REVISTA TOCNK:A INTEVEP

FURTHER PROCESSES TO UPGRADE HEA VY CRUDES AND

RESIDUALS DEVELOPED AT INTEVEP, S.A.

ROBERTO GAUASSO
ProcessDevelopmentDepartment
INTEVEP, S.A.

ABS11I.Acr:The research and development activities carried out by INTEVEP. S.A. for the upgrading
of heavy oils and residual s are summari~. These activities originated four process schemes
in 1983. and two commercial processes in 1987. The information obtained frorn these activities
allowed me development of other processes and provided INTEVEP with important know-how.
The majo scientific results are analy~. centering the discussion in me contributions associated
with the HR. HH. SHH and DHDS processes.

RESWMEN: Se resumenlas actividadescientíficas realizadaspor INTEVEP. S.A. en el áreade

conversiónde crudospesadosy residuales.las cualesdieron lugar a cuatroesquemasde procesos
en el año 1983Y a dos procesoscomercialesen 1987.La infonnación recabadaen el desarrollode
estasactividadespennitió la generaciónde otrosprocesosy de áreasdel conocimientoimportantes
parael nivel tecnológicode INTEVEP en la actualidad.Se analizalas contribucionescientíficas.
en particular.los aspectosque dieron lugar a los procesosHR. HH. SHH y DHDS.

Oel's carbon conversion (Combi-Cracking) applied during the

1. INTRODUCI'ION
From 1977,asa result of the nationalization of oil, Venezuela
began making integration and development efforts in the
hydrocarbon industry. Although the country had reservesoflight
and medium crudes, there were strong expectations about the
development of the Orinoco Oil Belt's heavy and exb'aheavy
cnIdes. Moreover, the market favored the sale of thesetypes of
hydrocarbon and at the world level there was interest in the
application and development of residue conversion processesto
transform residuesinto distillates. The economic benefits arising
from the application of conventional coking technologies
confirmed the area's potential.
In that sameyear,INTEVEP, S.A. regan its resean:hactivities
in its laboratories at Los Teques in the areas of production,
transportation and upgrading of heavy oils.
Basedon previous studiesdone in the VenezuelanInstitute of
Scientific Research - (IVIC - Instituto Venezolano de
Investigaciones Científicas) [1 l, it wa.~decided that the area of
greatest technological interest was that of hydrocracking and
hydrodemetallization, taking into accountthe problemsassociated
withexisting coking processes.At the time, therewascornrnercial
experience only in the areaof HRI ebullated bed hydrocracking
pnx:e.~s(H-Oil), Gulfs hydrodesulfurization (HDS), and Veba
war. Additionally, Shell was testing a new mobile bed
hydrodemetallization technology (HDM) in a pilot unir in
Gottemburg, Sweden.Othercompanies, suchasExxon, BP, IFP,
Chevron, Chiyoda. Idemitsu, as well as some researchcenters,
were developing processesandcatalyststo handlethesematerials
with high metal and sulfur contents.
INTEVEP, S.A. staned its activities with thecharacterization
of Venezuelan heavy crudes, and the development of catalYsts
and processes. Simultaneously, the necessary experimental
facilities were developed and young personnel with lirnited
expertise were trained in the new equipment and techniques.
This paper will describe the various aspects leading to the
formulation of the processes,as well as novel afeas in which
scientific contributions were made. Relevant aspectsin a heavy
crude conversion technology are as follows:
- F eedstockpreparation zone. The particular characteristics
of the feedstock considered (crude - residue - deasphalted -
distillate), especially its reactivity, generatedifferent altematives
in the process, and condition the selection of a catalyst and a
reactor.
- Reaction zone. Catalyst and reactor influence each other.
They must be developed as a function of each other. taking into
account the reactivity of the feedstock and the objective (type of
reaction required). As progress is made, they adjust the~selves
to the process scheme.

REV. TEC. INTEVEP 10(1): 47-61. ENERO - JUNIO 19CXJ/47

 - , -~
c. ,-" i I .. C I
. Upgradingprocf'sses
- Zone of separation of catalysts from liquid and gaseous
products. When a catalyst remains in the reactor, the only
separation that has to be made, by conventional means, is that
of gases (non-condensable) from liquids, an operation which
does not require any special equipment. But when the catalyst
leaves the reactor together with the liquid products, they have
to be separated. If their density is not different, the separation
requires special methods, and developments have to be made.
- Liquid product purification and separation zone. Insoluble
materials must be eliminated from liquid products in order to
seUthem or recycle them into fue reactor. Generally speaking,
fue purpose is to limit as much as possible fue formation of
insoluble materials in the chemical reaction stage SOthat the
separation stageswiU be conventional ones and less expensive
(such as the case of atmospheric and vacuum distiUation).
- Product hydrotreatment zone. The quality of fue products
is adjusted here, and in somecasesthe conversion into distiUable
products is completed. In fue caseof distiUares,the hydrotreating
technology requires fewer developrnents than in the case of
residues (total or deasphalted); if there are metals, special
processes are required.
The five process schemes studied from 1977 were as
foUows:
1- Elimination of most of the metals through deasphalting
to proceed to demetaUization and hydrotreatment of the
deasphaltedproduct (DHDS process).A synthetic crude
and asphalt are produced.
2- Treatment of complete residue or fue crude through a
dernetaUization stage, foUowed by a hydrotreating
stage in order to produce distiUates and non-con verted
residual (HH process).
3- Treatment of the residue or the complete crude in two
thermal stagesfor their hydroconversion, foUowed by a
product purification stage and hydrotreatment of
distiUates (SHH process). DistiUates and a residual are
produced.
4- Treatment ofthe crude or its residual in a hydrocracking
stage, foUowed by a catalyst separation stage, and
hydrotreatrnent of distiUates (HDH process). Non-
converted material mayor may not be recycled.
5- Residual treatment in a first dernetaUization stage,
foUowed by a thermal hydroconversion stage, and
afterwards, through hydrocracking, distiUates, wbich
are hydrotreated, and a residual (HR process) are
produced.
Particular developments were made in each scheme,
especiaUy catalysts and reactors. AU the zones are analyzed
below, starting with the feedstocks, foUowed by conversion
catalysts and reactors, and finaUy the purification of products
and the hydrotreabnent of distiUates. Finally, a summary is
made of the developrnents of DHDS, HH, SHH, and HR
48/REV.11!C. INTEVEP 10(1): 47.61. ENERO - JUNIO 1990
GALIASSO ".
.coi ,!o¡ .,
processes.Since the HDH processis dealt with in another
article ofthis issue[2). it will only be mentionedbriefly.
2. CHARACTERIZATION AND REACflVITY
OF EXTRAHEA VY CRUDES
The Orinoco Gil Belt' s extraheavy crudesarecharacterized
by aspecific gravity higherthan I.aresiduecontent higherthan
6Owt %. a metal content higherthan 400ppm. mainly vanadium
and nickel. and an asphaltene content higher than 12wt %.
In 1977. substantial efforts were made with a view to
developing anaIyticaI techniquesfordeep crude characterization
with the API 60 project. Particularly. techniques for the
separation and characterization of heavy fractions of light
crudes were established and applied. INTEVEP. together with
the US DepartmentofEnergy (DOE). beganthe characterization
of Cerro Negro crude. The first work made by Sánchez.
Murgia. Lubkowitz el al. [3] presentedthe main characteristics
of these heavy materials. A strategy was designed for the
analysis of feedstocks and conversion products. After a
distillation stageof up to 700°C. a preparatory chromatography
with exchange ionic columns is carried out to obtain acid
fractions. bases. and hydrocarbons. Various fractions with a
content of nitrogen. acids and phenols can be obtained from
acids through a silica preparatory chromatography. The second
family (bases) can also be separated into basic compounds of
different sizes and structures with the sametype of column and
group of solvents. The third family is separatedjoto aromatics
of different sizes with a silica column and a special stationary
phase. The Nipper 160 report deepensthe study of the routine
distillation and characterization stage. Nipper 161 develops
the improvements made in the separation and identification of
aromatics. Reports 322. 323 and 324 complement the
characterization ofbasic acid compoundsand aromatics. Report
325 anaIyzes sulfur distribution.
