

Many companies have explored whether it makes economic
sense to add a reactor in a conventional low-medium pressure
reactor or/and build a completely new high-pressure system
(reactor, plus high-pressure separator, plus new compressor).
Recently, a counter-current reactor technology has been
considered and a new process scheme developed. Other
possibility is to install a high-pressure grass-route unit with a
catalyst technology capable of coping with sulfur content and
aromatics. There are several technological options available in
the market. Some of them could complement existing low-
pressure units while others will require investing in a medium to
high pressure units. Recent papers (Babich and Moulijn, [1],
and Bharvani and Henderson [2], among others) describe in
detail the options and the economics.
The cracked diesel component (LCO) that is produced in
the Fluid Catalytic Cracking process could be sent to the fuel
oil pool as low sulfur diluent, but in there its valorization is
Actual address: ITQ, UPV, Naranjos sn, Valencia, Spain. Tel.: +58 2
9086232, +34 963690668.
E-mail address: gatairo@itq.upv.es.
0378-3820/$ - see front matter 2006 Published by Elsevier B.V.
doi:10.1016/j.fuproc.2005.12.005
hydrodesulfurizer to obtain low sulfur components for the
heating oil pool, where its high aromatic content low cetane
number does not affect its value. LCO can also be
incorporated in the on-road Diesel pool. There, aromatic
content affects its valorization and it can only be incorporated
in a limited proportion to the 15 or 500ppm sulfur Diesel
pool. Finally, the last option is using a deep hydrotreating
process to adjust both sulfur and cetane number. The standard
practice is to blend the LCO with other Light Gas Oils and
perform a high-pressure hydrotreatment altogether. The
economy is strongly dependent on hydrogen availability,
type of unit, and quality and proportion of LCO incorporated
in the feed. With more than 50% of LCO in the Hydrotreating
feed, a very low space velocity is required (Lee and Mc
Govern [3]) to obtain the 15 ppm sulfur and 42 cetane
number. Considerable attention has been devoted in recent
years to the development of catalysts and processes for LCO
upgrade, with particular reference to aromatic saturation (cf.,
Cooper and Donnis [4]). Optimal design and operation of
such hydrogenation process can be achieved using a reliable
simulation tools that, however, require a detailed knowledge
of kinetic pathways and rates. Currently, most of the proposed
models are limited to the simulation of single components or
760 R.G. Tailleur / Fuel Processing Technology 87 (2006) 759767
binary aromatic mixtures (cf., Toppinen [5]). One of the few
exceptions is the model developed by Chowdhury et al. [6],
which considered a trickle bed two-phase model that
accounted for desulfurization and hydrogenation.
This paper compares the effect of adding reactor volume to
existing units to produce a low-emission diesel fuel by using or
the SHP technology (Galiasso et al. [7]) or the conventional
TBR (trickle bed reactor). In particular, the study is focused in
assessing the aromatic hydrogenation and hydrogenolysis
reactions in both mode of reactor operations, and in building
up a simplified kinetic model for SHP scheme.
2. Experimental part
2.1. Catalyst and product characterization
The HDT1 catalyst (WNiPd/TiO2Al2O3) is a second
generation catalyst [7], having been the first one developed
in the 1990s [8]. HDT2 catalyst (WNi/Al2O3) was prepared
in the same way than HDT1 but without adding Ti and Pd.
Both catalysts were sulfided in situ as indicated below. The
physical properties of the catalysts are reported in Table 2.
The catalyst activity and selectivity were previously com-
pared (Galiasso et al. [9]) using 30% of naphthalene, 10% of
tetraline, 3% of dibenzothiophene, and 0.1% of quinoline
in hexadecane). Some of these results will be mentioned
here.
The feed and products were analyzed by conventional
ASTM methods. In addition, by employing a Gas Chromatog-
raphy coupled with a mass spectrometer (GCMS) own
developed method it was possible to determine families of
aromatic, paraffinic, and naphtenic compounds. The families
of sulfur and nitrogen compound were measured with the
same apparatus coupled with specific GC detectors. The
HNMR (nuclear magnetic resonance) analysis was performed
in parallel to discriminate iso-paraffin from n-paraffin in the
feed and in the products. The diesel was fractionated in three
cuts (F1, F2, and F3) with 60 C boiling range difference and
each cut was deeply characterized. Cetane number (CN) was
measured in a diesel engine using ASTM 0613 standard
procedure.
Diesel+H2
C
S H
R1 R2
TBR
Fig. 1. Trickle bed reactor without intermedia separation (left side), SHP reaction scheme (right side).
The specialized literature (ca. Heywood [10]) indicates some
dependency of exhaust gases emissions with Cetane number in
heavy duty diesel engines. Here, the differences in cetane for
hydrogenated products were compensated by cetane number
improver (see these modifications indicated with arrows in
Table 7). The NOx (nitrogen oxide) and PM (particulate)
emissions were measured in a high speed Detroit Diesel Series
90 (2002) direct injection engine operating at 2000rpm, 350 kW
power, 1364 kPa BMEP, 1630N m torque. To determine NOx
and PM, a micro-tunnel device coupled with on line micro-filter
and IR analyzer was used.
In addition, the trickle bed reactor (R1) products were doped
with dibenzothiophene before being sent to the hot separator
and then to the gas and liquid-phase reactors (R3 and R4, Fig. 1
right side). This was done to understand the vaporization effect
of kinetics on reactions.
2.2. Diesel hydroprocessing using trickle bed technology
To assess the reactivity of the feed (blend of 60% by weight
of LCO and 40% straight run gas oil), it was hydrotreated in a
micro-plant with two-trickle bed down flow reactors operating
in series (R1 + R2, Fig. 1 left side). The target was to produce
15ppm of sulfur using 5.1, 7.2, and 10.3MPa of total pressure.
The same temperature (either 350, 360, 370 C) was employed
for the three-space velocities, and the reactors were operated
isothermally. Feed 1 and H2 were loaded into the first reactor
(R1) with a H2 / HC ratio of 200 Nm3/m3 and with hydrogen
purity of 96%v, (the impurities were 0.015% H2S, 1.8% of C1
and 0.2%v of C2, and the rest Nitrogen). The space velocity of
the first reactor (R1) was kept constant at 0.5 h 1 whereas the
second reactor catalyst volume was changed to achieve the
sulfur target (15 ppm). The HDT2 catalyst was used in both
reactors diluted with 50% of inert material of 0.001 mm
diameter particles to improve their fluid dynamics (see De
Brujin [11], among others). The product properties for three
temperatures and three pressures are shown, as an example, in
Table 3. The R1 products were also analyzed to calculate the R2
contributions. Three product cuts were analyzed and character-
ized (Table 5). Table 8 presents the emission test results for
products 1a and 6a.
GPR
Diesel+H2 H2
R3
C
S S
R1 R4
LS Diesel
LPR
 R.G. Tailleur / Fuel Processing Technology 87 (2006) 759767 761

