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

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

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

 - , -~ GALIASSO ".
c. ,-" i I .. C I .coi ,!o¡ .,
. Upgradingprocf'sses

- Zone of separation of catalysts from liquid and gaseous processes.Since the HDH processis dealt with in another
products. When a catalyst remains in the reactor, the only article ofthis issue[2). it will only be mentionedbriefly.
separation that has to be made, by conventional means, is that
of gases (non-condensable) from liquids, an operation which 2. CHARACTERIZATION AND REACflVITY
does not require any special equipment. But when the catalyst OF EXTRAHEA VY CRUDES
leaves the reactor together with the liquid products, they have
to be separated. If their density is not different, the separation The Orinoco Gil Belt' s extraheavy crudesarecharacterized
requires special methods, and developments have to be made. by aspecific gravity higherthan I.aresiduecontent higherthan
- Liquid product purification and separation zone. Insoluble 6Owt %. a metal content higherthan 400ppm. mainly vanadium
materials must be eliminated from liquid products in order to and nickel. and an asphaltene content higher than 12wt %.
seUthem or recycle them into fue reactor. Generally speaking, In 1977. substantial efforts were made with a view to
fue purpose is to limit as much as possible fue formation of developing anaIyticaI techniquesfordeep crude characterization
insoluble materials in the chemical reaction stage SOthat the with the API 60 project. Particularly. techniques for the
separation stageswiU be conventional ones and less expensive separation and characterization of heavy fractions of light
(such as the case of atmospheric and vacuum distiUation). crudes were established and applied. INTEVEP. together with
- Product hydrotreatment zone. The quality of fue products the US DepartmentofEnergy (DOE). beganthe characterization
is adjusted here, and in somecasesthe conversion into distiUable of Cerro Negro crude. The first work made by Sánchez.
products is completed. In fue caseof distiUares,the hydrotreating Murgia. Lubkowitz el al. [3] presentedthe main characteristics
technology requires fewer developrnents than in the case of of these heavy materials. A strategy was designed for the
residues (total or deasphalted); if there are metals, special analysis of feedstocks and conversion products. After a
processes are required. distillation stageof up to 700°C. a preparatory chromatography
The five process schemes studied from 1977 were as with exchange ionic columns is carried out to obtain acid
foUows: fractions. bases. and hydrocarbons. Various fractions with a
1- Elimination of most of the metals through deasphalting content of nitrogen. acids and phenols can be obtained from
to proceed to demetaUization and hydrotreatment of the acids through a silica preparatory chromatography. The second
deasphaltedproduct (DHDS process).A synthetic crude family (bases) can also be separated into basic compounds of
and asphalt are produced. different sizes and structures with the sametype of column and
2- Treatment of complete residue or fue crude through a group of solvents. The third family is separatedjoto aromatics
dernetaUization stage, foUowed by a hydrotreating of different sizes with a silica column and a special stationary
stage in order to produce distiUates and non-con verted phase. The Nipper 160 report deepensthe study of the routine
residual (HH process). distillation and characterization stage. Nipper 161 develops
3- Treatment of the residue or the complete crude in two the improvements made in the separation and identification of
thermal stagesfor their hydroconversion, foUowed by a aromatics. Reports 322. 323 and 324 complement the
product purification stage and hydrotreatment of characterization ofbasic acid compoundsand aromatics. Report
distiUates (SHH process). DistiUates and a residual are 325 anaIyzes sulfur distribution.
produced. Cerro Negro crude contains 18.2% of acids. 17.6 % of
4- Treatment ofthe crude or its residual in a hydrocracking bases. and 14.7wt % of hydrocarbons. The latter contains
stage, foUowed by a catalyst separation stage, and cycloparaffins. Most of the aromatics are neutral poI yaromatic
hydrotreatrnent of distiUates (HDH process). Non- compounds. whose molecular weight grows continuously
converted material mayor may not be recycled. toward heavier fractions. This is the case of sulfur. whose
5- Residual treatment in a first dernetaUization stage, distribution is discontinuous. with a minimum in the diesel
foUowed by a thermal hydroconversion stage, and fraction. It is important to point out the high proportion of
afterwards, through hydrocracking, distiUates, wbich naphthenic acids in the heavy gasoil [4].
are hydrotreated, and a residual (HR process) are AIl characterization technologies dealt with distillates. but
produced. they gave no information on most of the crude. that is. the
Particular developments were made in each scheme, residue. That is why a study was initiated on heavy crude
especiaUy catalysts and reactors. AU the zones are analyzed separations through the SARA method and high pressure
below, starting with the feedstocks, foUowed by conversion liquid chromatography [5).
catalysts and reactors, and finaUy the purification of products In terms ofthe process.the study ofthe molecules containing
and the hydrotreabnent of distiUates. Finally, a summary is vanadium and nickel is of paramount importance to understand
made of the developrnents of DHDS, HH, SHH, and HR hydrocracking and demetallization reaction mechani~m~. For