Cerro Negro crude contains 18.2% of acids. 17.6 % of
bases. and 14.7wt % of hydrocarbons. The latter contains
cycloparaffins. Most of the aromatics are neutral poI yaromatic
compounds. whose molecular weight grows continuously
toward heavier fractions. This is the case of sulfur. whose
distribution is discontinuous. with a minimum in the diesel
fraction. It is important to point out the high proportion of
naphthenic acids in the heavy gasoil [4].
AIl characterization technologies dealt with distillates. but
they gave no information on most of the crude. that is. the
residue. That is why a study was initiated on heavy crude
separations through the SARA method and high pressure
liquid chromatography [5).
In terms ofthe process.the study ofthe molecules containing
vanadium and nickel is of paramount importance to understand
hydrocracking and demetallization reaction mechani~m~. For
 this reason, in 1980 research was initiated on the thennal
perfonnance of asphaltenes and resins. which comprise the
part of the residue that contains mainly metals. Both are
associations of complex molecules (extended porphyrins-
porphyrins and quelates). which are classified by precipitation
with paraffinic solvents and by solubility in aromatic solvents.
Asphaltene micelles stabilize through solvolysis; their size
depends on the concentration. temperature and physico-
chemical interaction ofthe molecules. Generally speaking. the
difference between resins and asphaltenes is given by the
association-polymerization degree of the basic molecules
already rnentioned. through alkyl-naphthene bridges. according
tooneofthe more widely accepted hypotheses in the literature.
When they are heated, these materials undergo important
transfonnations.
Cotte and Calderón (6 J studied the perfonnance of the
asphaltenes from various crudes at different temperatures. in
the absence of gaseous flow. They discovered that the first
stage corresponds to a loss of solubility of the aromatics
(100°C) due to infernal arrangements and polymerization;
later. decomposition sets in andoat 350-450°C. there is maxi-
mum loss of light compounds. depending on the temperature,
the origin and heating speed. Insoluble products in carbon
sulfide are fonned in this stage. when they become carboides
and coke. As temperatureincreases.asphaltenesaretransformed
into cok e through thennal cracking and polymerization.
Blanco and Galiasso (7J studied the heating of resins.
asphaltenes. and oil of the residue 500° C+ of Jobo crude.
together and separately. They demonstrated that this
performance is valid in resins and asphaltenes; however. when
they are combined. intensity changes. and this happens at
different ternperatures for each of them. Likewise. the
performance is different depending on whether they are
combined or in the residue. The stability ofthe residuesand the
cake formation at different heating speedswere also studied in
order to optimize the manner in which these material s are
carried to chemical reaction temperature (thermal or catalytic).
In addition, their performance in the presence of nitrogen,
hydrogen and solids was determined.
Similarly, Quintero. Larrauri and Galiasso (8) analyzed the
hydrocracking reaction in the presenceof inert solids. catalysts
and hydrogen. and they found that the presence of a catalyst
modifies the asphaltene conversion. reduces gas fonnation,
and increa.sesthe fonnation ofheavy gasoil and diesel. It was
demonstrated that total conversion does not depend much on
the presence of a catalyst at a pressure of 100 atm and
temperatures higher than 400°C. It was stated that the primary
cracking stage is not catalytic but the second and third ones are.
Gal iasso el al. 19)studied the residue of Cerro Negro crude
and the Products from thennal and catalytic conversion in the
presenceof additives and homogeneouscatalysts, It wa.,;found
that in the crude the aromaticity determined through RMN
changes from 0.44 to 0.32 and to 0.21 when going from the
asphaltene to the resin and to the oil. Likewise. the number of
aromatics per molecule is 16. 6 and 2; V IN i ratio is 4. 6 and 2;
the molecular weight (determined through osmometry) is
2.(xx); 1.250 and 1.(xx); respectively. After having convened
50% ofthe residue. the propenies ofthe products change in the
presenceof a larger number of aromatics per molecule ( 12-10-
3). less molecular weight (1.300-800 and 750) and a higher
C/H ratio in the asphaltenes.resins and oil. In the asphaltenes.
there is 70% of insoluble material in toluene and in carbon
disulfide with coke characteristics. These results explained the
decomposition stages of asphaltenes and resins. and product
poIyrnerization reactions.aswell asthe control of thesereactions
by the additives.
Galiasso and Blanco [IOJ conducted similar studies with
hydrodemetallization catalysts. It was demonstrated that the
propenies of resins and asphaltenes change in a different
manner from that mentioned earlier. to form less aromatic
products with a lower C/H ratio. a molecular weight between
1.200 and 900 um. and total solubility in aromatic solvents.
These basic studies on the transformation of heavy molecules
made it possible to design models on the reactivity and
deactivation speedofheterogeneous catalysts. The latter. which
is related to the homogeneous or heterogeneousdeposition of
the metal in the panicle, is associa&edwith the size-diffusivity
of the molecule in the pore.
Sánchez and Galiasso (11 J showed how the asphaltene or
the resin size affects the penetration of the catalyst' s pore~ and
its deactivation. due to vanadium deposition along the pore.
More detailed studies on the characteristics and the reactivity
of the various types of asphaltenesand resins were conducted
by Carbognani. García. Izquierdo. Di Marco. Pérez. Rengel
and Sánchez (12J. who pointed out that the residue percentage.
the gravity. the molecular weight. the content of metals. sulfur
and Conradson carbon cannot be usedas independentpropenies
to establish the reactivity of the residue. A more detailed study
with Morichal. Apure and Barinas residues made it possible to
prove that reactivity is associated with a combination of
propenies. such as age, distribution of molecule sizes. the
distribution of sulfur and metals in the asphaltenes and the
C/H ratio. even though so far there is no known correlation
between these properties and the reactivity 113]. A more
detailed study is being conducled with conversion products in
arder lo predicl their reactivity.
On Ihe other hand. during thedevelopmenl ofthe processes.
basic information wa.'iobtained on the characteristics of reaction
products as a function of opercttion condition~ and of differenl
types of cataly~ts. which allow~ the analy~is of the
hydrogenation-hydrocracking-denitrogenation and hydro-
desulfurization reaction~.
REV. TEC. INTEVEP 10(11:47-61. ENERO. JUNIO 1Cj(¡(J/4Q
 GAUASSO
.,
t Upgrading processes
3. HYDROTREA TMENT CA T AL YSTS
The development in the afea of catalysts was simultaneous
to the study of the characterization of heavy crudes. This
development was initiated in three main afeas: synthetic
catalysts. natural heterogeneous catalysts. and homogeneous
catalysts. The first one could have been designed according to
the requirements. but they were expensive andodue to their
deactivation. it was necessary to consider the possibility of
regenerating them. The second one could have been produced
with elernentsthat abound in nature. through simple procedures.
but with limited important Stnlctural changes. and since their
preparation was economical. it was not necessaryto regenerate
them.
In 1977. a large proportion of research efforts in the world
was centered on the development of demetallization synthetic
heterogeneous catalysts for commercial units and for most
developing processes.It had beenestablished that the selection
of an adequate pare size made it possible to penetrate heavy
molecules inside the pares, where they reacted in active sites.
giving a good vanadium and nickel dispersion, along the radius
of the particle. These metals were deposited inside the particles.
~
~
in active sites or nearby, and deactivated the catalyst with a
decrease of the number of such sites, and of the effective
I diffusivity of the reactives due to the reduction of pare size.
Taking this aspect into account. there were two application
manners: flrst of all. as small-size particles that could operate
in a fixed bed; nevertheless, the catalyst had to be changed after
~,
, a certain amount of vanadium accumulation. A variant of this
,
. altemative consisted in continuously rernoving the catalyst
~ from the reactor operating in a mobile bed or ebullated bed.