2.3. Hydroprocessing using SHP technology
The effects of using a SHP technology in a conventional
diesel hydrotreater (HDT) were studied in the same micro-
plant mentioned above. In the sequential mode, the diesel
was treated first using the trickle bed reactor (R1-HDT2
catalyst) the same reactor and catalyst employed before.
Then the outlet stream was sent to a hot separator (HS) that
was operating at substantially the same temperature and
pressure. The gas-phase leaving the top of the HS was sent to
the second reactor (GPR-R3) that operated in gas-phase at the
same temperature and pressure than the first reactor. There,
90% of the hydrogen coming from the trickle bed was sent to
the gas-phase reactor. The liquid leaving from the bottom of
HS was fed to a liquid-phase reactor (LP-R4) where it was
treated at the same temperature and pressure than R1 reactor.
In the liquid-phase reactor the HC vaporization was less than
8% due to the low H2 / HC ratio used there. Both reactors
were operated isothermally with the HDT1 catalyst diluted to
50% with smaller inert particles diameter. The ratio of reactors
volume (R3 / R4) was arbitrarily selected at 0.8. The streams
from both reactor outlets were mixed, cooled to 40 C, and
sent to a high-pressure cold separator (CS). The space
velocity for R3 and R4 reactor system is proportionally
adjusted to achieve the 15 ppm of sulfur in the combined
product which was then fractionated and analyzed. The
hydrogen rich stream that leaves from the top of CS was
recycled (see scheme in Fig. 1 right side). As an example,
the properties of the hydrotreated products for two tempera-
tures and three pressures are shown in Table 4. R1 outlet
product composition was also analyzed to calculate the R3
and R4 contributions.