48/REV.11!C. INTEVEP 10(1): 47.61. ENERO - JUNIO 1990

 this reason, in 1980 research was initiated on the thennal that in the crude the aromaticity determined through RMN
perfonnance of asphaltenes and resins. which comprise the changes from 0.44 to 0.32 and to 0.21 when going from the
part of the residue that contains mainly metals. Both are asphaltene to the resin and to the oil. Likewise. the number of
associations of complex molecules (extended porphyrins- aromatics per molecule is 16. 6 and 2; V IN i ratio is 4. 6 and 2;
porphyrins and quelates). which are classified by precipitation the molecular weight (determined through osmometry) is
with paraffinic solvents and by solubility in aromatic solvents. 2.(xx); 1.250 and 1.(xx); respectively. After having convened
Asphaltene micelles stabilize through solvolysis; their size 50% ofthe residue. the propenies ofthe products change in the
depends on the concentration. temperature and physico- presenceof a larger number of aromatics per molecule ( 12-10-
chemical interaction ofthe molecules. Generally speaking. the 3). less molecular weight (1.300-800 and 750) and a higher
difference between resins and asphaltenes is given by the C/H ratio in the asphaltenes.resins and oil. In the asphaltenes.
association-polymerization degree of the basic molecules there is 70% of insoluble material in toluene and in carbon
already rnentioned. through alkyl-naphthene bridges. according disulfide with coke characteristics. These results explained the
tooneofthe more widely accepted hypotheses in the literature. decomposition stages of asphaltenes and resins. and product
When they are heated, these materials undergo important poIyrnerization reactions.aswell asthe control of thesereactions
transfonnations. by the additives.
Cotte and Calderón (6 J studied the perfonnance of the Galiasso and Blanco [IOJ conducted similar studies with
asphaltenes from various crudes at different temperatures. in hydrodemetallization catalysts. It was demonstrated that the
the absence of gaseous flow. They discovered that the first propenies of resins and asphaltenes change in a different
stage corresponds to a loss of solubility of the aromatics manner from that mentioned earlier. to form less aromatic
(100°C) due to infernal arrangements and polymerization; products with a lower C/H ratio. a molecular weight between
later. decomposition sets in andoat 350-450°C. there is maxi- 1.200 and 900 um. and total solubility in aromatic solvents.
mum loss of light compounds. depending on the temperature, These basic studies on the transformation of heavy molecules
the origin and heating speed. Insoluble products in carbon made it possible to design models on the reactivity and
sulfide are fonned in this stage. when they become carboides deactivation speedofheterogeneous catalysts. The latter. which
and coke. As temperatureincreases.asphaltenesaretransformed is related to the homogeneous or heterogeneousdeposition of
into cok e through thennal cracking and polymerization. the metal in the panicle, is associa&edwith the size-diffusivity
Blanco and Galiasso (7J studied the heating of resins. of the molecule in the pore.
asphaltenes. and oil of the residue 500° C+ of Jobo crude. Sánchez and Galiasso (11 J showed how the asphaltene or
together and separately. They demonstrated that this the resin size affects the penetration of the catalyst' s pore~ and
performance is valid in resins and asphaltenes; however. when its deactivation. due to vanadium deposition along the pore.
they are combined. intensity changes. and this happens at More detailed studies on the characteristics and the reactivity
different ternperatures for each of them. Likewise. the of the various types of asphaltenesand resins were conducted
performance is different depending on whether they are by Carbognani. García. Izquierdo. Di Marco. Pérez. Rengel
combined or in the residue. The stability ofthe residuesand the and Sánchez (12J. who pointed out that the residue percentage.
cake formation at different heating speedswere also studied in the gravity. the molecular weight. the content of metals. sulfur
order to optimize the manner in which these material s are and Conradson carbon cannot be usedas independentpropenies
carried to chemical reaction temperature (thermal or catalytic). to establish the reactivity of the residue. A more detailed study
In addition, their performance in the presence of nitrogen, with Morichal. Apure and Barinas residues made it possible to
hydrogen and solids was determined. prove that reactivity is associated with a combination of
Similarly, Quintero. Larrauri and Galiasso (8) analyzed the propenies. such as age, distribution of molecule sizes. the
hydrocracking reaction in the presenceof inert solids. catalysts distribution of sulfur and metals in the asphaltenes and the
and hydrogen. and they found that the presence of a catalyst C/H ratio. even though so far there is no known correlation
modifies the asphaltene conversion. reduces gas fonnation, between these properties and the reactivity 113]. A more
and increa.sesthe fonnation ofheavy gasoil and diesel. It was detailed study is being conducled with conversion products in
demonstrated that total conversion does not depend much on arder lo predicl their reactivity.
the presence of a catalyst at a pressure of 100 atm and On Ihe other hand. during thedevelopmenl ofthe processes.
temperatures higher than 400°C. It was stated that the primary basic information wa.'iobtained on the characteristics of reaction
cracking stage is not catalytic but the second and third ones are. products as a function of opercttion condition~ and of differenl
Gal iasso el al. 19)studied the residue of Cerro Negro crude types of cataly~ts. which allow~ the analy~is of the
and the Products from thennal and catalytic conversion in the hydrogenation-hydrocracking-denitrogenation and hydro-
presenceof additives and homogeneouscatalysts, It wa.,;found 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 these feedstocks in long tests, made it possible to make the
necessary changes in the fonnulation.
The development in the afea of catalysts was simultaneous
to the study of the characterization of heavy crudes. This Demelallizalion Synlhelic Calalysls INT -RI and INT -R7
development was initiated in three main afeas: synthetic
catalysts. natural heterogeneous catalysts. and homogeneous Catalyst INT -R 1 was developed for the demetallization of
catalysts. The first one could have been designed according to residues (HH process) and deasphalted (HDS process); this
the requirements. but they were expensive andodue to their was prepared with a Ketjen alumina support through
deactivation. it was necessary to consider the possibility of impregnation with molybdenum and nickel. This catalyst is a
regenerating them. The second one could have been produced result of a long process of selection of supports to adjust the
with elernentsthat abound in nature. through simple procedures. porous distribution to a binodal system with pare diameters
but with limited important Stnlctural changes. and since their between 30 and 300 A.
preparation was economical. it was not necessaryto regenerate The demetallization of feedstocks with a different active
them. phasecomposition was studied through porphyrin adsorption,
In 1977. a large proportion of research efforts in the world whose molecules contain vanadium and nickel, in arder to
was centered on the development of demetallization synthetic detennine the necessary composition and dispersion [14].
heterogeneous catalysts for commercial units and for most Likewise, the preparation was analyzed by making adsorption
developing processes.It had beenestablished that the selection isothenns of the precursor (Mo, Ni) with different salts,
of an adequate pare size made it possible to penetrate heavy concentrations and acid or basic media, and checking its
molecules inside the pares, where they reacted in active sites. dispersion by means ofphotoelectron spectroscopy (XPS). In
giving a good vanadium and nickel dispersion, along the radius so doing, it was detennined that it was possible to obtain
of the particle. These metals were deposited inside the particles. maximum activity if the molar ratio Mo/(A 1) = 5 to 8 andNi/
~
~
in active sites or nearby, and deactivated the catalyst with a (AI)= 1 to5.
decrease of the number of such sites, and of the effective The first results were obtained by Morales el al. in 1978
I diffusivity of the reactives due to the reduction of pare size. [ 15], and its application was demonstrated in pilot plant tests of
Taking this aspect into account. there were two application seven months duration, up to a metal accumulation of70wt %.
manners: flrst of all. as small-size particles that could operate [16-17]. This catalyst is being sold today at intemationallevel.
in a fixed bed; nevertheless, the catalyst had to be changed after Likewise, a variation of this catalyst was prepared.
~, Phosphorus was added to its fonnulation in arder to increase
, a certain amount of vanadium accumulation. A variant of this
,
. altemative consisted in continuously rernoving the catalyst the mechanical strength and removal capacity of Conradson
~ from the reactor operating in a mobile bed or ebullated bed. carbon and hydroconversion (INT-R2) [18].
The second type of application was as a finely divided or Thedevelopment afilie secondcatalyst (INT -R7) started in
homogeneous catalyst. which was handled in suspension. and 1980,associatedwith the HR process.The support was obtained
which could be used in transported red reactors or in with INTEVEP's technology. The product obtained was an
suspensions. The use of hornogeneouscatalysts allowed for a alumina support with a binodal pare distribution and with a
higher contact efficiency at the expense of considerable special adsorptioncapacity [19-20]. Ittumed out that vanadium
separation difficulties. The catalyst design is associated with can have basic absorption sites in the support, so that not all the
the technology that is being used, and is influenced by the vanadium will deposit on the active metal phase, and the
functioning of such technology. catalyst will have a longer liCeoThe hydrogenation active phase
It was also known that molybdenum, cobaltonickel andoto is a molybdenum and nickel sulfide, which was optimized for
~
~ a certain extent, vanadium in the sulfide statecould dernetallize residue of Bachaquero and Tía Juanacrudes, whose reactivity
~ the residues. but no appropriate hydrotreatment and is different from that of the Orinoco Oil Belt 's crudes, in which
1 hydrocracking catalysts were known. the reactivity of the INT -R 1 is lower. The optimum pare
i
t INTEVEP started the development of hydrotreatment and distribution is still binodal. but the macropores have a wider
¡ hydrocracking catalysts by selecting and activating natural diameter to allow for the accessof vanadium molecules. The
1: material available in Venezuela. Likewise. synthetic supports optimum metal dispersion is now Mo/(A 1) =4.5-7.5 Ni/(A 1)=
were prepared and obtained from cornmercial manufacturers 3-6. and the acidity distribution is such that it has a higher
(AKZO, CY ANAMID. FIL TROL). which were impregnated numberof intennediate acidity sites than the INT -R 1measured
with active metals. Later. their optimization was started so as by arnoniadesorption. Thiscatalyst was studied in longduration
to apply them to specific technologies. Kinetic studies for tests with residue 500°C+ of Bachaquero Crude, and
particular feedstocks and the analysis of the peñorrnance of demonstrated that it had good stability.

~/REV. TEC.INTEVEP 10(1): 47-61. ENERO-JUNIO 1990

 G~
~"j,' 1"
'" Up,radin, proc~.s.s~.s "