The second type of application was as a finely divided or
homogeneous catalyst. which was handled in suspension. and
which could be used in transported red reactors or in
suspensions. The use of hornogeneouscatalysts allowed for a
higher contact efficiency at the expense of considerable
separation difficulties. The catalyst design is associated with
the technology that is being used, and is influenced by the
functioning of such technology.
It was also known that molybdenum, cobaltonickel andoto
~
~ a certain extent, vanadium in the sulfide statecould dernetallize
~ the residues. but no appropriate hydrotreatment and
1 hydrocracking catalysts were known.
i
t INTEVEP started the development of hydrotreatment and
¡ hydrocracking catalysts by selecting and activating natural
1: material available in Venezuela. Likewise. synthetic supports
were prepared and obtained from cornmercial manufacturers
(AKZO, CY ANAMID. FIL TROL). which were impregnated
with active metals. Later. their optimization was started so as
to apply them to specific technologies. Kinetic studies for
particular feedstocks and the analysis of the peñorrnance of
~/REV. TEC.INTEVEP 10(1): 47-61. ENERO-JUNIO 1990
these feedstocks in long tests, made it possible to make the
necessary changes in the fonnulation.
Demelallizalion Synlhelic Calalysls INT -RI and INT -R7
Catalyst INT -R 1 was developed for the demetallization of
residues (HH process) and deasphalted (HDS process); this
was prepared with a Ketjen alumina support through
impregnation with molybdenum and nickel. This catalyst is a
result of a long process of selection of supports to adjust the
porous distribution to a binodal system with pare diameters
between 30 and 300 A.
The demetallization of feedstocks with a different active
phasecomposition was studied through porphyrin adsorption,
whose molecules contain vanadium and nickel, in arder to
detennine the necessary composition and dispersion [14].
Likewise, the preparation was analyzed by making adsorption
isothenns of the precursor (Mo, Ni) with different salts,
concentrations and acid or basic media, and checking its
dispersion by means ofphotoelectron spectroscopy (XPS). In
so doing, it was detennined that it was possible to obtain
maximum activity if the molar ratio Mo/(A 1) = 5 to 8 andNi/
(AI)= 1 to5.
The first results were obtained by Morales el al. in 1978
[ 15], and its application was demonstrated in pilot plant tests of
seven months duration, up to a metal accumulation of70wt %.
[16-17]. This catalyst is being sold today at intemationallevel.
Likewise, a variation of this catalyst was prepared.
Phosphorus was added to its fonnulation in arder to increase
the mechanical strength and removal capacity of Conradson
carbon and hydroconversion (INT-R2) [18].
Thedevelopment afilie secondcatalyst (INT -R7) started in
1980,associatedwith the HR process.The support was obtained
with INTEVEP's technology. The product obtained was an
alumina support with a binodal pare distribution and with a
special adsorptioncapacity [19-20]. Ittumed out that vanadium
can have basic absorption sites in the support, so that not all the
vanadium will deposit on the active metal phase, and the
catalyst will have a longer liCeoThe hydrogenation active phase
is a molybdenum and nickel sulfide, which was optimized for
residue of Bachaquero and Tía Juanacrudes, whose reactivity
is different from that of the Orinoco Oil Belt 's crudes, in which
the reactivity of the INT -R 1 is lower. The optimum pare
distribution is still binodal. but the macropores have a wider
diameter to allow for the accessof vanadium molecules. The
optimum metal dispersion is now Mo/(A 1) =4.5-7.5 Ni/(A 1)=
3-6. and the acidity distribution is such that it has a higher
numberof intennediate acidity sites than the INT -R 1measured
by arnoniadesorption. Thiscatalyst was studied in longduration
tests with residue 500°C+ of Bachaquero Crude, and
demonstrated that it had good stability.
 G~
~"j,'
'" Up,radin,
Thanks to basic studies aimed at understanding the
interaction among organometallic compounds of (he crude and
the catalysts. it wasdemonstrated [14-21] that porphyrins were
adsorbed preferably in the molybdenum sulfides. through the
interaction of vanadium with these sulfides. Additionally. it
was demonstrated that neither the cobalt nor the nickel played
any important role in demetal1ization reactions. The importance
of diffusional controls in the reaction was also analyzed.
Galiasso and Morales [22] analyzed the diffusion of
porphyrinic and non-porphyrinic species to determine their
effective diffusion coefficient. GonzáJez and Galiasso [23]
modeled the activity and selectivity results in demetallization
vs. desulfurization of residues by applying the concept of a
structure interconnected in a probabilistic manner for (he
diffusion path in the pares. and established the importance of
the size distribution of as'phaheneparticles in the activity and
selectivity.
Likewise. (he aging of (he catalyst was analyzed by using
deasphalted feedstocks of Jobo crude [24] and of complete
crudes [25-26]. and (he effect of cake and vanadium in the
i., deactivation was demonstrated by a loss of effective diffusivity
and intrinsic activity. Particularly. it was established that the
three catalyst deactivation periods and (he selectivity depended
.1..
on the parameters for a given porous structure.
Galiasso eral. [27] studied the surface ofthe fourcatalysts
used. and the activity as whole particles and as powder in arder
to clarify separately the effects of diffusion and intrinsic
activity ofthecatalyst with theJoboresidue. It wasdemonstrated
that the deactivated catalyst. operating as whole particles. has
a 20% of initial molybdenum on the surface. while its activity
is only 10% of (he initial activity; nevertheless. after being
grinded. it still has 50% of the initial activity. which indicates
that the plugging of the structure in the pare interconnection
zones is the causeof the premature deactivation. The difference
in reactivity causeshigh reactivity molecules to dernetallize by
the mouth of the pares. and low reactivity ones to diffuse in the
pares. This explained (he need to use graduated beds of
catalysts with different pare distribution and activity in arder
to treat those types of molecule with the objective of obtaining
an appropriate life-span for the catalyst system.
On the other hand. Agudelo et al. [28] demonstrated that
elements Mo. Ni. Cr. and V are the most active ones for crude
dernetallization. Finally. Quintero and Galiasso [29] developed
a procedure for catalyst regeneration through cake oxidation
and treatrnent with a selective solventowhich makes it possible
to remove vanadium from the catalyst used.
Catalysts /NT8HC-I,/NTLHC-/
These natural catalysts were developed for the
hydrodesu Ifurization. hydrodemetallization and hydrocracking
1"
proc~.s.s~.s "
of heavy feedstocks. Both are used after the feedstock is
partially demetallized with the synthetic catalysts mentioned
above. This is because vanadium prefers highly acid sites.
which are necessaryforconversion. a situation that deactivates
them rapidly. The initial studies with these material s were
made by Arias ~I al. [30-31]. who worted with bauxites. iron
and nickel-containing laterites. These materials were activated
in such a way as to generate the best pare distribution possible
and an adequate suñace composition.
Arias and Rivas [32]. on the one bandoand Arias. Kum and
Galiasso [33]. on the other. initiated the development and the
catalytic test of catalyst INTBHC-l. incorporating different
active materials. which were impregnated to fonn the active
phase together with the components present on the suñace of
the Venezuelan baux ileso This study was continued by Garcfa
~tal. [34]. whoadded phosphorus tothecatalystandoptimized
the preparation method. In particular. they produced spheres
and extruded particles through a special treatment which
changed the mesopore distribution. while retaining high
mechanical strength. The good Ktivity of these catalysts
pointed to the possibility of hydrocracking heavy crudes as a
first or a second stage.
Kum ~I al. [35] studied the demetallization of Jobo crude.
The catalyst was assessedon fixed and ebullated red at bench
scale for its application in the HR or HH process. respectively.
CataIyst INTBHC-l was also tested in the pilar plant of
Lummus in New Jersey. U.S.A. [36] on an ebullated red with
Cerro Negro residue and crude. The results were successful.
dernonstnting the high activity and stability of this catalyst.