Table 1
Stoichiometry and reaction rates expressions for gas-phase

ADArgas 2:1H2 ANArgas 1 kg1iADAr CADAr CH2

2
kg2iANAr CANAr
RgADAr
1 KmTAr CTTAr KmTNAr CTNar 

ANArgas 3:1H2 ADNgas 2 kg3iANAr CANAr CH2

3
kg4iADN CADN
RgANAr
1 KmTAr CTAr KmTNAr CTNar 

ANArgas 1:3H2 AArgas 3 kg5iANAr CANAr CH2

0:8

RgANAr
1 KmTAr CTAr KmTNAr CTNar 

ADNgas 1:3H2 ANgas 4 kg6iADN CADN CH2

0:8

RgADN
1 KmTAr CTAr KmTNAr CTNar 

ADNgas 1:1H2 ADNgas 5 kg 1i

0:8
CADN CH2
RgADNA DV N 7 ADNAD

1 KmTAr CTAr KmTNAr CTNar 

ANArgas 1:1H2 ANargas 6 kg8iANArAAr CANAr CH2

0:8

RgANArAAr
1 KmTAr CTAr KmTNAr CTNar 

ANDgas 1:3H2 ANgas 7 kg9iADNAD CADN CH2

0:8

RgADNAD
1 KmTAr CTAr KmTNAr CTNar 

IPgas 1:4H2 0:22C1 C4 1:22C5 8 kg10iisopW Cisop CH2

0:5

Rgisoplightp V
1 KmTAr CTAr KmTNAr CTNar 

NPgas 1:3H2 0:26C1 C4 1:33C5 9 kg11inp VCnp CH2

0:5

Rgnplightp
1 KmTAr CTAr KTNAr CTNar 

ArSgas 1:1H2 RHgas SH2 10 kg12iRS CRS CH2

1

RgRS
1 KTAr CTAr KmTNAr CTNar 

ArNgas 2:3H2 RHgas NH3 11 kg13iRS CRS CH2

1

RgRS
1 KmTAr CTAr KmTNAr CTNar 
762 R.G. Tailleur / Fuel Processing Technology 87 (2006) 759767

Table 5 is useful for comparing the fractions obtained from adsorption constant and its concentration. For example, the
product 1a (trickle bed) with those from product 1b (SHP). aromatics hydrodealkylation rate expression is:
Their analysis allows understanding the internal compounds
transfer among cuts that happens during hydrotreatment. kl 7iADN ClADN Cl0:8
RlADN H2

Emissions were determined in a diesel engine for trickle bed 1 KnTAr CTAr KnTNAr CTNar KnSH2 CSH2 
and for SHP products, which are shown in Table 8.
The following isothermal mass balance equations and
2.4. Kinetics analysis objective function were used
" #11 " #11
The complex network of hydrogenation reactions is well dFg xij dFl xij
Rigj 1fw 0 ; Rilj fw 0 ;
described in the literature (Yui and Sanford [12], and Rautanen dV dV
1 1
et al. [13], among many others). Previous kinetic experiments
performed with pure compounds (Galiasso et al. [9,14]) allow Objective  function Cgi j f Cgi j model 
to establish the kinetic equations for a simple lump of
reactions representing what happens in diesel components. In Where j is the pseudo-compound, Fx is the molar gas flow (g)
the model, sulfur, nitrogen, aromatics, paraffin and naphthenic or liquid flow (l), and fw is the wetting efficiency. Cgi j represent
compounds are represented by pseudo-components in diesel the gas concentration for the component j, at the outlet of the
feed and products with average properties. The matrix of hete- reactor ( f ), or predicted by the model (model). To obtain the
rogeneous kinetic rate equations (LHHW type) considered here kinetics constant, the temperature (360370380 C), the space
for gas-phase reactor is indicated in Table 1, and they need to velocity (0.3, 0.4 and 0.5 h 1) of both reactors, as well as the
be solved together with fluid-dynamic related parameter. The temperature (360370380C) of the high pressure separator
liquid-phase reactor has similar matrix of equations that include were changed, providing a set of different reactor inlet
the effect of hydrogen sulfide in the denominator on top of the compositions to develop a limited kinetics lump of reactions
aromatic and naphthene. Based on previous work with pure model. The matrix of 22 mass balances differential equations
compound it was considered that there is no intra and inter- mentioned above for the isothermal plug flow reactors are
particle mass and heat transfer control of the reaction, the solved using the typical initial conditions with a numerical
reactors perform as an isothermal plug flow and that there is no method (Runge KuttaFelberg) programmed in VB. The
noticeable deactivation (checked by repeating the initial test at program employs a Genetic algorithm optimization loop to
the end of run). obtain the kinetics constants. The adsorption constant for
The alkyls-di-ring-aromatic (ADAr, ca: alkyls-naphthalene) aromatics, naphthenes, and H2S used here were determined in
hydrogenation proceeds in series to yield an alkyls-naphthene- previous studies [9,11]. Initially, the rate constants were seeded
ring-aromatic (ANAr, ca: alkyl-tetraline) and then alkyl-di- while the program search the best values for these constants by
cyclo-naphthene compounds (ADN, ca: alkyl-decaline). The mutation technique till the objective function defined above is
ANAr and ADN are hydrogenolyzed in series to open the minimized (1.5%). Details about the genetic algorithm can be
naphthenic ring to produce alkyls-aromatic (AAr) and alkyl- found in the literature (ca: Park and Froment [15]). The model
naphthenes (AN). The normal and iso-paraffins (np and ip) can with those constants is then used to optimize the concentration
also be hydrogenolyzed to lighter products (irreversible profile in both reactors.
reaction), so can be the ANAr and AND.
Table 1 presents a summary of the gas phase reactions and
their rate of reaction expressions. kg1 through kg4 are the 3. Results
reaction rate constants for hydrogenation in Eqs. (1) and (2) and
the kg5 through kg6 are for hydrodealkylation in Eqs. (3), (4), 3.1. Catalysts characterization
and (5). kg8, kg9i , kg10
i i
and kg11 are the rate constants in Eqs. (6),
i i
(7), (8), and (9) for hydrogenolysis reactions. kg12 and kg13 are Table 2 presents the catalysts properties. Catalyst HDT1
the hydrodesulfurization and hydrodenitrogenation reaction contains W, Ni, and Pd as active phase with a low acidity type
constants. The kmTAr, kmTNAr, CTar and CTNAr are the
adsorption constants in metal sites and the total aromatic and Table 2
Catalyst properties
naphthene-aromatic molecules present in gas-phase. The same
denominator is used in Eqs. (1)(11) for gas phase. The first Catalyst HDT1 HDT2
column in Table 1 summarizes the reactions and the apparent NiO wt.% 4.2 4
stoichiometry. Notice that reactions 1 and 2 are reversible WO3 wt.% 12.5 15
PdO wt.% 0.01 0.2
whereas the others are irreversible. The apparent kinetics order
TiO2 wt.% 10 0
with respect to the hydrogen is 0.8 for hydrodealkylation and Al2O3 wt.% Complement
0.5 for hydrogenolysis. Surface m2/g 245 211
The reaction rates in liquid phase are similar to those Volume cm3/g 0.52 0.48
observed for gas phase, but included in the denominator the Particle diameter m 0.001 0.001
Pore diameter nm 120 112
effect of hydrogen sulfide; KnmH2S and CH2S are the H2S
 R.G. Tailleur / Fuel Processing Technology 87 (2006) 759767 763

