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A Comparative study on hydrocracking and

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vacuum residue conversion

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DOI: 10.1016/j.fuel.2013.11.017

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 Fuel 119 (2014) 106–110

Contents lists available at ScienceDirect

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

A Comparative study on hydrocracking and hydrovisbreaking

combination for heavy vacuum residue conversion
M.F. Menoufy ⇑, H.S. Ahmed, M.A. Betiha, M.A. Sayed
Refining Department, Egyptian Petroleum Research Institute, Nasr City, 11727 Cairo, Egypt

h i g h l i g h t s g r a p h i c a l a b s t r a c t

 A process scheme; hydrocracking and
a combination with hydrovisbreaking
were done.
 Hydrocracking under reaction
temperatures was conducted using
hydrocracking catalyst.
 The heavy residue was converted to
produce high quantity and quality
fuel fractions.
 A combination of hydrovisbreaking–
hydrocracking inhibited fast catalyst
deactivation.
 Best conversions and light fuel
productions were resulted from
The results of the two successive running hydrovisbreaking–hydrocracking processes (i.e. combination)
had relaxed reaction conditions, high HVR conversion and higher HDS reaction compared to hydrocrack-
ing process. The combination process characterized with liquid distillates of low sulfur contents, high
middle distillates yield, and long catalyst regeneration period. In addition, the remaining heaviest residue
fraction, i.e. 350°+, represents either boiler fuel feedstock or a heavier product used as feedstock for other
conversion processes (catalytic cracking or delayed coking) due to its acceptable quality. Comparison of
hydrodesulfurization (HDS) under hydrocracking and successive hydrovisbreaking/hydrocracking-
combination processes at variable reaction temperatures.
100
Hydrocracking
90
Hydrovisbreaking/Hydrocracking
80
70
HDS-Conversion, wt-%

contaminants reduction. 60

50

40

30

20

10

0
350 380 400 425
Reaction temperature

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

Article history: Upgrading of heavy vacuum residue (302.3 ppm Ni + V, 4.36 wt% S, and 13 wt% asphaltenes) into valuable
Received 15 January 2013 lighter fuels has been studied in a batch autoclave reactor by hydroconversions over bifunctional sulfided
Received in revised form 6 November 2013 catalyst W–Ni–P/SiO2–Al2O3, at different reaction temperatures, 350–425 °C and 12 MPa hydrogen pres-
Accepted 7 November 2013
sure. The activity of the sulfided catalyst towards hydrocracking reactions scheme alone has been com-
Available online 26 November 2013
pared with a combination scheme (hydrovisbreaking followed by hydrocracking) in order to produce
light fractions suitable for automotive fuels. The catalyst gave, at higher temperature 425 °C, about
Keywords:
80% feedstock conversion, 5% coke make, 98% hydrodesulfurization (HDS) and 73% asphaltenes reduction,
Hydrovisbreaking
Sulfide catalyst
when applying the combination scheme, compared with hydrocracking alone. The presence of hydrogen
Heavy vacuum residue conversion in the hydrovisbreaking reaction medium was necessary to limit coke production. These results indicated
Upgrading that hydrovisbreaking was a suitable alternate treatment option for heavy vacuum residue before hydro-
Hydrocracking cracking process.
Ó 2013 Elsevier Ltd. All rights reserved.

⇑ Corresponding author. Tel.: +20 1223614989; fax: +20 222747433.

E-mail addresses: mohammedfathyh@yahoo.com, mohammed2002@link.net
(M.F. Menoufy).