The second catalyst.INTLHC-l. was developed by Garcfa
~I al. [37] with a Venezuelan nickel-containing laterite which
was properly activated. impregnated with molybdenum and
extruded in various proponions with a macroporous alumina.
This catalyst proved to have more hydrocracking activity than
commercial catalysts [351. high macroporosity. a layer
structure and an adequate substitution of magnesium for other
ions. which makes it possible to create acidity coming from
metals. necessary for asphaltene hydrocracking.
These twonatural catalysts (INTBHC-I and LHC-I) were
characterizedby RamírezandGalarraga [38]. whodetennined
the suñace composition. metal dispersion. acidity and the
valence state of the active elements.
The catalysts already used in the reaction were
characterized by Galiasso t't al. [391. who realized that the
total acidity had decreased to a feeble acidity. attributed to the
cake. and a medium acidity. attributed to the metal sulfides.
Fony percent ofthe sulfides had been eliminated by coverage.
with a 60% reduction of the mesopores and almost all the
micropores elimination. The cok e produces the main
deactivation (20 wt %). and vanadium to a lower degree
(7 wt %).
REV.1K.INTEVEP 1011):47-61. ENERO-JUNIO I~/~I
~'
I
GALIASSO
Upgrading prOC~SMI
Homop,eneousHydrocracking Calalysl
This catalyst is used in bubbling column-type reactors. The
catalyst goes through the reactor to contact the hydrocarbon
and the hydrogen. Afterreacting, the catalyst must be separated
from hydrocarron products through special means. Since the
active metal is in a homogeneous phase, there can be close
contact with the hydrocarbon. This catalyst was used in the
SHH process in the presenceof water steamand hydrogen. The
reaction was called hydroconversion. The catalyst was obtained
by Morales [40] and used in high pressure and medium
temperature batch equipmenL Morales studied the use of
different compounds of molybdenum, and demonstrated that
variable amounts, between 500 and 1,500 ppm, substantially
decreased the coke and gases, and increased the amount of
distillates, similar to that producing heterogeneous catalysts.
Later, Toms and Salazar [41] rnade a comparative study of
hydroconversion catalysts, and studied the effect of deuterated
water; it was detennined that when deuterated water was used,
it would participate in the reaction, because hydrogen was
replaced for deuterium in the light hydrocarbons produced.
Additionally, it was demonstrated that molybdenum was the
best additive. Galiasso et al. [42] proved that regardless of the
initial metal compound, at the reaction temperature, it
decomposes to become part of an asphaltene micelle which
contains Molybdenum. Thus, when the reaction products are
deasphalted, there is a compound of sulfurized molybdenum in
materials insoluble in benzene, where the V IC ratio is higher,
and N/C and SIC ratios are smaller than that of the original
asphaltene. Molybdenum was not found in the product soluble
in benzene (asphaltene). The presenceof water accentuatesthe
perfonnance, and the RMN analysis indicates that there are
deuterated molecules in the asphaltene, and a smaller content
of sulfur in the total molecule. X-ray diffraction studies
conducted in an electronic microscope indicate that there is
surface molybdenum in these insoluble particles, whose size is
close to the micron, and which has a turbostatic structure. The
work done by Núñez and Galiasso [43] demonstrated that
asphaltene hydrocracking occurs with fonnation of resins,
which later crack to produce distillates. The depolymerization
mechanism seems to be associated with the presence of
molybdenum adsorbed on asphaltene.
The same concept was studied in an effort to deposit
molybdenum on a support during the reaction, in order to
replace that which is eliminated in the demetallized catalyst,
due to the reaction of vanadium with the feedstock. Several
studies were carried out which brought about no results due to
aheterogeneous molybdenum deposition in the particle, which
is useless from the technological point of view. Likewise.
studies were made of hydroconversion with molybdenum and
steam water. prior to a fixed red hydrodemetallization with
S2/REV. TEC.INTEVEP 10(1):47-61. . JUNIOI~
catalyst INT -R l. Plugging occunoedwhen conversion severity
is high in the hydrothermal stage. since there occurs the
deposition of insoluble material in benzene. which rapidly
deactivates the catalyst. A stage of low conversion hydro-
visbreaking is only possible when one wants to operate with
fixed red after this stage [44). In this case. molybdenum
remains on the catalyst in an inactive manner. for it does not
change the catalyst activity.
Hydrogen Donor Additives
Research was conducted in the afea of hydrogen donor
additives. It was determined that. at high temperature and
pressures. high molecular naphthenic molecules tend to
dehydrogenate to free hydrogen in the liquid phase. which can
be used in hydrocracking reactions. INTEVEP carried out its
first study together with Chem System (U.S.A.) in 1978. Cotte
[45) participated in the development of a conversion process
for Boscan crude using tetraline as the donating agent. Even
though original results were promising. for it was proved that
the additive had a positive effect. this line of research was not
followed up. The second study was carried out together with
the German company Lurgi. beginning in 1980 within the
frarnework of aV enezuelan-Germanagreement. Studies were
made of Cerro Negro. Jobo and Cogollar crudes. using light
gasoil cut asadonating agent.which hydrogenatedsubstantially
at a high pressure stage (150 atm) to transform aromatics into
naphthenes. During the hydroconversion stage and in the
presenceof gaseoushydrogen. the latter were dehydrogenated
joto aromatics. The presenceof this hydrogenatedhydrocarbon
cut favored conversion and reduced the Conradson carbon in
the non-converted residue [46]. This processwas lessinteresting
than others that were being developed; as a consequence. the
research was stopped.
4. REACfORS
The cataIysts and additives described above are used in
high pressure and temperature reactors. In general. they are
adiabatic. and since the hydrocracking reaction is exothermal.
they haveaggregatesofcold hydrogen tocontrol the temperature
within desired limits. One or various series reactors can be
used. with or without intermediate separation. and the
fundamental variants in the design are associated with the
catalyst and the tluid dynamics.
Four basic reactor concepts were considered during the
1977-1983 periodo which defined the four process schemes
already mentioned:
1) Fixed bed catalyst reactor (the mobile red is only a
variant of the same scheme). This type of reactor is
widely known. (Fig. loa). The particle diameter of the
catalyst is between 1 and 1.5 mm.
,~-' J
. GALIASSO
Unrading proce.rle$
2) Ebullated bed reactor (Fig. I-b). In this reactor the solid
is suspended and perfectly agitated. thanks to the
dynamic pressureof the liquid coming from the bottom
and leaving from the top of the reactor. This pressure is
generated by an internal or external recirculation pump.
The catalyst can be removed from the bottom of the
reactor and added from the top; the particle diameter of
the catalyst ranges between 0.5 and l mm.
Three-phase-bubbling-column-type reactor. in which
3)
the catalyst is in a powder forro (in suspension). the
hydrogen and the liquid enter from the bottom and leave
from the top with the sarne salid concentration. The
catalyst is transported thanks to gas dynamic pressure.
which generates a certain degree of mixture inside.
affecting the temperature profile and hydrocarbon
concentrations. ahd the catalyst distribution in the
reactor. The salid concentration inside can be higher
than in the feedstock [2].
Two-phase-bubbling-type reactor. In this reactor the
4)
homogeneous additive mixed with the hydrocarbon
enters from the bottom together with the hydrogen. and
leaves from the topo Again. there rnay be a profile of
concentrations and temperatures depending on the
selected tluid dynamics (Fig. l-c).
1. "'«0 KO
Fig. l. Types of reKtors.
Fixed or Mobi/~ B~d R~actors
As has already been stated. the application ofthis reactor is
widely known in the areaofhydrocracking and demetallization.
The studies carried out were intended. first of all. to explain the
laboratory reactor fluid dynamics so that their conditions al
industrial level could be reproduced on a small scale [47).
Likewise, the manner of removing the catalyst from the reactor
was studied, because when operating with high metal content
crudes, deactivation is very fast and life cycles are shorter than
one year.