support based on TiO2Al2O3 (see in reference [7] details about
formulation and characterization) whereas HDT2 is a conven-
tional WNi/Al2O3 highly hydrogenating catalyst. Physical
properties for both catalysts indicate a high surface, medium
pore volume solid structure. Both catalysts have a large
contribution of interconnected mesopores with an average
pore diameter of 12 and 11.2 nm, respectively. Both catalysts
were sulfided in situ with straight run gas oil spiked with 1% of
CS2, at 300 C during 6 h. These activated catalysts contain
5.6% and 5.1% weight of sulfur and less than 0.1% of Carbon.
A previous study [9] showed that HDT1 has 30% and 15%
better hydrogenation and denitrogenation, and 15% lower
desulfurization capabilities than HDT2, but HDT1 main
contribution is in performing tetraline ring opening reaction
(15% higher than HDT2).
3.2. Trickle bed reactors (TBR)
The feedstock is composed by 40% of straight run gas oil
and 60% of LCO. The latter was produced from a FCC unit
operating at 65% conversion into gasoline, and using a 0.1%
sulfur content VGO feed. Table 3 shows the properties of the
feed which is high in sulfur, nitrogen, and aromatics content.
The 58% of aromatics are mainly composed by families of di-
ring-aromatic resulting in a low CN material that has no value
as diesel component. The naphthenes are mainly composed
by alkyl-mono- and alkyl-di-cyclo-paraffins. Discrimination
by families of sulfur indicates the presence of 24% of
thiophene, 40% of benzothiophene, and 33% of dibenzothio-
phene molecules in the feed (plus 3% of non-identified
naphthothiophenes). Nitrogen families are composed by 15%
of indole, 55% of quinoline, and 35% of carbazole
compounds. There is less than 0.01% of oxygen content in
the feed.
The 15ppm sulfur products generated with a trickle bed
system (Fig. 1) at 350C and at different pressures are
shown in Table 3, third (1a), fourth (2a), and fifth (3a)
columns. These products have nearly the same amount of
sulfur and almost zero nitrogen, achieved by adjusting
hydrotreating pressure from 5.1 to 10.1 MPa, and space
velocity of R2 from 0.2 to 0.31h 1. As a result, when the
pressure augments, the total aromatics are reduced while the
naphtheno-aromatics remain quite high. Operating in trickle
bed mode did not allow a complete hydrogenation of the
aromatics and as a consequence a limited improvement in
cetane number occurred. The same results are confirmed at a
higher temperature (370 C), although the space velocity
needed was higher than that used at lower temperature for all
pressures, with a little better improvement in cetane number.
The products (1a, 3a, and 6a) can be used in the low sulfur
pool but all of them still have low cetane and need to be
compensated by other high CN, low sulfur components. The
cetane number blending values of these hydrotreated
products were 0.9, 0.92, and 0.94, respectively, which
improved when hydrogenating reaction deepens by increas-
ing the operating pressure. These numbers below 1 that
multiplied the actual cetane number of products 1a, 1b, and
1c in the blend, teach about the effective cetane number of
the products that affects the economics of incorporating
hydrotreated products into the diesel pool. The distribution of
properties along the boiling range for the trickle bed products
will be discussed below, along with the SHP products
distribution.
3.3. SHP test results
The same feed than those used in the previous case is
employed here (Table 4 second column). The third, fourth, and
fifth columns depict the values of the diesel properties after
being processed by SHP in sequential operation at 350C, and
different pressures and space velocities in the gas and liquid-
phase reactors. Products 1b, 2b, and 3b show again the well-
known hydrogenation characteristic: the higher the pressure, the
higher is the aromatic saturation. However, here most of the
alkyl-di-ring-aromatics and a great part of alkyl-mono-ring-
aromatics are converted into paraffin. This is done in the SHP at
a higher space velocity (lower catalyst volume) than that
required by the TBR (Table 2), for the same throughput. The