0016-2361/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.fuel.2013.11.017
 M.F. Menoufy et al. / Fuel 119 (2014) 106–110
1. Introduction
Upgrading of heavy petroleum residues into valuable light frac-
tions has attracted more attention due to growing worldwide de-
mand for transportation petroleum fuels from declining reserves
of light crude oils. Hydrocracking processes are commercially
available to process a wide range of different characteristics feed-
stock to produce a broad range of products [1,2] and deeply to re-
move heteroatoms. Most of hydrocracking catalysts are dual
functional catalysts. They have hydrogenation–dehydrogenation
function as well as acidic function. The cracking activity was con-
trolled meanly by the support, which is acidic in nature, whereas
the hydrogenation–dehydrogenation activity is due to the metals
loaded on the support [3,4]. Even though, the Egyptian refineries
need to maximize the amount of premium products from each bar-
rel of crude or heavy residues as environment-friendly products.
Consequently, understanding the variable options for residue pro-
cessing and their impact on refinery yields and economics allows
the refiner to select the optimum residue-processing route consis-
tent with both the quantity and quality of the available residue and
the required products distribution. This can overcome by selecting
some upgrading methods, either by addition of hydrogen, or reject-
ing carbon, or using a combination of both methods [5–9].
Attempts to increase conversion of heavy oils during visbreak-
ing will bring on sediments deposition. However, this can change
by the use of hydrovisbreaking [10]. Among the thermal process
of hydroconversion, the hydrovisbreaking differs from visbreaking
in the addition of excess hydrogen in the thermal treatment. One
attractive option to achieve the maximum benefits is by combining
various technologies. That is, using more than one process to
upgrade heavy petroleum, in such a way the advantages of each
approach are put together in an integrated process scheme and this
synergy may yield higher benefits than using a single process.
Some of these have been already reported and tested at commer-
cial scale while others are still being proposed and under evalua-
tion. The Institute Francais du Petrole (IFP) has proposed variants
of processes that call for the use of hydrogenating atmospheres,
i.e. hydrovisbreaking [10]. Through comparison of the chemical
analogies of visbreaking, hydrovisbreaking and hydrocracking
[11], found that the driving force of the conversion reaction is
essentially thermal activation in the applied temperature ranges.
Hydrogen in the usual hydrovisbreaking reactions of petroleum
residues or heavy oils has an inhibitor effects on condensation reac-
tions that leads to coke formation. In this study, hydrovisbreaking is
a possible alternate option prior to hydrocracking process, named
as a combination scheme. A comparative study of hydrocracking
and a combination of hydrovisbreaking followed by hydrocracking
of heavy vacuum residue was studied, in order to produce light or
middle distillates within the environmental specifications.
2. Experiments
2.1. Raw materials
Strait-run heavy vacuum residue, SR-HVR obtained from an
Egyptian refinery, Suez Oil Processing Company (SOPC) was used
as a feedstock for hydrocracking and hydrovisbreaking–
hydrocracking combination experiments. The characteristics of
the feedstock are shown in Table 1.
2.2. Hydrocracking reactivity experiments
Hydrocracking of petroleum, heavy vacuum residue HVR
(350 g) was performed in a batch bench-scale autoclave reactor
(500 mL, Parr-model 7575, USA). The total amount of the available
107
Table 1
Properties of heavy vacuum residue (>565° + C) feedstock.
Characteristic
Specific gravity at 70 °C 0.993
API-gravity 18.6
Total sulfur, wt% 4.36
Conradson Carbon Residue (CCR), wt% 18.7
Nickel content, wppm 138.0
Vanadium content, wppm 164.3
Asphaltenes (n-C7 insoluble), wt% 13.0
C/H, wt% 84.8/10.2
SARA, wt%:
Saturates 24.2
Aromatics 35.7
Resins 17.7
Asphaltic resins 9.4
commercially pre-sulfiding catalyst was 35 g. The catalyst was
composed of 15 wt% W, 4 wt% Ni, as metal oxides, and 1.2 wt%
phosphor as promoter, loaded on silica–alumina support. Its char-
acteristics are; surface area of 220 m2 g 1, pore volume of
0.48 cm3 g 1 and pore size of 4.5 nm and 9.6 nm, which character-
ized as mesoporous materials [12,13]. This catalyst showed
WO/NiO and silica/alumina ratios of 3.6 and 3.8 respectively, and
its sulfur content after sulfidation was 5 wt%. The experiment runs
were carried out at different reaction temperatures of 350–425 °C
under a total hydrogen pressure of 12 MPa, and catalyst-to-feed ra-
tio of 1:10 (wt/wt) and run period of 3 h. The products (gases and
liquids) were collected and quantified for further analysis.
Hydrovisbreaking of the petroleum vacuum residue (350 g) was
performed in the same batch-autoclave reactor, without catalyst
addition. The experiment runs were carried out under the same
operating conditions of hydrocracking runs. After each hydrovis-
breaking run, the autoclave was allowed to cool down to room
temperature and the reaction pressure was recorded, purged out
the produced gases to quantify, then the autoclave was opened,
and reloaded with the required sulfide catalyst (35 g). The combi-
nation experiment runs were carried out under the previous
hydrocracking operating conditions.
2.3. Analysis of products
The liquid products of hydrocracking and combination runs
were separated by distillation into four fractions (gasoline, kero-
sene, gas oil and residue) in order to obtain fractions suitable as
transportation fuels. Physicochemical properties of all analyzed
fractions were determined using the standard test procedures des-
ignated for petroleum products. Solid spent of the investigated cat-
alyst after purging the liquid products was collected and washed
with toluene under reflux to remove adsorbed residual oil whereas
solids obtained (spent catalyst and coke) were dried at 100 °C.
Dried spent catalyst was regenerated by oxidation under air atmo-
sphere at 500 °C during period time of 4 h, and the amount of coke
was determined as the weight difference among solid after and be-
fore calcinations.
3. Results and discussion
3.1. Hydrocracking reactivity experiments
Fig. 1 represents the conversion of the HVR as a function of tem-
perature variables through production of total liquid yields, hydro-
carbon gases, and coke formation. The highest yields of gases and
coke were produced after the run of hydrocracking at temperature
of 425 °C. On the other hand, the liquid yield was decreased at this
temperature.
108 M.F. Menoufy et al. / Fuel 119 (2014) 106–110