The technology available to solve this problem consisted in
using two reactors in parallel, one out of service or working in
a different stage of life cycle, and another operating with the
whole feedstockormostofit(Gulf HDS usesthis system). The
other possibility is to remove the catalyst in a continuous way.
At the time, Shell was developing a bunker type reactor, in
which the catalyst would come down in a discontinuous way,
be added from the top and removed from the bottorn. The liquid
and the hydrogen would be red from the top of the reactor and
removed from the bottom. The problems in fuesesystems were
increased investment in the first case,and solid agglomeration
and bad fluid distribution in the loading zone in the secondcase.
In 1980, INTEVEP started developing a new type of
mobile bed reactor in which the fluid and the hydrogen would
flow upstream, while the catalyst would be added from the top
and removed from the bottom. This new system was developed
by Belandria. Galiasso and Núñez [48). It has the advantage
that the solid does not agglomerate because the fluid dynamic
pressure aIlows to maintain a certain degreeof expansion of the
bed, additionally, it does not use rotational unloading valves,
the sol id being unloaded through dynamic pressure against the
solid arch. On the other hand, it is oot necessary to put the
reactor out of service; this reactor aIlows the deactivated solid
to contact the fresh feedstock in the lower part, where the most
reactive molecules diffuse in the pores, and vanadium does not
deposit outside the particle. Then in the upper part, the less
reactive molecule meet with the fresh catalyst. and again they
have a better chance to diffuse and react along the pore.
Galiasso el al. [49) demonstrated the advantage of the
unloading operation in the activity. selectivity and distribution
of metals and carbon in the catalyst, operating a high pressure
unit in the demetallization of Jobo crude. Hidalgo and Galiasso
[50) studied the fluid dynamic effects of the upstream flow in
the reactions, and they concluded that the best hydrocarbon-
particle contact increases demetallization, as compared with
the traditional operation with a downstream tlow.
For their part, Di Marco and Cabrera [51) confirmed the
existenceof a higher content of liquid in the reactor with this new
type of fIow, which produced changes in reaction of
demetallization, desulfurization, hydrocracking, removal of
asphaltenesand Conradson caroon. Di Marco determined the
intluence of gas speedon the volume of the liquid accumulated
in the reactor. Finally, Belandria and Mayorga [52) from the
UniversidOOdelos Andesdeterminedtheparametersthat intluence
the unloading of the catalyst by using a cold modelo They
establishedthe criteria for the changeof scaleof the new reactor.
REV. TEC.INTEVEP 1011):47-61. ENERO - JUNIO 1990/53
 GALlASSO
Upgrading processes
Ebullated 8ed Reactor
This type of reactor was developed by the companies HRI,
City Service and Lurnmus, which havebuilt severalcornmercial
units under the process name of H-Oil and LC Fining.
Originally, the idea was to apply this technology with
INTEVEP's catalysts in the form of spherical or cylindrical
particles. The advantage of this system is that the selectivity
of the reactions and the vanadium deposition in the catalyst can
be controlled better than in the fixed bed becausethe catalyst
is suspended and works at constant temperatures and
concentration. Therefore, the removal and addition of the
catalyst is simple, which allows for a constant vanadium
content in the reactor during the operation cycle.
At INTEVEP, it was necessary to test the catalyst and the
process in a bench scale unit. To this end, it was necessary to
have equipment capable of simulating the industrial reactor. A
continuous agitated tank-type reactor with a special internal
was designed and built, in which the catalyst was suspended.
The first designs were tested by Baudet [53], who optimized,
in cold equipment, different forms to tluidize the catalyst
without fines or dead zones being formed. Later, Caprioli et al.
[54] designed and built a high pressure plant with that reactor.
Its operability and the reproducibility of the results were
demonstrated for different operation conditions. Caprioli and
Galiasso [55] analyzed tluid dynamic problems with chemical
tracers, and determined transfer constants for hydrogen and a
model molecule, from the tluid phase to the catalyst. The
possibility to improve the internals of the commercial system
was confirmed. In the higher zone, where the catalyst is
separated from the liquid and the gas, a new detlection plate
was designed, which could make the separation in a highly
efficient manner, so as to prevent the salid from being dragged
with the liquid to the external recirculation parto In so doing,
the liquid drag is also reduced through the gas that leaves from
the top of the reactor.
Two-Phase-Bubbling-Column-Type Reactor
Two phasestlow upstream in this reactor: hydrocarbon and
hydrogen. lt is characterized by the fact that liquid and gas
contents depend on the hydrocarbon properties and the gas
velocity. By 1981, when INTEVEP developed the SHH
hydroconversion process, several studies had already been
done in the world on model molecules (airor hydrocarbon), but
there was little information on its application to heavy crude
hydroconversion.
Studies were initiated on the tluid dynamics, taking into
account existing knowledge on visbreaking with soaker type
reactors (Lummus technology). Thus Barbarrosa, Huskey and
Galiasso [56] determined the mixing degree and the bubble
S4/REV. TEC.INTEVBP 10(1):47-61. ENERO- JUNIO I~
size as a function of the gas linear velocity in the reactor. To
that end. they used model molecules (air-kerosene) and tracers
in a cold model with one or various gasdistribution plates. This
is important for the contact between the homogeneouscatalyst.
fue water steam and (be hydrogen controls the coke forrnation.
Cotte and Galiasso [57] perforrned fue process tests in a high
pressureand temperature unit. which was designed and built to
evaluate the effects of operational variables on the stability
(coke forrnation). It wasdemonstratedthat waterand a minimum
hydrogen-feedstock ratio had a favorable effect on a low coke
and rnesophaseforrnation.
The works conducted by Salazar and Huskey [58]. which
were canied out in fue same unit for longer periods. showed
that feedstockpreheatingis a critical stage.becausefue forrnation
of coking precursors regios during vaporization. The study on
the hydroconversion reactor was complemented with a
helicoidal tubular reactor. in which feedstock preheating is
done in a fiírnace. in fue presente of water and a homogeneous
catalyst [58].
5. EXTRACrlON OF ASPHALTENES AND
INSOLUBLES BY SOLVENT SEPARAll0N
STAGE
Due to the fact that asphaltenes and resins constitute a
problem in the processingofheavy crude residues,the possibility
to deasphalt them was anaJyzed to facilitate upgrading. In
1976, even though there was abundant infonnation on the
deasphaJtingprocess with light solvents, propane and butane,
little was k-nown about heavy crude processing. The initial
works were conducted by Aquino el al. [59-61J, who showed
that heavy solvents allowed for a selective extraction of
asphaJtenesand increased the yield of high metal content
products (in regios) and Conradson carbono As a consequence,
from 1979, INTEVEP developed a deep deasphaIting process
in which participated Aquino, Rodríguez, Granados, Solari,
and Krasuk [62-63 J. Their main conhibution wasto demonstrate
the feasibility of deasphaIting with heavy solvent to produce
solid asphaltenes with a limited particle size, which could be
transported in a suspension fonn. To control the particle size,
a tlocculation stage was developed, in which a particle size
wider than 10 microns was obtained in the separation stage,
through temperature and residence time. Fig. 2 shows the
scheme of this process. A preliminary technical-economic
study for commercial application [64] was initiated, whose
resuIts made it possible to detennine the feasibility of its
intemational commercialization [65]. The deep deasphaIting
associated with a deasphaIteddemetallization led to the DHDS
process.
Simultaneously, a study was initiated on the possibility of
decreasing resins and asphaItenes prior to the deasphaIting
 GALlASSO
" Upgradingpr~s
stage through a hydroconversion process. As for the SHH
process, Huskey and Aquino [66J demonstrated that, after a
hydroconversion stage, asphalteneswould deasphalt by means
of a heavy solvent and water. The results were promising, for
the low resin amount, the presenceof cake microparticles and
of a mesophase facilitated the separation of particles such as
small size solids. Later, the deasphalting prior to visbreaking
was evaluated together with the Institut Fran~ais du Pétrole
(IFP). With this institute the "INTEVEP path" was studied,
which consisted in a hydroconversion followed by a pentane
deasphalting (IFP process), and hydrotreatment of the
deasphaIted oil and the distillates with INTEVEP's catalysts
[67). The results suggestedthat from the technicaI and economic
viewpoint, it was an interesting way for the Orinoco Oil Belt' s
heavy crudes [68J. As ~ result, the two companies would
proceed to commercialize it.