Table 3
Feed and products properties in trickle bed mode of operation
Temperature C 350 350 350 360 360 360
LHSV h 1 0.2 0.26 0.31 0.23 0.29 0.34
Pressure MPa 5.1 7.1 10.1 5.1 7.1 10.1

(Reactor 1/2) catalysts HDT2

Properties (wt.%) Feed Prod 1a Prod 2a Prod 3a Prod 4a Prod 5a Prod 6a
Density g/cc 0.8988 0.8785 0.8721 0.8689 0.8699 0.8688 0.8655
Sulfur wt ppm 19,000 15 15 15 15 15 15
Nitrogen wt ppm 450 10 7 3 0 0 0
n + isoparaffins 15.1 21.1 22.5 24.0 26.0 25.0 24.5
Mono-cycloparaffins 15.5 23.4 27.5 29.6 29.3 31.2 34.2
Di-cycloparaffins 13.1 16.2 13.4 13.0 15.0 16.8 17.9
Tri-cycloparaffins 8.9 5.5 4.2 4.2 3.1 2.8 2.1
Mono-ring aromatics 21.1 21.0 22.0 20.4 12.0 13.0 14.0
Di-ring aromatics 26.0 12.0 10.2 8.8 14.0 10.3 7.0
Cetane number () <35 39.0 40.0 41.0 40.0 41.0 41.5
764 R.G. Tailleur / Fuel Processing Technology 87 (2006) 759767

Table 4
Feed and products properties in SHP mode of operations
Temperature C 350 350 350 360 360 360
LHSV h 1 0.25 0.33 0.38 0.3 0.35 0.4
Pressure MPa 5.1 7.1 10.1 5.1 7.1 10.1

(Reactor 1/3 and 4) catalysts (R1) HDT2 / (R3R4) HDT1

Properties (wt.%) Feed Prod 1b Prod 2b Prod 3b Prod 4b Prod 5b Prod 6b
Density g/cc 0.8988 0.8745 0.8688 0.8649 0.8659 0.8638 0.8615
Sulfur wt ppm 19,000 15 15 15 15 15 15
Nitrogen wt ppm 450 0 0 0 0 0 0
n + isoparaffins 15.1 25.5 28.0 29.0 28.0 29.0 30.0
Mono-cycloparaffins 15.5 28.3 29.8 30.8 29.0 31.0 32.0
Di-cycloparaffins 13.1 17.9 17.5 18.3 17.8 17.0 17.8
Tri-cycloparaffins 8.9 0.0 0.0 0.0 0.0 0.0 0.0
Mono-ring aromatics 21.1 16.3 14.5 13.1 14.0 13.0 12.0
Di-ring aromatics 26.0 12.0 10.2 8.8 11.0 9.7 8.0
Cetane number () <35 41.0 42.0 44.0 41.5 43.0 45.0