100 40
14 35 Gasoline (C5-160 °C) Kerosene 160-250 °C) Light gas oil (250-350 °C)
95
30

Yeild, wt-%
12 90 25
20

wt-% (Total Liquid yield)

Coke, wt% 85
10 15
Hydrocarbon gases (C1-C4), 80 10
wt-%

8 wt% 5
75
Total Liquid yield, wt% 0
6 70 350 380 400 425
Reaction Temperature
65
4
Fig. 2. Effect of reaction temperatures on HVR hydrocracking for distillates
60 production.
2
55

0 50
345 355 365 375 385 395 405 415 425
Reaction temperature (°C)
Fig. 1. Effect of reaction temperatures on HVR hydrocracking for total liquid yields,
hydrocarbon gases and coke production.
It is known that the major goal of hydroconversion is hydro-
cracking the feedstock with simultaneous refining of the cracked
products and asphaltenes conversion under the catalytic reactions.
Residue conversion is considered mainly thermal, but a catalytic
effect could be seen from the data. According to Sanford [14,15]
most of the distillates and gases came directly from common rad-
ical precursors formed by thermal activation of labile chemical
bonds of the residue molecules. The coke yield was slightly in-
creased due to asphaltenes conversion. The resulted data revealed
that the principal function of the sulfided catalyst is to eliminate
the condensation reactions of the converted hydrocarbons, which
are responsible to coke formation, via hydrogenation of the highly
produced unsaturated compounds (e.g. asphaltenes) during heavy
residue conversions. It means that asphaltene molecules adsorbed
or decomposed on catalyst surfaces, converted to coke and the
unsaturated compounds were hydrogenated.
Fig. 2 shows patterns of asymptotic curves, as functions of con-
verting the studied feedstock (HVR) to lighter fractions under the
effect of both hydrocracking catalyst and reaction temperatures.
The figure summarized a dependence of each product on reaction
temperature for HVR conversion. It was evident that the hydro-
cracked liquid products, after distillation were lightened (gasoline,
kerosene and gas oil) as the cause of increasing temperatures. The
hydroconversion reactions of the feedstock sample used in this
work at temperature 425 °C provided the largest amount of gases
and liquid fractions, including middle distillate mixtures (kerosene
and gas oil) accompanied with lowest yield of heavy residue 350°+.
As kerosene fraction is a middle type used for diesel production, re-
mix middle distillate fraction (i.e. 160–350°) can be prepared by
up to 95 wt% at 425 °C. However, HDS rate is probably depending
upon catalyst amounts in the reactor (i.e. removing sulfur as
H2S), part of HDS is resulting from cracking of feedstock, since
desulfurization rate is not reducing to zero without catalyst. More-
over, sulfur bridge in molecules may be weak points where crack-
ing may occur thermally. Therefore, the applied catalyst (sulfided
WNi–P/SiO2–Al2O3) favored the hydrogenation and HDS reactions
of products.
The fission function in this catalyst is provided by its support
(SiO2–Al2O3). Its splitting activity is depending on SiO2–Al2O3 acid
sites strength, which follows the ionic mechanism [13,16]. It was
found that the conversion of HVR (Fig. 3) was independent on
catalyst concentrations, which suggested that HVR cracking reac-
tions are predominantly thermal (C–C cleavage) reactions and
hydrogenation reactions [17,18]. The hydrogenation function is
the duty of the transition metals W–Ni– dispersed over the sup-
porting surface, while phosphor as a catalytic activity promoter.
The hydrogenation reactions catalyzed by those metals follow
the free-radical mechanism.
The data of Fig. 3 revealed that the catalyst has higher activity
and resistance to sulfur, and nitrogen compounds. This may be
due to the hydrogen spillover, which makes the reactive hydrogen
species cover on the catalyst surface. When the catalyst encounters
the sulfur and nitrogen compounds containing in the feedstock, the
reactive hydrogen covering the catalyst surface will react with sul-
fur and nitrogen compounds and inhibit poisoning of the catalyst
by heteroatoms [13,19,20]. It is evident from the data that the
highly loaded W–Ni–P/SiO2–Al2O3 catalyst exhibits higher activity
for hydrocracking the HVR feedstock. Hao et al, [21] found that the
high amounts of tungsten loading on the Ni/SiO2 catalyst increases
the amount of both hydrogen adsorbed and Bronsted and Lewis
acid sites on the catalyst. Both catalyst and reaction temperatures
110
100
HVR HDS CCR Asphaltenes
90
Conversion, wt-%