Fig. 2. neasphaltingprocessin a solid phase.
Another way to optimize deep deasphalting processeswas
coking of sol id products. To that end, together with Lurgi and
within the cooperation frarnework with the German government,
studies were made of the feasibility of using LR Coker
technology with asphaltenesproduced in the IFP's pilot plant
in Solaize, France. The distillates produced with this process
were hydrotreated at INTEVEP. Aquino and Solar [69]
demonstrated that the process was feasible and that it was
possible to improve the liquid yield thanks to a 50% solids
conversion (asphaltene) joto distillates. Lurgi and INTEVEP
patented the process scheme.
Finally, several studies were carried out topurify, bymeans
of solvents, streams from hydrocracking reactors in arder to
sell free-of-solid residues (coke and catalyst microparticles) or
to recycle non-converted material into the hydrocracking stage.
The ideas developed in the case of deep deasphalting could be
applied in this case with special equipment to separatethe sol id
from the non-converted hydrocarbon (residues). This was
successfully dernonstratedby Drago el al. [70J. whoconducted
tests on a pilot scale and cornmercial scale.
6. PRODUcr HYDROTREA TMENT
Since its beginnings, INTEVEP has been doingimponant
work in the hydrotreating afea. First of all, experimetal facilities
were completed and a study of commercial catalysts for
refinery's feedstocks was initiated, with works conducted by
García and pazos [71-72] and pazos et al. [73]. The best
experimental conditions were established for the kinetic
evaluation ofthe activity, and studieswere madeof die properties
of the catalysts having more influence on the commercial
application. Later, deactivation and economic. evaluation
concepts were incorporated for the selection of commercial
catalysts. Within this frarnework, Salazaret al. [74] developed
an accelarated deactivation test and established the parameters
influencing the activity and the stability of the catalysts. A
methodology was established to Speedup aging and to make it
possible to evaluate the catalyst activity cycle in 45 days. This
was later complemented by Salazar, González, and Rodríguez
[75]. During thedeveloprnent ofthe processschemes,distillated
products were hydrotreated to improve their quality by using
cornmercial catalysts and the technology mentioned above.
These studies made it possible to evaluate the performance of
these feedstocks coming from hydroconversion and
hydrocracking processes [76].
Since 1984, within the framework of the Venezuelan-
German agreement (Annex IlIb), studies were made of the
behavior in hydrotreating of naphthafractions, kerosene,diesel,
and heavy gasoil coming from the Orinoco Oil Belt's Morichal
crude, which had been produced through delayed coking,
Coker, Veba Combi Cracking processes and simple direct
distillation. It was found that the reactivity in hydrotreating
depended on the characteristics and origin of the feedstock.
According to the characteristics of the conversion process, the
reactivity of the cut produced ch~ges for cataJysts and
cornmercial hydrotreating operation conditions. Rodríguez et
al. [77] obtained kinetic expressionsfor die hydrodesulfurization
of thesefeedstocks, in which the reaction order and deactivation
did not depend on the feedstock, because its effect was taken
into account by means of a parameter adjustable in terrns of its
aromatic contento The other properties of the products were
established in terms of operation severity and amount of sulfur
removed.
With the inforrnation collected, Rodríguez, García and
Badra built data bases which store most of the inforrnation
obtained at INTEVEP and Petróleos de Venezuela subsidiaries
[78]. Likewise, a seriesof correlations was developed between
feedstock quaJity, operation conditions, type of catalyst and
product propenies. These correlations made it possible to
REV. TEC.INTEVEP 10(1): 47-61. ENERO-JUNIO 1~/.5.5
~I
simulate the performance of units and/or catalysts. Design
programs for hydrotreating vacuum naphtha, diesel and gasoil
units were written, which led to the development of a manual
on cracked feedstock hydrotreating units (79). This knowledge
allowed Badra el al. (80) to prepare the design bases for the
HDH process hydrotreating unir. which were used to draw up
the basic engineering.
Likewise, efforts were made to develop INTEVEP's own
hydrotreatment catalysts. From 1981, Morales, Satazar,
Agudelo, Manínez and Carrasquel developed moderate
hydrocracking and hydroteatment catalysts to treat cracked
gasoil called INTGOV-IOandINTGOV-20,respectively (81).
These catalysts proved to be highly stable in situations of
desulfurization and conversion thanks to a surface composition
where there is a molybdenum, nickel orcobaltand phosphorus-
based active phase.
Galiasso el aJo(821 summarized the main mass and surface
characteristics of commercial catalysts, and demonstrated that
there was no direct con'elation between a particular property
and the activity or selectivity in desulfurization and
denitrogenation. They also demonstrated that a catalyst whose
weight has increased by 6-9% with cake during the first days
and then operates for several years, has surface properties
different from those of fresh catalysts. This same aspect was
analyzed by Galias~ 1831,who studied several commercial
catalysts which have worked fordifferent periods in industrial
Unil'i. The acidity reduction and accessible metal content in
these catalysts were demonstrated. The acidity of original
commercial catalysts was sudied by Ayerbe el al. (841 and
Gajardo el al. 1851,who confirmed that a proper balance of
acidity and metal dispersion can produce a catalyst with an
adequate activity in conversion and desulfurization. Morales
el al. 186-871 demonstrated that phosphorus control s the
catalyst'!i acidity and metal di!ipersion.
On the other hand, Martínez el al. (881developed a catalyst
for moderate hydrocracking a.1ipart of the development of the
conversion technology for ga.'ioil~ in diesel. Prada. Romero
and Muñoz made another highly hydrogenated hydrocracking
cataly~t: INTHHC-I 1891, which make~ it po!i~ible to treat
conver!iion product~ by !iaturating the aromatic~ and reducing
nitrogen and ~ulfur to minimum value~.
7. PROCESSES TO UPGRADE HEA VY
CRUDES
HydrrJdemelCJllizCJlirln
CJndHydrr/("'CJ('kin.l,'
Prr/('e,\',\'(HH)
Thi!i proce!i!icon!ii!it!i ba!iically()ftwo !itage!iwith orwith()U\
recycle()fnon-convened produc\!i: unebullated hydrocrucking
()rIc. which u!ie!icataIY!i\MoP/bauxi\e(INTBHC.1 ).undam)\her
in a fixed hed with cataIY!i\ NiM(~AI (INT -R 1). Their pnx.'C!i!i
~ I REV Tf'.(' INTEVF.P 111I I r 47-6' EN!"") , JUNIO ..,...
scheme did not require any change of scale. becauseboth the
ebullated bed reactor and the fixed bed reactor had been tested
at cornrnerciallevel. Operation temperature ranged from 390
to 4300 C. and pressure between 130 and 150 alm. Space
velocity was 0.4-0.7. and hydrogen-feedstock ratio was I.(xx)
and 2.(xx) N 1/1.Fig. 3 shows the processschernein which none
of the stages.apan frorn the reactor, needsany special studies,
since they are conventional as far as hydrocracking operations
~coocemed.
I
I 1
--
Lo-
I - -- - - _.~~~!!'~\1 \ 1
1 :
r---'
Fig. 3 HH PnM:essScIIeme.
The results suggested that from an 80 API virgin Cerro
Negro crude a good quality synthetic crude could be obtained
with variable API gravily between 27 and 34. depending on the
severity. containing less than 1% of sulfur and 50 ppm of
vanadium, the residues conversion being 5W C+ between 80
and 85 wl %. The prodUCIslate showed a formal ion of 10% of
gasoline. 25% of diesel. 40% of vacumm gasoil. and 25% of
residual volume; this distribution corresponds lo the mínimum
conversion. If increa.'ied.by recycle or notogasoline produclion
would increase.