Thanks to basic studies aimed at understanding the of heavy feedstocks. Both are used after the feedstock is
interaction among organometallic compounds of (he crude and partially demetallized with the synthetic catalysts mentioned
the catalysts. it wasdemonstrated [14-21] that porphyrins were above. This is because vanadium prefers highly acid sites.
adsorbed preferably in the molybdenum sulfides. through the which are necessaryforconversion. a situation that deactivates
interaction of vanadium with these sulfides. Additionally. it them rapidly. The initial studies with these material s were
was demonstrated that neither the cobalt nor the nickel played made by Arias ~I al. [30-31]. who worted with bauxites. iron
any important role in demetal1ization reactions. The importance and nickel-containing laterites. These materials were activated
of diffusional controls in the reaction was also analyzed. in such a way as to generate the best pare distribution possible
Galiasso and Morales [22] analyzed the diffusion of and an adequate suñace composition.
porphyrinic and non-porphyrinic species to determine their Arias and Rivas [32]. on the one bandoand Arias. Kum and
effective diffusion coefficient. GonzáJez and Galiasso [23] Galiasso [33]. on the other. initiated the development and the
modeled the activity and selectivity results in demetallization catalytic test of catalyst INTBHC-l. incorporating different
vs. desulfurization of residues by applying the concept of a active materials. which were impregnated to fonn the active
structure interconnected in a probabilistic manner for (he phase together with the components present on the suñace of
diffusion path in the pares. and established the importance of the Venezuelan baux ileso This study was continued by Garcfa
the size distribution of as'phaheneparticles in the activity and ~tal. [34]. whoadded phosphorus tothecatalystandoptimized
selectivity. the preparation method. In particular. they produced spheres
Likewise. (he aging of (he catalyst was analyzed by using and extruded particles through a special treatment which
deasphalted feedstocks of Jobo crude [24] and of complete changed the mesopore distribution. while retaining high
crudes [25-26]. and (he effect of cake and vanadium in the mechanical strength. The good Ktivity of these catalysts
i., deactivation was demonstrated by a loss of effective diffusivity pointed to the possibility of hydrocracking heavy crudes as a
and intrinsic activity. Particularly. it was established that the first or a second stage.
three catalyst deactivation periods and (he selectivity depended Kum ~I al. [35] studied the demetallization of Jobo crude.
.1..
on the parameters for a given porous structure. The catalyst was assessedon fixed and ebullated red at bench
Galiasso eral. [27] studied the surface ofthe fourcatalysts scale for its application in the HR or HH process. respectively.
used. and the activity as whole particles and as powder in arder CataIyst INTBHC-l was also tested in the pilar plant of
to clarify separately the effects of diffusion and intrinsic Lummus in New Jersey. U.S.A. [36] on an ebullated red with
activity ofthecatalyst with theJoboresidue. It wasdemonstrated Cerro Negro residue and crude. The results were successful.
that the deactivated catalyst. operating as whole particles. has dernonstnting the high activity and stability of this catalyst.
a 20% of initial molybdenum on the surface. while its activity The second catalyst.INTLHC-l. was developed by Garcfa
is only 10% of (he initial activity; nevertheless. after being ~I al. [37] with a Venezuelan nickel-containing laterite which
grinded. it still has 50% of the initial activity. which indicates was properly activated. impregnated with molybdenum and
that the plugging of the structure in the pare interconnection extruded in various proponions with a macroporous alumina.
zones is the causeof the premature deactivation. The difference This catalyst proved to have more hydrocracking activity than
in reactivity causeshigh reactivity molecules to dernetallize by commercial catalysts [351. high macroporosity. a layer
the mouth of the pares. and low reactivity ones to diffuse in the structure and an adequate substitution of magnesium for other
pares. This explained (he need to use graduated beds of ions. which makes it possible to create acidity coming from
catalysts with different pare distribution and activity in arder metals. necessary for asphaltene hydrocracking.
to treat those types of molecule with the objective of obtaining These twonatural catalysts (INTBHC-I and LHC-I) were
an appropriate life-span for the catalyst system. characterizedby RamírezandGalarraga [38]. whodetennined
On the other hand. Agudelo et al. [28] demonstrated that the suñace composition. metal dispersion. acidity and the
elements Mo. Ni. Cr. and V are the most active ones for crude valence state of the active elements.
dernetallization. Finally. Quintero and Galiasso [29] developed The catalysts already used in the reaction were
a procedure for catalyst regeneration through cake oxidation characterized by Galiasso t't al. [391. who realized that the
and treatrnent with a selective solventowhich makes it possible total acidity had decreased to a feeble acidity. attributed to the
to remove vanadium from the catalyst used. cake. and a medium acidity. attributed to the metal sulfides.
Fony percent ofthe sulfides had been eliminated by coverage.
Catalysts /NT8HC-I,/NTLHC-/ with a 60% reduction of the mesopores and almost all the
micropores elimination. The cok e produces the main
These natural catalysts were developed for the deactivation (20 wt %). and vanadium to a lower degree
hydrodesu Ifurization. hydrodemetallization and hydrocracking (7 wt %).

REV.1K.INTEVEP 1011):47-61. ENERO-JUNIO I~/~I

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I

GALIASSO

Upgrading prOC~SMI

catalyst INT -R l. Plugging occunoedwhen conversion severity

Homop,eneousHydrocracking Calalysl
is high in the hydrothermal stage. since there occurs the
This catalyst is used in bubbling column-type reactors. The deposition of insoluble material in benzene. which rapidly
catalyst goes through the reactor to contact the hydrocarbon deactivates the catalyst. A stage of low conversion hydro-
and the hydrogen. Afterreacting, the catalyst must be separated visbreaking is only possible when one wants to operate with
from hydrocarron products through special means. Since the fixed red after this stage [44). In this case. molybdenum
active metal is in a homogeneous phase, there can be close remains on the catalyst in an inactive manner. for it does not
contact with the hydrocarbon. This catalyst was used in the change the catalyst activity.
SHH process in the presenceof water steamand hydrogen. The
reaction was called hydroconversion. The catalyst was obtained Hydrogen Donor Additives
by Morales [40] and used in high pressure and medium Research was conducted in the afea of hydrogen donor
temperature batch equipmenL Morales studied the use of additives. It was determined that. at high temperature and
different compounds of molybdenum, and demonstrated that pressures. high molecular naphthenic molecules tend to
variable amounts, between 500 and 1,500 ppm, substantially dehydrogenate to free hydrogen in the liquid phase. which can
decreased the coke and gases, and increased the amount of be used in hydrocracking reactions. INTEVEP carried out its
distillates, similar to that producing heterogeneous catalysts. first study together with Chem System (U.S.A.) in 1978. Cotte
Later, Toms and Salazar [41] rnade a comparative study of [45) participated in the development of a conversion process
hydroconversion catalysts, and studied the effect of deuterated for Boscan crude using tetraline as the donating agent. Even
water; it was detennined that when deuterated water was used, though original results were promising. for it was proved that
it would participate in the reaction, because hydrogen was the additive had a positive effect. this line of research was not
replaced for deuterium in the light hydrocarbons produced. followed up. The second study was carried out together with
Additionally, it was demonstrated that molybdenum was the the German company Lurgi. beginning in 1980 within the
best additive. Galiasso et al. [42] proved that regardless of the frarnework of aV enezuelan-Germanagreement. Studies were
initial metal compound, at the reaction temperature, it
made of Cerro Negro. Jobo and Cogollar crudes. using light
decomposes to become part of an asphaltene micelle which
gasoil cut asadonating agent.which hydrogenatedsubstantially
contains Molybdenum. Thus, when the reaction products are at a high pressure stage (150 atm) to transform aromatics into
deasphalted, there is a compound of sulfurized molybdenum in naphthenes. During the hydroconversion stage and in the
materials insoluble in benzene, where the V IC ratio is higher, presenceof gaseoushydrogen. the latter were dehydrogenated
and N/C and SIC ratios are smaller than that of the original
joto aromatics. The presenceof this hydrogenatedhydrocarbon
asphaltene. Molybdenum was not found in the product soluble cut favored conversion and reduced the Conradson carbon in
in benzene (asphaltene). The presenceof water accentuatesthe the non-converted residue [46]. This processwas lessinteresting
perfonnance, and the RMN analysis indicates that there are than others that were being developed; as a consequence. the
deuterated molecules in the asphaltene, and a smaller content
research was stopped.
of sulfur in the total molecule. X-ray diffraction studies
conducted in an electronic microscope indicate that there is 4. REACfORS
surface molybdenum in these insoluble particles, whose size is
close to the micron, and which has a turbostatic structure. The The cataIysts and additives described above are used in
work done by Núñez and Galiasso [43] demonstrated that high pressure and temperature reactors. In general. they are
asphaltene hydrocracking occurs with fonnation of resins, adiabatic. and since the hydrocracking reaction is exothermal.
which later crack to produce distillates. The depolymerization they haveaggregatesofcold hydrogen tocontrol the temperature
mechanism seems to be associated with the presence of within desired limits. One or various series reactors can be
molybdenum adsorbed on asphaltene. used. with or without intermediate separation. and the
The same concept was studied in an effort to deposit fundamental variants in the design are associated with the
molybdenum on a support during the reaction, in order to catalyst and the tluid dynamics.
replace that which is eliminated in the demetallized catalyst, Four basic reactor concepts were considered during the
due to the reaction of vanadium with the feedstock. Several 1977-1983 periodo which defined the four process schemes
studies were carried out which brought about no results due to already mentioned:
aheterogeneous molybdenum deposition in the particle, which 1) Fixed bed catalyst reactor (the mobile red is only a
is useless from the technological point of view. Likewise. variant of the same scheme). This type of reactor is
studies were made of hydroconversion with molybdenum and widely known. (Fig. loa). The particle diameter of the
steam water. prior to a fixed red hydrodemetallization with catalyst is between 1 and 1.5 mm.

S2/REV. TEC.INTEVEP 10(1):47-61. . JUNIOI~

,~-' J
. GALIASSO
Unrading proce.rle$

industrial level could be reproduced on a small scale [47).