the appropriate amounts of kerosene and light gas oil fractions. 80

Addition of kerosene caused, as expected, decrease of flash point, 70
which will be within the limits specified by the Egyptian Standard 60
for diesel fuel and slight decrease in density and cetane index. 50
Fig. 3 shows the conversion performances (conversion of HVR, 40
HDS reactions and reductions in conradson carbon residue (CCR) 30
and asphaltenes) as a function of variable reaction temperatures. 20
As expected, conversion of the feedstock increased as temperature 10
increasing from 53.1 wt% at 350 °C up to 74.1 wt% at 425 °C. The 0
350 380 400 425
same trend was observed for; asphaltenes, conradson carbon resi-
Reaction temperature
due and sulfur contents of the produced cracked liquids. Therefore,
due to temperature increased, the hydrodesulfurization (HDS) Fig. 3. Effect of reaction temperatures on HVR-conversion under hydrocracking
reaction increased with conversion, ranging from 78% at 350 °C process.
 M.F. Menoufy et al. / Fuel 119 (2014) 106–110 109

are principally influenced the depth of HDS in the feedstock, while Table 2
hydrogen pressure is limited, and hence does not control the rate Hydrovisbreaking/hydrocracking combination – process for heavy vacuum residue
conversion at different reaction temperatures.
of hydrogenation process [17,22–24].
Characteristics Reaction temperature, °C
350 380 400 425
3.2. Combination reactivity experiments
Total liquid yield, wt% 94.6 91.1 87.2 81.4
Coke, wt% 1.4 1.9 2.8 5.1
Hydrovisbreaking of heavy vacuum residue (HVR) is a preferred Hydrocarbon gases (C1–C4), wt% 4.0 7.0 10.0 13.5
process applied to medium- and high-sulfur heavy petroleum feed- Pour Point, °C 16 21 24 28
Distillate up to 350 °C, wt% 49.5 55.9 63.3 66.5
stock in order to pre-treate its characteristics to be suitable for
Aromatic contents, wt% 52.0 44.0 36.0 21.0
hydrocracking process. In this study, applying this non-catalytic
Distillates production, wt%
hydrovisbreaking process then followed by hydrocracking one,
Gasoline (C5-160 °C) 23.0 25.7 27.5 28.5
using the same catalyst (sulfided WNi–P/SiO2–Al2O3) under the Kerosene (160–250 °C) 12 13.2 15.3 17
same operating conditions, is an option for heavy vacuum residue Light gas oil (250–350 °C) 14.5 16.7 20.5 21.0
conversion to light and middle fuels. Residue 350 °C+ 45.1 35.2 23.9 14.9
In order to determine the catalytic conversion of HVR under the Middle distillates (160–350 °C) 26.5 30.2 35.8 38
Total conversion, wt% 53.5 62.9 73.3 80
combination scheme, the reactions are conducted in the same reac-
Selectivity to middle distillates, % 49.5 48.4 48.8 47.5
tor and same operating conditions of hydrocracking. The data illus-
trated in Fig. 4 shows conversion performances of the feedstock
and reductions in sulfur, asphaltenes and CCR. The conversion of
these constituents was higher in case of the combination process Table 3
than hydrocracking alone. The same trends follow the effects of Effects of hydrovisbreaking/hydrocracking combination-process on distillates sulfur
reaction temperature, but more increases if compared with data contents (wt%) at different reaction temperatures.