The process wa.~tesled at bench scale wilh one-month long
tests for lhe hydrocracking stage. and one-month for lhe
demetallization stage. Nevenheless. lhe laner stage had been
lesled for seven monlh~ wilh a non-hydrocracked residue. The
hydrocracking stage was alS() lested in Lummus 3 bpd pilol
plant with INTEVEP'~ catalyst 1901. During the process
development. new element~ were generated ~uch a.~catalyst
and reactor array wilh or wilhout recycle.
Dt'asphallinx and HydrlJdt'.\"u/furi:alinn PrlH't'.\".\"
(DHDSJ
Thi~ processis ba~d on a deepcrude or re~iduedea.~phalling
~Iage followed by hydrotrealmenl of the dea...pi1altedoil.
Dea~phalting i~ done with heavy !iOlvenl~ (C".). and Ihe
a~phallene~ separation is carried out in a !iOlid phase in
accordance wilh the pruce~s~hown in Fig. 2. Once the ~olvent
is recovered. Ihe dea~phalled product obtained from the
cenlrifugal ~"Iing tank is treated in two ~tages.()f1eof which
deal~ wilh the demetal I i.,.ationand the other, which is in ~erie~.
with Ihe de~ulfuri.,.alion. From an Ho API Cerro Negro heavy
crude 12.4'~, of ga.'i()line. J l. 9~, of diesel. 2H~, of vacuum
 GALIASSO
UpgrQdin.~ proc't'sst's
gasoil, and 11.6% of residue volume are obtained. The yield of
asphalt is 13.5 wt % of feedstock. The total product has 210
API, 0.65 wt % ofsulfur. 15 ppm ofmetals and less than 1 wt
% of asphaltenes. Deep deasphalted pressure ranges between
4 and 15 bar, temperature between 20 and 1500C, and solvent/
feedstock ratio between 4/1 and 9/1. Hydrotreatment is done
underpressure of approximately 100atm, variable temperatures
between 375 and 4300 C. and LHSV between 0.4 and 0.7 h-l.
Hydrogen/feedstock ratio is I,OOONI/I. Thecatalystofthefirst
stageis INT -R 1and thatofthe secondstageis a HDS commercial
catalyst. The deasphalted product is hydrotreated on a fixed
bed, this being demonstrated in tests lasting longer than three
months.
A second version of the same process (Fig. 4) uses a
preliminary stage ofhydrovisbreaking, which improves yields
and the metal content in the'deasphaltedproducto The treatment
iscarried out underpressures in theorderof 1OOatm.at variable
temperatures between 400 and 46()° C, and residence time of
several minutes [91]. Someaspectsofthe processare protected
by patents 163,92].
New aspects of this process are associated with deep
deasphalting and demetallization catalysts.
co.
Fig.4. DHDS 11Proces~ Scheme.
Water Steam Hydr(x'()nver.{;on Proce.{.{a)/d Hydr(}treatment
(SHH)
The SHH process can convert heavy crudes or their long
residues intodistillated products by meansof a thennal treatment
in a low-residence time tubular reactor, and a second thennal
stage in a bubbling column-type reactor ("soaker") under the
same pressureand temperature. Later, the products are separdted
under high temperature and pressure.and purified at the bottom
of a separating unit by means of a heavy solvent and water,
Once the solvent is separated,the heavy hydrocarbon is treated
together with distillated products in a conventional
hydrotreatment stage. or recycled into the second
hydroconversion reactor. This reactor usesup to 10% of water
with the feedstock and 500-1(XX) ppm of a molybdenum
additive. This additive. as well as most of the vanadium. is
recovered from the solid precipitate obtained in the purification
stage (solid combustion and ashes extraction). Fig. 5 shows
the process scheme. The operation temperature of the first
reactor is variable. between 400 and 4600 C. the operation
pressure is between 130 and 150 atm. and the residence time
rangesbetween 10and 25 minutes. The secondreactoroperates
at a variable temperature. between 400 and 4600 C, and
basically under the same pressure as the first reactor. The
separating unir operatesat the sametemperature and under the
same pressure as the second reactor, and the liquid phase
purifier at 500 C and under a pressureof 150 atm. The solvent
recovery stage occurs at the same temperature. but under less
pressure. The hydrotreatment of each of the units is done
according to the need to adjust the properties of the distillates.
The SHH processproduces. 13.51% of gasoline. 43.56% of
diesel. 37.50% of heavy gasoil and 5.43 wt % of residue from
an 80 API Cerro Negro crude. The conversion and quality of
a synthetic crude increaseswith recycling. Conversion is in the
order of 90% and production of insoluble solids less than 5 wt
% [93-94]. The SHH process [95-96] has been tested at bench
scale in 20-day tests. Nevertheless. the reactor's operation in
appropriate f1uiddyanmic conditions hasnotbeen demonstrated
at bench scale.
The technological contributions ofthis processare the type
of reactor used. the use of homogeneous additives. and the
product treatment for the additive recovery and the production
of a free-of-solid residue.
Fig. 5. SHH Prtx:e"" Scheme.
REV TEC INTEVEP 10(1): 47.61. ENERO. JUNKJ 1~/57
 ResidualHydrocrackingProcess(HR)
From 1983.INTEVEP continued the development of mobile
bed technology able to hydrocrack anddemetallize conventional
crude residuals with medium-size investment. This happened
up until 1987. that is. until the completion of the development
at bench scale of a two-stage process which used catalyst
INTR -7 for demetallization purposes in a mobile bed reactor.
and catalyst INTLHC-I for the hydrocracking stage on mobile
or fixed beds. Between the two reactors there is a thennal stage
in a low residence time tubular reactor to adjust the size and the
reactivity of asphaltenes(Fig. 6). The first studies were carried
out by Caprioli. Kum and Núñez [97J. followed by the studies
by Kum and Núñez [98J. and arpa. Di Marco and Núñez [99J.
It was demonstrated that it was possible to obtain variable
conversions between 50 and 60%. depending on the stability of
the residual produced under operation pressuresof 137 atm. at
variable temperatures between 370 and 430°C. and residence
times of 0.3 h-l. Bench scale tests for 50 continuous days
demonstrated that the quality of the products and the conversion
could remain stable during the operation cycle [IOOJ.
Fig.6. ResidualHydrocracking
~s Scheme
(HR).
A technicaVeconomic study was done to compare the HR
process to the Gulf HDS for the conversion of Cerro Negro
crude [101]; the advantages of the HR process were
demonstrated from the technical point of view, with a smaller
reactor volume and catalyst consumption, and from the point
of view of profitability. This process, as well as the mobile bed
reactor, are protected with a patent [48, 102); its novelty is
associated with the type of reactor, in the catalysts and in the
thermal conversion intermediate stage which modifies the
particle size so that hydrocracking conversion can occur.
"'REY. TEC.INTEVEP 10(1): 47-61. ENERO. JUNIO 1990
8. CONCLUSION
INTEVEP has technology and know-how in the afea of
heavy crudes and residual s conversion. backed with patents and
experience in the cataIysis afea. and in processes and basic
engineering to proceed to a commercial application oí its own
catalysts and technology in this afea.
REFERENCES
l. KRASUK, J.; ANDREU, P.; BARROET A, N. Desulphurization
and Demetallization ofHeavy Crude and Residues.Acta Cient{jica
Venezolana, 25 (2): 45. 1974.
2. DRAGODEG.et.aI. Desarrollo del proceso HDHrM, Rev. Técn.
lntevep, 9 (2): 111-133.1989.
3. GIRZZLE, P.; GREEN J. B.; SANCHEZ, V.; MURGIA, E.;
LUBKOWrrz, J. Characterization of Cerro Negro Crode. Pan l.
PhysicaI and ChemicaI Separation. Rev. Técn.lntevep. 2 (1): 13-
21.1981.