fact is that the lighter part of the diesel is vaporized in the HS, cooling the product, the unconverted compounds returned to the
and goes into the gas-phase reactor (R3). There, the gas fully liquid phase contaminating the low sulfur diesel product. This
contacts the catalyst, instead of having partial contact like in the seems to be one of the reasons why the use of a very low space
trickle bed mode operation. This modified the activity and velocity to achieve the 15ppm of sulfur in conventional trickle
selectivity, as it was seen in previous studies (Galiasso and bed operations was reported. The aromatic compounds
Palmisano [16]). A similar effect was previously reported by distribution indicated that alkyl-mono and alkyl-di-ring-aro-
Reinhoudt et al. [17]. matic, and alkyl-mono-cycloparaffin are also concentrated in
Simultaneously the liquid stream from HS is processed in the lighter cut (F1a). This might indicate that the dealkylation
the liquid-phase reactor (R4), where there is a small amount of and cracking reactions transfer aromatic and naphthene
gas phase (H2 and HC) in equilibrium. The R4 has a little lower compounds from the heavy cut to the low boiling range.
catalyst wetting (92%), hydrogen concentration and back Cracking and dealkylation reactions are also responsible for
mixing than in the trickle bed reactor (Galiasso and Pieretti producing the 5% of heavy gasoline and changing the diesel
[18]). The properties of the combined effluent from both distillation curves. It can be observed that feed ratio F1 / F2 / F3
reactors indicated that the system is more capable of (mass distribution) is 24 / 40 / 36%, while product ratio (F1a /
hydrogenating all kind of aromatics, and especially the mono- F2a / F3a) is 25 / 45 / 30%, respectively. For example, around
ring-aromatics, than the TBR above mentioned. The higher the 65% of the F1a cut was vaporized when the reaction system
pressure and temperature, the higher is the difference between operated in trickle bed mode at high temperature low pressure.
both of reactors performances (see 6b/6a vs. 1b/1a). SHP These vaporized light aromatics (original and formed by
scheme always produces a higher naphthene ring-opening dealkylation reactions) encountered difficulties in contacting
reaction and lower dealkylation of the alkyl-aromatics and the catalyst remaining partially converted. Even by hydroge-
alkyl-naphthene-aromatics molecules. In this way, by operating nating the feed at high pressure, aromatics are always
TBR at 360C and 10.1 MPa, it produces 3.4% of C1C4 and concentrated in the lighter part of the diesel since the
6.5% of naphtha, while SHP only generates 2.5% and 5.5%, hydrogenation and hydrogenolyisis reactions do not proceed
respectively of these by-products at the same conditions. The further. In TBR, the HDT2 catalyst is able to open in some
lowest C1C4 production occurred in the gas-phase reactor in extend the cyclo-paraffins ring (ca: poly-alkyl-tetraline poly-
spite of the lack of the cracking-depressing effect of the liquid alkyl-benzene), but the dealkylation reactions (ca: poly-alkyl-
phase heavy aromatics adsorption.
Products from SHP and TBR schemes, 1b and 1a were
fractionated in three cuts F1 (180240C), F2 (240300C) Table 5
Distribution of sulfur and aromatics compounds in Diesel
and F3 (300360C) and Table 5 below shows the properties of
these cuts; the F1 cuts are depicted on the left side (F1a, F2a, Cuts from 1a and 1b F1a F2a F3a F1b F2b F2b
and F3a) and do not include the naphtha produced. The sulfur Diesel produced wt.% 25 45 30.0 32 41 27
components are close to the range of no detection and the values Thiophenes, S ppm 0 0 0 0 0 0
Benzothiophenes, S ppm 35 8 4 0 10 18
reported here have to be taken only as qualitative observations.
Total sulfur in Diesel ppm 40 11 4 0 16 28
The cut F1a cut shows a higher concentration of sulfur than Mono-ring aromatics wt.% 35.50 29.70 26.50 16.00 24 33
F3a (mostly of them as dibenzothiophene). This may have Di-ring aromatics wt.% 22.00 15.00 16.00 10.00 13 16
indicated that part of the light sulfur molecules was vaporized in Mono cyclo-paraffins wt.% 10.00 22.00 28.00 23.00 20 19
the trickle bed and went into the gas phase, where they remained Di-cyclo-paraffins wt.% 14.00 14.00 12.00 14.00 15 16
Paraffins wt.% 18.50 19.30 17.50 37.00 28.00 16.00
un-reacted due to its low contact with the wet-catalyst. After
 R.G. Tailleur / Fuel Processing Technology 87 (2006) 759767 765