2) Ebullated bed reactor (Fig. I-b). In this reactor the solid
is suspended and perfectly agitated. thanks to the Likewise, the manner of removing the catalyst from the reactor
dynamic pressureof the liquid coming from the bottom was studied, because when operating with high metal content
and leaving from the top of the reactor. This pressure is crudes, deactivation is very fast and life cycles are shorter than
generated by an internal or external recirculation pump. one year.
The catalyst can be removed from the bottom of the The technology available to solve this problem consisted in
reactor and added from the top; the particle diameter of using two reactors in parallel, one out of service or working in
the catalyst ranges between 0.5 and l mm. a different stage of life cycle, and another operating with the
Three-phase-bubbling-column-type reactor. in which whole feedstockormostofit(Gulf HDS usesthis system). The
3)
the catalyst is in a powder forro (in suspension). the other possibility is to remove the catalyst in a continuous way.
hydrogen and the liquid enter from the bottom and leave At the time, Shell was developing a bunker type reactor, in
from the top with the sarne salid concentration. The which the catalyst would come down in a discontinuous way,
catalyst is transported thanks to gas dynamic pressure. be added from the top and removed from the bottorn. The liquid
which generates a certain degree of mixture inside. and the hydrogen would be red from the top of the reactor and
affecting the temperature profile and hydrocarbon removed from the bottom. The problems in fuesesystems were
concentrations. ahd the catalyst distribution in the increased investment in the first case,and solid agglomeration
reactor. The salid concentration inside can be higher and bad fluid distribution in the loading zone in the secondcase.
In 1980, INTEVEP started developing a new type of
than in the feedstock [2].
Two-phase-bubbling-type reactor. In this reactor the mobile bed reactor in which the fluid and the hydrogen would
4)
homogeneous additive mixed with the hydrocarbon flow upstream, while the catalyst would be added from the top
enters from the bottom together with the hydrogen. and and removed from the bottom. This new system was developed
leaves from the topo Again. there rnay be a profile of by Belandria. Galiasso and Núñez [48). It has the advantage
concentrations and temperatures depending on the that the solid does not agglomerate because the fluid dynamic
pressure aIlows to maintain a certain degreeof expansion of the
selected tluid dynamics (Fig. l-c).
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.
1. "'«0 KO
For their part, Di Marco and Cabrera [51) confirmed the
existenceof a higher content of liquid in the reactor with this new
Fig. l. Types of reKtors.
type of fIow, which produced changes in reaction of
demetallization, desulfurization, hydrocracking, removal of
Fixed or Mobi/~ B~d R~actors asphaltenesand Conradson caroon. Di Marco determined the
intluence of gas speedon the volume of the liquid accumulated
As has already been stated. the application ofthis reactor is in the reactor. Finally, Belandria and Mayorga [52) from the
widely known in the areaofhydrocracking and demetallization. UniversidOOdelos Andesdeterminedtheparametersthat intluence
The studies carried out were intended. first of all. to explain the the unloading of the catalyst by using a cold modelo They
laboratory reactor fluid dynamics so that their conditions al 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 size as a function of the gas linear velocity in the reactor. To
that end. they used model molecules (air-kerosene) and tracers
This type of reactor was developed by the companies HRI, in a cold model with one or various gasdistribution plates. This
City Service and Lurnmus, which havebuilt severalcornmercial is important for the contact between the homogeneouscatalyst.
units under the process name of H-Oil and LC Fining. fue water steam and (be hydrogen controls the coke forrnation.
Originally, the idea was to apply this technology with Cotte and Galiasso [57] perforrned fue process tests in a high
INTEVEP's catalysts in the form of spherical or cylindrical pressureand temperature unit. which was designed and built to
particles. The advantage of this system is that the selectivity evaluate the effects of operational variables on the stability
of the reactions and the vanadium deposition in the catalyst can (coke forrnation). It wasdemonstratedthat waterand a minimum
be controlled better than in the fixed bed becausethe catalyst hydrogen-feedstock ratio had a favorable effect on a low coke
is suspended and works at constant temperatures and and rnesophaseforrnation.
concentration. Therefore, the removal and addition of the The works conducted by Salazar and Huskey [58]. which
catalyst is simple, which allows for a constant vanadium were canied out in fue same unit for longer periods. showed
content in the reactor during the operation cycle. that feedstockpreheatingis a critical stage.becausefue forrnation
At INTEVEP, it was necessary to test the catalyst and the of coking precursors regios during vaporization. The study on
process in a bench scale unit. To this end, it was necessary to the hydroconversion reactor was complemented with a
have equipment capable of simulating the industrial reactor. A helicoidal tubular reactor. in which feedstock preheating is
continuous agitated tank-type reactor with a special internal done in a fiírnace. in fue presente of water and a homogeneous
was designed and built, in which the catalyst was suspended. catalyst [58].
The first designs were tested by Baudet [53], who optimized,
in cold equipment, different forms to tluidize the catalyst 5. EXTRACrlON OF ASPHALTENES AND
without fines or dead zones being formed. Later, Caprioli et al. INSOLUBLES BY SOLVENT SEPARAll0N
[54] designed and built a high pressure plant with that reactor. STAGE
Its operability and the reproducibility of the results were
demonstrated for different operation conditions. Caprioli and Due to the fact that asphaltenes and resins constitute a
Galiasso [55] analyzed tluid dynamic problems with chemical problem in the processingofheavy crude residues,the possibility
tracers, and determined transfer constants for hydrogen and a to deasphalt them was anaJyzed to facilitate upgrading. In
model molecule, from the tluid phase to the catalyst. The 1976, even though there was abundant infonnation on the
possibility to improve the internals of the commercial system deasphaJtingprocess with light solvents, propane and butane,
was confirmed. In the higher zone, where the catalyst is little was k-nown about heavy crude processing. The initial
separated from the liquid and the gas, a new detlection plate works were conducted by Aquino el al. [59-61J, who showed
was designed, which could make the separation in a highly that heavy solvents allowed for a selective extraction of
efficient manner, so as to prevent the salid from being dragged asphaJtenesand increased the yield of high metal content
with the liquid to the external recirculation parto In so doing, products (in regios) and Conradson carbono As a consequence,
the liquid drag is also reduced through the gas that leaves from from 1979, INTEVEP developed a deep deasphaIting process
the top of the reactor. in which participated Aquino, Rodríguez, Granados, Solari,
and Krasuk [62-63 J. Their main conhibution wasto demonstrate
Two-Phase-Bubbling-Column-Type Reactor the feasibility of deasphaIting with heavy solvent to produce
solid asphaltenes with a limited particle size, which could be
Two phasestlow upstream in this reactor: hydrocarbon and transported in a suspension fonn. To control the particle size,
hydrogen. lt is characterized by the fact that liquid and gas a tlocculation stage was developed, in which a particle size
contents depend on the hydrocarbon properties and the gas wider than 10 microns was obtained in the separation stage,
velocity. By 1981, when INTEVEP developed the SHH through temperature and residence time. Fig. 2 shows the
hydroconversion process, several studies had already been scheme of this process. A preliminary technical-economic
done in the world on model molecules (airor hydrocarbon), but study for commercial application [64] was initiated, whose
there was little information on its application to heavy crude resuIts made it possible to detennine the feasibility of its
hydroconversion. intemational commercialization [65]. The deep deasphaIting
Studies were initiated on the tluid dynamics, taking into associated with a deasphaIteddemetallization led to the DHDS
account existing knowledge on visbreaking with soaker type process.
reactors (Lummus technology). Thus Barbarrosa, Huskey and Simultaneously, a study was initiated on the possibility of
Galiasso [56] determined the mixing degree and the bubble decreasing resins and asphaItenes prior to the deasphaIting