4. GREEN, J. B.; GRlZZLE, P. L.; THOMSON, J. S.; SHAY, J.;
DIEHL Y, B. H.; HOMMEY, K. W.; SANCHFZ, V. Analysis o/
Heavy Oils Method Development and Application to Cerro Negro
Heavy Petroleum. Repon for rOE from National Institute for
Petroleum and Energy Research. May, 1988.
5. SOL, B.; ROMERO, E.; CARBOGNANI, L.; SANCHEZ, V.;
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6. COTI'E,E.; CALDERON,J. L PyrolysisofBoscanAsphaithenes:
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7. BLANCO, R.; GALIASSO, R. Estudio termogravimétrico de
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Technical Note project RPOO2PA.INTEVEP, S.A. Los Teques,
Venezuela, 1981.
8. QUINTERO, N.; LARRAURI, J.; GALIASSO, R. Hidrocra-
queo de as!altenas y resinas de crudo Jobo en presencia de
sólidos inertes y lateritas. TechnicaI Note project RP002PA.
INTEVEP, S.A. Los Teques, Venezuela, 1981.
9. GALIASSO, R.; SALAZAR, J. A.; BLANCO, R.; MORALES,
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28 (1): 54-62.1985.
10. GALIASSO, R.; BLANCO, R. Hidrodemetalización de crudo
Jobo. Technical Note project RAX)2RG. INTEVEP, S.A. Los
Teques, Venezuela, 1982.
11. SANCHEZ, V.; GALIASSO, R. Desactivación de catalizadores
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MARCO, M. P.; PEREZ, C.; RENGEL, A.; SANCHEZ, V.
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 GALIASSO
,~" c Upgradingprocellel
13. IZQUIERDO, A.; CARBOGNANI, L.; LEON, V.; PARISI, A.
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14. MORALES, A.; GALIASSO, R. Adsorption Mechanismof
BoscanPorpiIyrinson MoO3Co)0and CoMo/AI20) Catalysts.
Fu~/. 61 (1): 13-17,1982.
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16. MORALES, A.; GALIASSO, R.; CARRASQUEL, A. R.
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simultáneadecrudospesados.R~v. Tic. /nt~p, 3 (2): 135-140.
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MORALES, A.; GALIASSO, R.; AGUDELO, M. M.;
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SALAZAR, J. A.; CARRASQUEL, A. R., USA Processfor
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Metal Retention Capacity and Good Stability, Pat~nt
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SALAZAR, J. A.; CARRASQUEL,A. R. USA Cata1ystHaving
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19. ARIAS, B.; MARTINEZ, N.; REYES, E. D~sarrollo d~1
catalizador d~ hidrod~smetalización para tratami~nto d~
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20.
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21. ANDREU, P.;GALIASSO, R.; MORALES, A.; ABRAMS, O.;
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3O-luly 4. 1980.
22. GALIASSO, R.; MORALES, A. Diffusion of Vanadium
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23. GONZALEZ, C.; GALIASSO, R. A Mathematical Modello
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of HDS/HDM Catalysts. Rev. Ticn.lntev~p. 3(1): 3-9. 1983.
24. GAUASSO, R.; GARCIA. l.; CAPRIOU, L Porphyrim and lXX1
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25. GALIASSO, R.; BLANCO, R.; GONZALEZ, C.; QUINTERO,
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26. VELAZCO, L.; GALIASSO, R.; OCHOA, O.; ANDREU, P.
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calalizadores de hidrodemetalización de crudos pesados
venezolanos. Acta C;~ntlfica V~n~zolana. 32138-143,1981.
27. GALIASSO, R.; GONZALEZ, C.; CAPRIOLI, L.; GARCIA, l.
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29. GALIASSO. R.; QUINTERO. N. Extracción de vanadio en
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30. ARIAS. B.; LARRAURI. l.; GALlASSO. R. Bauxitas y lateritas.
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31. ARIAS. B.; LARRAURI. l.; GALIASSO. R. USA
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32. ARIAS. B.; RIV AS. L. Caracterización de bauxitas. Technical
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33. ARIAS. B.; KUM. H.; GALIASSO. R. USA Method of Prepar-
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38. RAMIREZ. M. M.; GALARRAGA, C. Caracterización
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39. GALlASSO. R.; G AR CIA. l.; RAMIREZ. M. M. Caracterización
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40. MORALES. A. Hidroconversión de-f:rudos pesados. Technical
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41. TORRES. E.; SALAZAR, l. A. Estudio comparativo de aditivos
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42. GALIASSO. R.; GAlARDO. P.; SALAZAR. l.A.
Caracterización de precursores del catalizador homogéneo del
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43. NUÑFZ. A.; GALIASSO. R. Hidrocraqueo de asfalteno en
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44. SALAZAR. l. A. Efecto de la hidroconversión térmica en el
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GAUASSO
l' Upgradi"g prOC~.f~.f
4S. CO1TE. E. Inlorm~ 2final d~sarrollo d~1 proc~so d~
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INrEVEP. S.A. Los Teques. 1981.
46. LURGI GMH. Donor SoIwnJ Hydrovisbr~aking. Final Note.
ConvenioVenezolanoAIemM.Anexolvol.B4. 103-109. 1981.
47. GARCIA. W.; PAZOS. l. M. Effect of the Mean P8I1icle Size
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48. BELANDRlA. l.; GALIASSO, R.; NUÑEZ. A. D~.sarrollo d~
un r~actor "trick/~ bed" con r~tiro d~ catalizador. Technical
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49. GALIASSO. R.; BELANDRlA. l.; CAPRIOu. L. U.S.A.
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S2. BELANDRlA.l.; MAYORGA.P.DeSQ"oIlodeun"actor~n
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1989.
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56. GALIASSO. R.; HUSKEY. D.; BARBARROSA, l. Simulación
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61. AQUINO.L.;PACHANO.J.;RODRIGUfZ.l. V.; KRASUK.
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63. KRASUK, J.; SOLARI, B., AQUINO, L.; RODRIGUEZ.J. V.;
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64. AQUINO, L.; GRANADOS, A.; SANCHEZ. J.; RAMIREZ. L.
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65. THE NW KELLOG. T~c/utical and Economical Stlldy of
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66. HUSKEY, D.; AQUINO, L. De.ras!altación de lo.rproducto.r d~
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67. HUSKEY, D.; AQUINO, L. Re.rultMo.r preliminare.r ~ la
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68. AQUINO, L.; SOLARI, B.; HUSKEY, D. Convenio de
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70. DRAGO, G.; AQUINO, L.; SOLARI, B.; SOUTO, A.;
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72. GARCIA, W.; PAZOS, J. M. Actividad dt' catalizador~s
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73. PAZOS,J.M.;GONZALEZ,J.C.;GARCIA, W.EVQluaciÓlld~
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74. SALAZAR, J. A.; GONZALEZ J. C.; RODRIGUEZ. E.;
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78. BADRA. C.; RODRIGUEZ. E.; CABRERA. L. Manejo de las
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81. MORALES, A.; SAL~ZAR. J. A.; AGUDELO. M. M.;
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95. GALIASSO, R.; SALAZAR, J. A.; MORALES, A.;
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96. GALIASSO, R.; SALAZAR, J. A.; HUSKEY, D.; MORALES,
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in the Presence of Steam Ammonia and HYdrogen, Paten! ~
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97. CAPRIOU, L.; KUM,H.; NUÑEZ. A. Desa"ollode un esquema
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98. KUM, H.; NUÑEZ, A.Desarrollode un esquemade conversión
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100. ZERPA, C.; DI MARCO, M. P.; GALIASSO, R.; GARCIA, A.;
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Process for the Conversion of Heavy Hydrocarbon Feedstock
Characterized by High Molecular Weight, Low Reactivity and
High Metal Contento Patent N9 4.62634. 1987.
REV. TEC.INTEVEP 10(1): 47-61. ENERO -JUNIO 1990/61