benzene alkyl-benzene) minimizes the hydrogenation benefit Table 6

on cetane number. For that reason, the light alkyl-aromatics and Reactions rate constants for gas (left) and liquid (right) phase
light alkyl-cyclo-paraffin have short paraffins in their branches Constants kogi \ Kogi Egi \ gi koli \ Koli Eli \ li
chains. The cracking of the alkyl groups and paraffins produces k1 1.40E + 05 12000 1.00E + 05 13,000
compounds out of the diesel boiling range (naphtha). The high k2 1.90E + 10 32000 1.10E + 11 33,000
mono-aromatic concentration in the light part is extremely k3 1.70E + 04 11000 1.20E + 04 10,500
k4 8.00E + 12 41000 4.00E + 12 40,500
important for its behavior in the diesel engine chamber during
k5 1.60E + 06 15000 3.30E + 05 14,000
initial vaporization and thermal cracking (see emission test k6 7.20E + 07 17000 5.20E + 06 16,000
below). k7 6.50E + 05 12000 8.30E + 04 12,600
The SHP cuts F1b/F2b/F3b properties (Table 5, right side) k8 4.40E + 06 13000 6.50E + 06 12,000
show that sulfur and aromatics are now concentrated in the k9 3.70E + 06 14000 3.30E + 06 14,000
k10 2.60E + 06 15000 1.00E + 06 14,500
medium and heavy cuts (compare F1b with F2b, and F3b).
k11 1.90E + 07 16000 5.10E + 06 15,000
Remember that in the SHP system, light molecules (65% of k12 1.50E + 08 18000 4.50E + 07 17,000
F1 and 45% of F2) are transferred by the hot separator to the k13 3.00E + 08 19000 6.00E + 07 19,000
gas-phase reactor where they fully contact the catalyst. In KmDAr 2.00E + 01 100 3.30E + 01 900
consequence, the total volume of catalyst needed for 15 ppm KmNAr 1.40E + 01 900 1.80E + 01 1200
KmHAS 4.60E + 01 1300
is lower with SHP technology than it is with trickle bed. The
result was confirmed by adding 2% by weight of sulfur as (Reaction rates in mol/l h) and activation energies and heat of adsorption in cal/
mol).
dibenzothiophene to the 15ppm diesel and compared SHP
with TBR space velocity needed to desulfurize 99%. The
SHP scheme always requires less catalyst (between 30% and adsorption coefficients and the H2S adsorption (well known in
40%) than the latter, because 60% of DBT was in gas phase the literature [1]).
in trickle bed conditions. Cracking and dealkylation reactions The model developed here is able to predict the product
are responsible for producing 3% of heavy gasoline and for distributions along the reactors and can be used to optimize the
changing the diesel distillation curves. The ratio F1b / F2b / hot separator temperature. The model allows tracking the
F3b (mass distribution along the boiling range) is now 32 / hydrogenation and hydrodealkylation reactions in gas and
41 / 27% for SHP product. The paraffin is quite evenly liquid phase. Fig. 2 compares the behavior of aromatic,
distributed along the distillation range, so are the di-ring- naphthene and paraffin as a function of reactor volume
cycloparaffins. The HDT1 catalyst in gas phase produces a required for 15ppm of sulfur in the combined product keeping
controlled cracking, and it is mainly responsible for the VR3 / VR4 = 0.8. The left side presents the concentration of
hydrogenation aromatics, the hydrogenolysis, and the ring AMAr, ADAr, AMN, AND, and P for the gas phase reactor
opening reactions of the light materials. The naphthenic-ring (product 1b). The right side of the figure shows the
opening of heavy poly-alkyl-naphthene-aromatics molecules concentration for the same families in the liquid-phase reactor.
occurred in the liquid-phase reactor. There the HDT1 catalyst In gas-phase the hydrogenation, and the hydrogenolysis
hydrogenated of heavy poly-alkyl-di-ring-aromatics giving a reactions that open the naphthenic ring of ANAr, convert the
high amount of the poly-alkyl-mono-ring-aromatics and poly- ADAr into AMAr, which is fast hydrogenated to AN, and its
alkyl-cycle-paraffin that augment the cetane number. The concentration decreases. In liquid phase, the rate of forming
blending values measured for 1b, 3b, and 6b products are AMAr is higher than the rate of disappearance and its
0.94, 0.96 and 0.97, respectively. concentration augments. The model indicated the advantage
of having a higher temperature in the HS and in the gas-phase
3.4. Kinetics interpretation and reactor modeling reactor and a lower one in liquid-phase reactor to minimize the
total volume. In other words, the best catalyst distribution
The hydrogenation mechanism follows a complex path of depends on vaporization and on the difference in the activation
reactions that include dealkylation and ring-opening reactions energies between gas and liquid phase reactions. The ability to
[12,13]. To understand the performance of SHP gas-phase and improve the cetane number and reduce emission is mainly
liquid-phase reactors, the system was modeled using the 11 associated to ring opening reactions.
kinetic rate equations mentioned in Table 1 for gas phase, and The HDT1 catalyst produces a deep hydrogenation of the
another 11 for liquid phase. The rate constants obtained are aromatics, increasing the naphthene and paraffin molecules
shown in Table 6, for gas phase in second and third columns, content in the lighter fraction. The analysis of the type of
and for liquid phase in fourth and fifth columns. The model molecules present in the three cuts from 1b (aromatic,
reproduces the aromatics, naphthenes, and paraffins families paraffin, and naphthene) confirms the extent of ring-opening
content with a relative deviation of 1.5% for all the conditions and dealkylation reactions. The heaviest aromatics are either
studied as seen in Table 7, where the prediction is compared hydrogenated or converted into light aromatics that move into
against the 60 experimental values. Notice the difference in F1a cut, where they are transformed into cyclo-paraffins. The
activation energies between hydrogenation, hydrodealkylation, higher operating pressure, the higher is the aromatics
and hydrogenolysis reactions. The reactions in liquid phase hydrogenation rate and the cyclo-paraffin production. The
have always showed lower rates due to the higher aromatics higher the temperature, the higher is the dealkylation
766 R.G. Tailleur / Fuel Processing Technology 87 (2006) 759767