S4/REV. TEC.INTEVBP 10(1):47-61. ENERO- JUNIO I~

 GALlASSO
" Upgradingpr~s

stage through a hydroconversion process. As for the SHH successfully dernonstratedby Drago el al. [70J. whoconducted
process, Huskey and Aquino [66J demonstrated that, after a tests on a pilot scale and cornmercial scale.
hydroconversion stage, asphalteneswould deasphalt by means
of a heavy solvent and water. The results were promising, for 6. PRODUcr HYDROTREA TMENT
the low resin amount, the presenceof cake microparticles and
of a mesophase facilitated the separation of particles such as Since its beginnings, INTEVEP has been doingimponant
small size solids. Later, the deasphalting prior to visbreaking work in the hydrotreating afea. First of all, experimetal facilities
was evaluated together with the Institut Fran~ais du Pétrole were completed and a study of commercial catalysts for
(IFP). With this institute the "INTEVEP path" was studied, refinery's feedstocks was initiated, with works conducted by
which consisted in a hydroconversion followed by a pentane García and pazos [71-72] and pazos et al. [73]. The best
deasphalting (IFP process), and hydrotreatment of the experimental conditions were established for the kinetic
deasphaIted oil and the distillates with INTEVEP's catalysts evaluation ofthe activity, and studieswere madeof die properties
[67). The results suggestedthat from the technicaI and economic of the catalysts having more influence on the commercial
viewpoint, it was an interesting way for the Orinoco Oil Belt' s application. Later, deactivation and economic. evaluation
heavy crudes [68J. As ~ result, the two companies would concepts were incorporated for the selection of commercial
proceed to commercialize it. 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
Fig. 2. neasphaltingprocessin a solid phase.
crude, which had been produced through delayed coking,
Coker, Veba Combi Cracking processes and simple direct
Another way to optimize deep deasphalting processeswas distillation. It was found that the reactivity in hydrotreating
coking of sol id products. To that end, together with Lurgi and depended on the characteristics and origin of the feedstock.
within the cooperation frarnework with the German government, According to the characteristics of the conversion process, the
studies were made of the feasibility of using LR Coker reactivity of the cut produced ch~ges for cataJysts and
technology with asphaltenesproduced in the IFP's pilot plant cornmercial hydrotreating operation conditions. Rodríguez et
in Solaize, France. The distillates produced with this process al. [77] obtained kinetic expressionsfor die hydrodesulfurization
were hydrotreated at INTEVEP. Aquino and Solar [69] of thesefeedstocks, in which the reaction order and deactivation
demonstrated that the process was feasible and that it was did not depend on the feedstock, because its effect was taken
possible to improve the liquid yield thanks to a 50% solids into account by means of a parameter adjustable in terrns of its
conversion (asphaltene) joto distillates. Lurgi and INTEVEP aromatic contento The other properties of the products were
patented the process scheme. established in terms of operation severity and amount of sulfur
Finally, several studies were carried out topurify, bymeans removed.
of solvents, streams from hydrocracking reactors in arder to With the inforrnation collected, Rodríguez, García and
sell free-of-solid residues (coke and catalyst microparticles) or Badra built data bases which store most of the inforrnation
to recycle non-converted material into the hydrocracking stage. obtained at INTEVEP and Petróleos de Venezuela subsidiaries
The ideas developed in the case of deep deasphalting could be [78]. Likewise, a seriesof correlations was developed between
applied in this case with special equipment to separatethe sol id feedstock quaJity, operation conditions, type of catalyst and
from the non-converted hydrocarbon (residues). This was 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 scheme did not require any change of scale. becauseboth the
programs for hydrotreating vacuum naphtha, diesel and gasoil ebullated bed reactor and the fixed bed reactor had been tested
units were written, which led to the development of a manual at cornrnerciallevel. Operation temperature ranged from 390
on cracked feedstock hydrotreating units (79). This knowledge to 4300 C. and pressure between 130 and 150 alm. Space
allowed Badra el al. (80) to prepare the design bases for the velocity was 0.4-0.7. and hydrogen-feedstock ratio was I.(xx)
HDH process hydrotreating unir. which were used to draw up and 2.(xx) N 1/1.Fig. 3 shows the processschernein which none
the basic engineering. of the stages.apan frorn the reactor, needsany special studies,
Likewise, efforts were made to develop INTEVEP's own since they are conventional as far as hydrocracking operations
hydrotreatment catalysts. From 1981, Morales, Satazar, ~coocemed.
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- I
I 1
--
based active phase. Lo-
I - -- - - _.~~~!!'~\1 \ 1
1 :
Galiasso el aJo(821 summarized the main mass and surface
characteristics of commercial catalysts, and demonstrated that r---'
there was no direct con'elation between a particular property Fig. 3 HH PnM:essScIIeme.
and the activity or selectivity in desulfurization and
denitrogenation. They also demonstrated that a catalyst whose The results suggested that from an 80 API virgin Cerro
weight has increased by 6-9% with cake during the first days Negro crude a good quality synthetic crude could be obtained
and then operates for several years, has surface properties with variable API gravily between 27 and 34. depending on the
different from those of fresh catalysts. This same aspect was severity. containing less than 1% of sulfur and 50 ppm of
analyzed by Galias~ 1831,who studied several commercial vanadium, the residues conversion being 5W C+ between 80
catalysts which have worked fordifferent periods in industrial and 85 wl %. The prodUCIslate showed a formal ion of 10% of
Unil'i. The acidity reduction and accessible metal content in gasoline. 25% of diesel. 40% of vacumm gasoil. and 25% of
these catalysts were demonstrated. The acidity of original residual volume; this distribution corresponds lo the mínimum
commercial catalysts was sudied by Ayerbe el al. (841 and conversion. If increa.'ied.by recycle or notogasoline produclion
Gajardo el al. 1851,who confirmed that a proper balance of would increase.
acidity and metal dispersion can produce a catalyst with an The process wa.~tesled at bench scale wilh one-month long
adequate activity in conversion and desulfurization. Morales tests for lhe hydrocracking stage. and one-month for lhe
el al. 186-871 demonstrated that phosphorus control s the demetallization stage. Nevenheless. lhe laner stage had been
catalyst'!i acidity and metal di!ipersion. lesled for seven monlh~ wilh a non-hydrocracked residue. The
On the other hand, Martínez el al. (881developed a catalyst hydrocracking stage was alS() lested in Lummus 3 bpd pilol
for moderate hydrocracking a.1ipart of the development of the plant with INTEVEP'~ catalyst 1901. During the process
conversion technology for ga.'ioil~ in diesel. Prada. Romero development. new element~ were generated ~uch a.~catalyst
and Muñoz made another highly hydrogenated hydrocracking and reactor array wilh or wilhout recycle.
cataly~t: INTHHC-I 1891, which make~ it po!i~ible to treat
conver!iion product~ by !iaturating the aromatic~ and reducing Dt'asphallinx and HydrlJdt'.\"u/furi:alinn PrlH't'.\".\"
(DHDSJ
nitrogen and ~ulfur to minimum value~.
Thi~ processis ba~d on a deepcrude or re~iduedea.~phalling
7. PROCESSES TO UPGRADE HEA VY ~Iage followed by hydrotrealmenl of the dea...pi1altedoil.
CRUDES Dea~phalting i~ done with heavy !iOlvenl~ (C".). and Ihe
a~phallene~ separation is carried out in a !iOlid phase in
HydrrJdemelCJllizCJlirln
CJndHydrr/("'CJ('kin.l,'
Prr/('e,\',\'(HH) accordance wilh the pruce~s~hown in Fig. 2. Once the ~olvent
is recovered. Ihe dea~phalled product obtained from the
Thi!i proce!i!icon!ii!it!i ba!iically()ftwo !itage!iwith orwith()U\ cenlrifugal ~"Iing tank is treated in two ~tages.()f1eof which
recycle()fnon-convened produc\!i: unebullated hydrocrucking deal~ wilh the demetal I i.,.ationand the other, which is in ~erie~.
()rIc. which u!ie!icataIY!i\MoP/bauxi\e(INTBHC.1 ).undam)\her with Ihe de~ulfuri.,.alion. From an Ho API Cerro Negro heavy
in a fixed hed with cataIY!i\ NiM(~AI (INT -R 1). Their pnx.'C!i!i crude 12.4'~, of ga.'i()line. J l. 9~, of diesel. 2H~, of vacuum

~ I REV Tf'.(' INTEVF.P 111I I r 47-6' EN!"") , JUNIO ..,...