of Fig. 3. Conversion of the feedstock increases from 53.5 to Products, wt% Reactor temperature, °C
80 wt% as temperature increasing from 350 to 425 °C, respectively. 350 380 400 425
At 53.5 and 80 wt% conversions, the removal of vanadium and
Gasoline 0.10 0.08 0.06 0.01
nickel was expected as indication of asphaltene contents reduction. Kerosene 0.13 0.11 0.09 0.02
These reductions are also reflected on sulfur, i.e. HDS, reaching Light gas oil (LGO) 0.19 0.16 0.12 0.02
highest amount, 98% at 425 °C. Fuel oil residue (>350°+) 0.39 0.24 0.13 0.02
Further treatment by choosing a suitable combination process
could result in a balance between process economics and products.
Hence, process temperatures strongly affect the conversion of the
vacuum residue, and the combination scheme enhanced HVR con- especially sulfur contents. The lowest sulfur contents were ob-
version. Table 2 shows liquid products and their distillate fractions tained at 425 °C for gasoline, kerosene, gas oil and residue 350°+,
under the combination process. All yields vary similarly as a func- i.e. reached; 0.01, 0.02, 0.02 and 0.02 wt% respectively. The data
tion of catalytic conversion under 12 MPa hydrogen pressure and suggest that the success of the catalytic upgrading of the investi-
variable reaction temperatures. The reaction temperature plays gated feedstock depends on the characteristics of the employed
more important role, as seen from the observed increase in gaso- catalyst.
line, kerosene and gas oil yields when the reaction temperature
was increased from 350 to 425 °C. The yield of middle distillate 4. Conclusions
was highest at temperature 425 °C, if compared to hydrocracking
scheme. The reason is that both kerosene and light gas oil yields The obtained data suggest that hydrocracking reactions are not
were increased with temperature increasing as the conversion of affected by mass transfer of heavy vacuum residue reactant to the
heavy fraction, 350°+, to light distillates. This residue, due to its active surface of the catalyst due to certain inhibition of either
characteristics can be fed to the catalytic cracking units for produc- asphaltenes or total sulfur contents. When using the sulfided cata-
tion of low sulfur fractions of motor fuels. lyst, WNi–P/SiO2–Al2O3, more hydrocracking and HDS activities
Data of Table 3 indicating the effects of cracking catalyst under were obtained through the combined scheme compared with
investigation towards upgrading of the produced distillates, hydrocracking scheme, producing lighter distillates of moderate
qualities and reductions in feedstock contaminants. At higher reac-
tion temperature, i.e. 425 °C, total coke formations was nearly the
110 same, 5.0%, but 98.0% hydrodesulfurization (HDS) and 80.0% feed
100 conversion were obtained when using the combination reactions
HVR HDS CCR Asphaltenes
90 compared with 95.0% HDS and 74.0% feed conversion for hydro-
cracking alone.
Conversion, wt-%

80
70 The results of the two successive processes (i.e. combination
60 process) indicated that this combination had relaxed reaction con-
50 ditions, high middle distillates or diesel yields, and long catalyst
40 regeneration period. In addition, the heaviest residue fraction, i.e.
30 350°+, represents either boiler fuel feedstock or applying to other
20 conversion processes (catalytic cracking or delayed coking) due
10 to its acceptable qualities. The improvement in performances,
0 when using hydrovisbreaking, in terms of HDS activity is, however,
350 380 400 425
limited to values of around 20% compared with the classical vis-
Reaction temperature
breaking. Therefore, hydrovisbreaking process was the possible
Fig. 4. Effect of reaction temperatures on HVR-conversion under hydrovisbreaking/ alternate option routes for HVR feedstock treatment before hydro-
hydrocracking-combination process. cracking process, which names a combination scheme.
110 M.F. Menoufy et al. / Fuel 119 (2014) 106–110
Acknowledgements
The authors gratefully acknowledge the opportunity to carry
out this work by the petroleum-refining group, Egyptian Petroleum
Research Institute (EPRI), Academy of Scientific Research and
Technology (ASRT).
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