Table 7 Table 8
Comparison between experimental and model global concentration prediction Diesel engine emissions (NOx and PM)
Compounds wt.% Model Experimental Deviation Toxics Product 1a Product 1b Product 6a Product 6b
n + isoparaffin 26.5 29.0 0.8 NOx g/bhp h 8 4 5 2
Monocycloparaffin 34 33.0 1.6 PM g/bhp h 0.21 0.06 0.16 0.04
Dicycloparaffin 17.4 16.7 1.3 Cetane number 39 to 45 41 to 45 41 to 45 45
Mono ring aromatics wt.% 13 12.0 1.4 Aromatics wt.% in F1 33 28 21.0 19.5
Di ring aromatics 9 8.0 0.9 Adjusted with Ethyl's Cetane number improver.
Average, % of relative deviation for 60 experimental points. (Engine EPA 98/No EGR/2000 rpm/350 kW/1364 kPa BMEP).

reactions. The HDS and HDN reactions were the fastest,
followed by aromatics hydrogenation and by hydrogenolysis
ones.
3.5. Diesel engine test
To demonstrate the effect of light aromatics in cetane number
two synthetic diesels were built by adding either 30% of F1a, or
30% of F1b, to 40% of F2a and 30% of F3a. Both synthetic
diesel fuels were tested in a diesel engine (ASTM) to determine
their cetane number. A difference of 2 numbers was observed
when employing F1b (44) instead of F1a (42CN). Products 1a,
1b, 6a, and 6b were tested in a commercial light duty diesel
engine, in the conditions mentioned above, to evaluate the
emission of particulate and NOx at the same cetane number. In
this way, the emission associated to the aromatic and cyclo-
paraffins content can be evaluated with depressed cetane
number effect. The test shows that the lowest emission is
produced by the most hydrogenated product (lower total
aromatics and mono-ring-aromatics). When the fuel is injected
into the chamber after the engine is cranked, the liquid is
atomized and the ignition begins. In this phase, called
uncontrolled burning or flame propagation period, most of the
PM precursors are formed by thermal cracking in which the
aromatics play an important role. Then, the second phase starts
with full combustion resulting in peaks of pressure and
temperature. From that point on, most of the NOx is formed
associated to the maximum temperature attained. The pressure
volume curve for product 6b is flatter than that for 6a. It is
equivalent to an earlier (and better) vaporization and a lower
maximum temperature for the SHP products. All of that
produces a lower NOx and PM (Table 8). It was speculated that
the lower light aromatics in the volatile part of F1b helped to
achieve a better engine behavior. Testing the synthetic diesel
made with the light part of product F1b (30%), added to the
middle (F2a), and heavy part (F3a) product decreased the
emission with respect to the product 1a (F1a + F2a + F3a) that
showing the effect of the cetane number in the vaporized
fractions in the chamber.
4. Conclusion
SHP technology which adds to the existing HDT reactor a
hot separator and gas and liquid phase reactors, requires less
reactor volume than adding a conventional trickle bed reactor to
produce low sulfur low aromatics diesel for the same
operational pressure and temperature. The major part of sulfur,
nitrogen, aromatics, naphthenes, and paraffins compounds react
first in the existing trickle bed reactor, but then, the vaporized
part of the diesel is treated in gas phase reactor and the non-
vaporized one in liquid phase reactor. The poly-ring-alkyl-
aromatics are hydrogenated and hydrogenolyzed to poly-rings-
alkyl-naphthenes and then, to iso and normal paraffins. In
addition, a limited formation of lighter aromatic and napthenes
via dealkylation and cracking reactions take place. All of these
reactions modified the compositions along the diesel distillation
range, improving the cetane number distribution and reducing
the emissions.
It has been demonstrated that SHP concept improves the
selectivity toward light paraffin and naphthene formations due

AMAr ADAr AMN 350C, 5.1MPa

40 40
AND P
35 35
R3 GP R4 LP
30 30

25 25

20 20

15 15

10 10

5 5
0 25 50 75 100 0 25 50 75 100
Reactor Volume

Fig. 2. Gas phase (left) and liquid phase (right) compound concentration along the reactor.
 R.G. Tailleur / Fuel Processing Technology 87 (2006) 759767
to the better performance of hydrogenation and hydrogenolysis
reactions in gas phase than in trickle bed. In particular, it was
demonstrated that the lower the mono-ring-aromatic concen-
tration in the lighter part of the diesel, the better is the cetane
number, and the lower are the NOx and PM emissions.
Using a lump of 11 reactions for the gas and other 11 for the
liquid phase reactor, the SHP system was modeled and the
kinetics constants have been obtained with a Genetic algorithm
tool. The simplified model allows the optimization of the
catalytic system used in gas and in liquid phase reactor.
Acknowledgment
I wish to acknowledge the efforts of Jose Patrelli, Juan
Arroyo and Saul Restifo who participated in the kinetics tests,
and Dr. Josef Ramesive for the diesel engine testing.
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