 GALIASSO

UpgrQdin.~ proc't'sst's

gasoil, and 11.6% of residue volume are obtained. The yield of together with distillated products in a conventional
asphalt is 13.5 wt % of feedstock. The total product has 210 hydrotreatment stage. or recycled into the second
API, 0.65 wt % ofsulfur. 15 ppm ofmetals and less than 1 wt hydroconversion reactor. This reactor usesup to 10% of water
% of asphaltenes. Deep deasphalted pressure ranges between with the feedstock and 500-1(XX) ppm of a molybdenum
4 and 15 bar, temperature between 20 and 1500C, and solvent/ additive. This additive. as well as most of the vanadium. is
feedstock ratio between 4/1 and 9/1. Hydrotreatment is done recovered from the solid precipitate obtained in the purification
underpressure of approximately 100atm, variable temperatures stage (solid combustion and ashes extraction). Fig. 5 shows
between 375 and 4300 C. and LHSV between 0.4 and 0.7 h-l. the process scheme. The operation temperature of the first
Hydrogen/feedstock ratio is I,OOONI/I. Thecatalystofthefirst reactor is variable. between 400 and 4600 C. the operation
stageis INT -R 1and thatofthe secondstageis a HDS commercial pressure is between 130 and 150 atm. and the residence time
catalyst. The deasphalted product is hydrotreated on a fixed rangesbetween 10and 25 minutes. The secondreactoroperates
bed, this being demonstrated in tests lasting longer than three at a variable temperature. between 400 and 4600 C, and
months. basically under the same pressure as the first reactor. The
A second version of the same process (Fig. 4) uses a separating unir operatesat the sametemperature and under the
preliminary stage ofhydrovisbreaking, which improves yields same pressure as the second reactor, and the liquid phase
and the metal content in the'deasphaltedproducto The treatment purifier at 500 C and under a pressureof 150 atm. The solvent
iscarried out underpressures in theorderof 1OOatm.at variable recovery stage occurs at the same temperature. but under less
temperatures between 400 and 46()° C, and residence time of pressure. The hydrotreatment of each of the units is done
several minutes [91]. Someaspectsofthe processare protected according to the need to adjust the properties of the distillates.
by patents 163,92]. The SHH processproduces. 13.51% of gasoline. 43.56% of
New aspects of this process are associated with deep diesel. 37.50% of heavy gasoil and 5.43 wt % of residue from
deasphalting and demetallization catalysts. 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
co. 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.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 Fig. 5. SHH Prtx:e"" Scheme.

REV TEC INTEVEP 10(1): 47.61. ENERO. JUNKJ 1~/57

 ResidualHydrocrackingProcess(HR) 8. CONCLUSION
From 1983.INTEVEP continued the development of mobile INTEVEP has technology and know-how in the afea of
bed technology able to hydrocrack anddemetallize conventional heavy crudes and residual s conversion. backed with patents and
crude residuals with medium-size investment. This happened experience in the cataIysis afea. and in processes and basic
up until 1987. that is. until the completion of the development engineering to proceed to a commercial application oí its own
at bench scale of a two-stage process which used catalyst catalysts and technology in this afea.
INTR -7 for demetallization purposes in a mobile bed reactor.
and catalyst INTLHC-I for the hydrocracking stage on mobile REFERENCES
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 l. KRASUK, J.; ANDREU, P.; BARROET A, N. Desulphurization
reactivity of asphaltenes(Fig. 6). The first studies were carried and Demetallization ofHeavy Crude and Residues.Acta Cient{jica
out by Caprioli. Kum and Núñez [97J. followed by the studies Venezolana, 25 (2): 45. 1974.
by Kum and Núñez [98J. and arpa. Di Marco and Núñez [99J. 2. DRAGODEG.et.aI. Desarrollo del proceso HDHrM, Rev. Técn.
It was demonstrated that it was possible to obtain variable lntevep, 9 (2): 111-133.1989.
conversions between 50 and 60%. depending on the stability of 3. GIRZZLE, P.; GREEN J. B.; SANCHEZ, V.; MURGIA, E.;
the residual produced under operation pressuresof 137 atm. at LUBKOWrrz, J. Characterization of Cerro Negro Crode. Pan l.
variable temperatures between 370 and 430°C. and residence PhysicaI and ChemicaI Separation. Rev. Técn.lntevep. 2 (1): 13-
21.1981.
times of 0.3 h-l. Bench scale tests for 50 continuous days
4. GREEN, J. B.; GRlZZLE, P. L.; THOMSON, J. S.; SHAY, J.;
demonstrated that the quality of the products and the conversion
DIEHL Y, B. H.; HOMMEY, K. W.; SANCHFZ, V. Analysis o/
could remain stable during the operation cycle [IOOJ.
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.;
SUCRE, L. Estudio comparativo entre HPLC y FID para el
análisis cuantitativo de fracciones pesadasde petróleo. Rev. Técn.
lntevep, 4 (2): 127-132.1984.
6. COTI'E,E.; CALDERON,J. L PyrolysisofBoscanAsphaithenes:
Process Description and Nature of the Products. Rev. Técn.
lntevep, I (2): 97-102. 1981.
7. BLANCO, R.; GALIASSO, R. Estudio termogravimétrico de
resinas y as!altenas de crudo Ce"o Negro. Tia Juana y Zuata.
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,
A. Hydrovisbreaking ofCerro NegroCrode Oíl; Sekiyu Gakkaishi,
Fig.6. ResidualHydrocracking
~s Scheme
(HR). 28 (1): 54-62.1985.
10. GALIASSO, R.; BLANCO, R. Hidrodemetalización de crudo
Jobo. Technical Note project RAX)2RG. INTEVEP, S.A. Los
A technicaVeconomic study was done to compare the HR
Teques, Venezuela, 1982.
process to the Gulf HDS for the conversion of Cerro Negro
11. SANCHEZ, V.; GALIASSO, R. Desactivación de catalizadores
crude [101]; the advantages of the HR process were de desmetalización. In Actas del X Congreso Iberoamericano de
demonstrated from the technical point of view, with a smaller Catálisis, IUT. X Congreso Iberoamericano de Catálisis, Mérida;
reactor volume and catalyst consumption, and from the point 1203-1205. Julio, 6-12,1986.
of view of profitability. This process, as well as the mobile bed 12. CARBOGNANI, L.; GARCIA, C.; IZQUIERDO, A.; DI
reactor, are protected with a patent [48, 102); its novelty is MARCO, M. P.; PEREZ, C.; RENGEL, A.; SANCHEZ, V.
associated with the type of reactor, in the catalysts and in the Correlation between PhysicaJChemical Propenies and Reactivity
thermal conversion intermediate stage which modifies the in Hydroprocessing of Venezuelan Heavy Ends. Preprints ACS
particle size so that hydrocracking conversion can occur. Div. PetoChem., 32 (2): 406-412,1987.

"'REY. TEC.INTEVEP 10(1): 47-61. ENERO. JUNIO 1990

 GALIASSO

,~" c Upgradingprocellel

hidrotratarniento de crudos pesadosy residuos con alto contenido

13. IZQUIERDO, A.; CARBOGNANI, L.; LEON, V.; PARISI, A.
Characterizationof VenezuelanHeavyVacuumResidues,Fuel de vanadio y carbono Conradson. Col(M¡uio Franco Venezolano.
Sci T~chnol, 17: (5-6) 561-570, 1981. Francia. Rueil Malmaison. Apri121. vol. l. 157-1671. 1985.

14. MORALES, A.; GALIASSO, R. Adsorption Mechanismof 28. AGUDELO. M. M.; GAJARDO. P.; GONZALEZ. R. The Role
BoscanPorpiIyrinson MoO3Co)0and CoMo/AI20) Catalysts. ofTransition Metal Sulphides in Hydrotreatment 1.1ron Sulphide
u Catalyst Preprints ACS. Div. Pet. Chem. 27 (3): 712-722.
Fu~/. 61 (1): 13-17,1982.
ISo MORALES, A.; GALIASSO, R.; CARRASQUEL, A. R.; 1982.
SALAZAR, J. A. USA Catalystfor RemovingSulfur andMetal 29. GALIASSO. R.; QUINTERO. N. Extracción de vanadio en
Contaminantsfrom Heavy Crudes and Residues.Pat~nt N'. catalizadores de demetalización. Technical Note project
RPOO2JK.INTEVEP. S.A. Los Teques. 1982.
4642/79. 1987.
16. MORALES, A.; GALIASSO, R.; CARRASQUEL, A. R. 30. ARIAS. B.; LARRAURI. l.; GALlASSO. R. Bauxitas y lateritas.
Catalizadorpara la hidfodesulfuracióne hidrodesmetalización Technical Note project RP002PA. INTEVEP. S.A. Los Teques.
simultáneadecrudospesados.R~v. Tic. /nt~p, 3 (2): 135-140. 1979.
1983. 31. ARIAS. B.; LARRAURI. l.; GALIASSO. R. USA
MORALES, A.; GALIASSO, R.; AGUDELO, M. M.; Hydrotreatment Catalyst. Patent N9 4465784. 1984.
17.
SALAZAR, J. A.; CARRASQUEL, A. R., USA Processfor 32. ARIAS. B.; RIV AS. L. Caracterización de bauxitas. Technical
Demetallizationof Heaf/yCrudeusinga CatalystHaving High Note NV~15 project RPOO2PA.INTEVEP. S.A. Los Teques.
Metal Retention Capacity and Good Stability, Pat~nt 1981.
N' 4579649.1986. 33. ARIAS. B.; KUM. H.; GALIASSO. R. USA Method of Prepar-
MORALES, A.; GALIASSO, R.; AGUDELO, M. M.; ing Hydrocracking Catalysts. Patent N9 4632414. 1986.
18.
SALAZAR, J. A.; CARRASQUEL,A. R. USA Cata1ystHaving 34. GARCIA. l.; GALIASSO. R.; AGUDELO, M. M.; RIV AS. L.;
High Metal RetentionCapacityand Good Stability. Pat~nI N' HURTADO. l.; USA Catalyst and Method of Preparation from
Natural Ocurring Material. Patent N9 47014035. 1987.
4520/28. 1985.
19. ARIAS, B.; MARTINEZ, N.; REYES, E. D~sarrollo d~1 35. KUM. H.; GARCIA. l.; MORALES, A.; CAPRIOLI. L.;
GALIASSO. R.; A YERBE. A. Hidrotratamiento de crudos
catalizador d~ hidrod~smetalización para tratami~nto d~
pesados y ~iduos. Rev. Técn. lntevep, 5 (1): 17-27. 1985.
r~siduo/~s.Technical Report. N° INT-O1487,85. INTEVEP,
S.A. Los Teques,1985. 36. LUMMUS. LC Fining of Atmospheric and Vacuum Cerro Negro
ARIAS, B.; MARTlNEZ, N.; REYES, E. D~sarrollo d~1 Resid Reportfor
S.A. Los Teques.lNTEVEP.
1983. S.A. Reponproject
. 8018. INTEVEP.
20.
catalizador de hidrometa/izaciónpara tratamiento de resi-
duo/es.Tcchnica1Report.NO1NT-O1715,86.INTEVEP,S.A., 37. GARCIA. l.; RIVAS. L.; HURTADO. l.; GALlASSO, R.
Desarrollo del catalizador LEC -1.TechnicalNoteproject8051.
Los Teques,1986.
21. ANDREU, P.;GALIASSO, R.; MORALES, A.; ABRAMS, O.; INTEVEP. S.A. Los Teques. 1986.
KATAN, L.; PANTOJA, L.; SOlO, P.; VERGARA, E. 38. RAMIREZ. M. M.; GALARRAGA, C. Caracterización
Adsorption Mechanismof BoscanPorphyrinson Hydrodeme- fisicoquimica de cata/izadores naturales de hidroconversión de
tallization Catalysts.l.Adsorptionon suppon.In Proceedingsof residuoles. Technical Repon NVINT -O1692.86. INTEVEP. S.A.
th~ 7th /nt~rnationalCongresson Catalysis.KodanshaUd. 7th Los Teques. 1986.
IntemationalCongresson Catalysis,Tokio; pp. 877-886.June 39. GALlASSO. R.; G AR CIA. l.; RAMIREZ. M. M. Caracterización
3O-luly 4. 1980. de catalizadores naturales desactivados en corridas de larga
22. GALIASSO, R.; MORALES, A. Diffusion of Vanadium duración. Technical Note project 8051. INTEVEP. S.A. Los
arganometallic Molecules in Hydrodemetallization Catalysts. TeqUt;.5.1986.
R~v. Tic.lnt~v~p. 3 (1): 59-68. 1983. 40. MORALES. A. Hidroconversión de-f:rudos pesados. Technical
23. GONZALEZ, C.; GALIASSO, R. A Mathematical Modello Repon NV 1NT-8021-O3. INTEVEP, S.A. Los Teques. 1981.
Sludy the Effecl ofPore Structure in Ihe Activity and Selectivily 41. TORRES. E.; SALAZAR, l. A. Estudio comparativo de aditivos
of HDS/HDM Catalysts. Rev. Ticn.lntev~p. 3(1): 3-9. 1983. para sMprimir laformación de coqueen el proceso SHH. Technical
24. GAUASSO, R.; GARCIA. l.; CAPRIOU, L Porphyrim and lXX1 Repon INT -00700.83. INTEVEP, S.A. Los Teques. 1983.
POIphyrlns MoI«:uJes RelM::tionsduring H~lizatjoo of 42. GALIASSO. R.; GAlARDO. P.; SALAZAR. l.A.
Heavy Crudes,PreprintsACS. Div. Pet Chem. 30( 1): 50-61. 1985. Caracterización de precursores del catalizador homogéneo del
25. GALIASSO, R.; BLANCO, R.; GONZALEZ, C.; QUINTERO, proceso SHH. Technical Note project 8021. INTEVEP. S.A. Los
N. Deactivation of Hydrodemelaltizalion Catalyst by Pore Teques. 1982.
Plugging. Fu~/, 62 (7): 817-822.1983. 43. NUÑFZ. A.; GALIASSO. R. Hidrocraqueo de asfalteno en
26. VELAZCO, L.; GALIASSO, R.; OCHOA, O.; ANDREU, P. presencia de agua deulerada y naftenatode molibdeno. Technical
Efecto del tamaño de poros del catalizador en la desactivación de Note NVRPDP/2-O77. project 8021. INTEVEP. S.A. Los Teques.
calalizadores de hidrodemetalización de crudos pesados 1980.
venezolanos. Acta C;~ntlfica V~n~zolana. 32138-143,1981. 44. SALAZAR. l. A. Efecto de la hidroconversión térmica en el
27. GALIASSO, R.; GONZALEZ, C.; CAPRIOLI, L.; GARCIA, l. taponamiento del lecho cata/ltico. Technical Repon NV802 lOS.
l.; AGUDELO, M. M. Envenenamiento de catalizadores de INTEVEP. S.A. Los Teques. Marzo 1983.

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l' Upgradi"g prOC~.f~.f

4S. CO1TE. E. Inlorm~ 2final d~sarrollo d~1 proc~so d~ de desasfaltación profunda con .reparaciÓII~ asfalteno.r enfas~
hidrocroqu~o con Qg~nJ~donant~ d~ hidróg~no. Technical Note .rólida. Technical Repon NV INT-OI122, 84. INTEVEP, S.A.
INrEVEP. S.A. Los Teques. 1981. Los Teques, 1984.
46. LURGI GMH. Donor SoIwnJ Hydrovisbr~aking. Final Note. 63. KRASUK, J.; SOLARI, B., AQUINO, L.; RODRIGUEZ.J. V.;
ConvenioVenezolanoAIemM.Anexolvol.B4. 103-109. 1981. GRANADOS, A. USA Solvent Deasphaiting in Solid Ptwe.
47. GARCIA. W.; PAZOS. l. M. Effect of the Mean P8I1icle Size Pate1ll N9 4572781. 1986.
and Liquid Velocity on the Peñonnance of Trickle Red 64. AQUINO, L.; GRANADOS, A.; SANCHEZ. J.; RAMIREZ. L.
Laboratory ReactOr!. Rt'V. Tkn.lnJ~'~, 3 (1): 47-54.1983. Prediseño ~ IUIQ planta ~ 25.fXXJ bp.sd ~ d~.rasfaltación
48. BELANDRlA. l.; GALIASSO, R.; NUÑEZ. A. D~.sarrollo d~ proftmda COlt.reparaciÓII~ asfalteno.r enfa.re .rólida. Technical
un r~actor "trick/~ bed" con r~tiro d~ catalizador. Technical Repon NV INT -01126, 84. INTEVEP, S.A. Los Teques. 1984.
Note project 80S l. INTEVEP. S.A.. Los Teques. 1984. 65. THE NW KELLOG. T~c/utical and Economical Stlldy of
49. GALIASSO. R.; BELANDRlA. l.; CAPRIOu. L. U.S.A. INTEVEP Of'ep Deaspilalting Proc~.fS.Report Number J 6689,
Method Cm'WidMb8wing Paniculale SoIid fnMn a Higb Preu~ Housroo, Texu. 1986.
Vessel. Pat~nt NW4664762. 1987. 66. HUSKEY, D.; AQUINO, L. De.ras!altación de lo.rproducto.r d~
SO. HIDALGO. R.; GALIASSO, R. E/~cto d~ la dir~cción d~1flujo hidroconwr.riÓII. TechnicaJ Note project 8021.INTEVEP, S.A.
~n rHccion~s d~ hidrotratamienJo en "Qctor~s trifdsicos. Los Tequea. 1983.
Technical Report. N9 1NT-O1243. 8S. INrEVEP. S.A. Los 67. HUSKEY, D.; AQUINO, L. Re.rultMo.r preliminare.r ~ la
Teques. 1985. t'valuaciÓllt«nica de la rllla INTEVEP ~ mejoramiento d~
S l. DI MARCO. M. P.; CABRERA. L. Influencia del s~nJido d~ crudos pe.rado.r. TechnicaJ Report NV INT -O 1618, 86.INTEVEP,
flujo en hidrotratami~nJo de r~siduos. Technical RepoI1. N9 S.A. Los Teques. 1986.
INT -O1887. 88. INTEVEP. S.A. Los Teques. 1988. 68. AQUINO, L.; SOLARI, B.; HUSKEY, D. Convenio de
S2. BELANDRlA.l.; MAYORGA.P.DeSQ"oIlodeun"actor~n cooper8Ción de INTEVEP.ASV AHL; evaluaciÓII de la ruta
lecho móvil con r~tiro d~ catalizador. Final ~ agreement INTEVEP de mejorami~nto~ crudo.rpe.sados.TechnicaJReport
ULA-INTEVEP. project 80S l. INTEVEP. S.A. Los Teques. NV 1NT-O1619, 86.INTEVEP, S.A. Los Teques, 1986.
1989. 69. INTEVEP, S.A. LIlrgi GMH LR Coking of A.rpltaltene -
S3. BAUDET. A. Estudio fluidodinálnico de un reactor de l~cho V~1an Gem1an Agreement. Final Repon U/KYEOS/I.
ebull~nt~ para ~l hidrocroqu~o de crudos ~sados. BS Thesis. Caracas-Frankfun, 1987.
Chemical Engineering. Univ. Metropolitana. Sep. 1982. 70. DRAGO, G.; AQUINO, L.; SOLARI, B.; SOUTO, A.;
54. CAPRIOLI. L.; KUM. H.; GALlASSO. R. D~sarrollo de la GONZALFZ. C.; KRASUK, J. U.S.A. Recycle Uncorvened
etapa de hidrocraqwo en It'CM ~/enJ~ del proceso HH. HydrocrKked Residual to Hydrocr8Cker alter Removal of
Technical Repon. N9 1NT-00707. 83. INTEVEP. S.A. Los Unstable Poly Nuclear Hydrocarbons. Pat~ntN9465590J. 1989.
Teques, 1983. 71. GARClA, W.; PAZOS, J. M. Catalizadores y condicione.r de
SS. CAPRIQLI. L.; GALlASSO. R. FluiJodinámica de "actor~s operación para el hidrotratamiento d~ gasó/eo.r ~ voc(o.
en I~CM ebull~nI~, Technical N- ~ject 8018. INTEVEP. TedU1jcal RepwtNVlNT.ros 17,82INTEVEP ,S.A. LosTeq~,
S.A. Los Teques. 1982. 1982.
56. GALIASSO. R.; HUSKEY. D.; BARBARROSA, l. Simulación 72. GARCIA, W.; PAZOS, J. M. Actividad dt' catalizador~s
fuidodin4mica de un reactor de hidroconvenión a escala conll'rciale.r de hidrod~.rulf.,ración d~ gá.roleo.r d~ ~'ac(o.
IabcM'atorio.Rt'V. Tkn./nlevep. 7 (1): 33-41. 1987. Technical RepwtNV80I302INTEVEP,S.A. LosTeques, 1981.
S7. CO1TE. R.; GALIASSO, R. Pr~liminary T~st 01 73. PAZOS,J.M.;GONZALEZ,J.C.;GARCIA, W.EVQluaciÓlld~
Hydrovisbr~aking lor the Se/~ction of two Crude Oils to be la actividad d~ calalizadon.r de "idrod~.ru/fllración d~ ga.róleos
T~st~d with the Kombi and DSV Processes. Par1 l. Technical d~ voc(o. Technical Repon NV 802201 INTEVEP, S.A. Los
Repon. NV INT ~. 82. INTEVEP. S.A. Los Teques. 1982. Teques. 1982.
SS. SALAZAR. J. A.; HUSKEY. D. Techllical Not~ project SO21. 74. SALAZAR, J. A.; GONZALEZ J. C.; RODRIGUEZ. E.;
Vol. 1, Chapter 3. INTEVEP, S.A. Los Teques, 1982. MORALES, A.; GALIASSO. R. Desarrollo de un test de
S9. AQUINO. L. Desasfaltación d~ crudos ~SQdos venezolanos. desactivación acelerada para Mild Hydrocracking. In Prim~r
BS Thesis Chemistry, Univenidad Central de Venezuela. s~minari() de rf'/inaciÓII de la indllSlria fWlro/~ra nacional. Vol.
~as. Julio 1977. l. T. 3.CORPOVEN. S.A. Primerseminarioderefinación de la
60. AQUINO, L. Desasfaltac;ón d~ tr~s r~s;duos d~ crudos ~sados industria petrolera nacional, Valencia, Venezuela. Noviembre,
usando h~xano como solvenJ~. Technical Note project 8021. 22-24, 1984.
INTEVEP. S.A. Los Teques. 1980. 7S. SALAZAR, J. A.; GONZALEZ. J. C.; RODRIGUEZ. E.
61. AQUINO.L.;PACHANO.J.;RODRIGUfZ.l. V.; KRASUK. D~.rarro/lo d~ un '~Sl d~ d~saclivación ace/~rada para
l. D~asplWllt;ng C~"o N~gro Cogollar andJohoCrIIde Oil with calalizadore" ~ /tidroc-raqwo .ruaw. TechnicaJ Report NVINT -
Propan~ and H~xan~. Technical Rep>n N" 17.KX)2INTEVEP, 01713, 87.INTEVEP, S.A. Los Teques, 1987.
S.A. Los Teques, 1979. 76. DRAGO, G.; GONZALEZ, R.; MATAMOROS. N. Oplimiza-
62. AQUINO. L.; GRANADOS. A.; RODRIGUEZ, J. V. Proc~.r(1 ciÓII de la ftO/Nl d~ hidrmratamit'nl(} ~n ~I proc~.ro HDA.

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Upgrading proct'sst's

TechnicalReponNVINT-02030,88.INTEVEP.S.A.Los Teques, 91. AQUINO, L.; GONZALEZ. F.; PACHANO, J.; PINZON, P.;
1988. RODRIGUEZ, J. l.; SOLARI, B.; ZERPA, C. Proceso DHDS
77. RODRIGUEZ. E.; BADRA. C.; GALIASSO, R. Correlaciones de mejoramiento de crudos pesados TechnicaJ Repon NQINT -
de hidrotratamiento para destilados no convencionales. 00657, 83. INTEVEP, S.A. Los Teques, 1983.
Technical Repon N° 1NT-O194S, 88. INTEVEP, S.A. Los 92. PACHANO, J.; GUITIAN, J.; RODRIGUEZ, O.; KRASUK, J.
Teques. 1988. U.S.A. Multiple Stepped Process for Demetallization and
78. BADRA. C.; RODRIGUEZ. E.; CABRERA. L. Manejo de las Desulfurization ofHeavy Feedstocks. Patent ~ 4752376. 1988.
bases de datos de hidrotratamiento. Primera versión. Manual 93. SALAZAR,J.A.; HUSKEY, D. Resu/tadosjina/esde/proceso
N9 INT -M-<XXX>30.88. INTEVEP. S.A. Los Teques, 1988. SHH. TechnicaJReportNQINT-00662, 83. INTEVEP, S.A. Los
79. BADRA, C.; RODRIGUEZ. E.; LOPEZ. R.; DIAZ, D.; DI Teques, 1983.
MARCO, M. Manual de diseño de unidades ~ hidrotratamiento 94. GALIASSO, R.; SALAZAR, J. A.; HUSKEY, D.
Tome I (to be published).INTEVEP, S.A. Los Teques, 1m. Hydrovisbreaking ofCerro Negro Crode Oil,J. Pet./nst., 28 (2):
80. BADRA, C.; SALAS. R. Especificaciones ~ proceso de una 54-62, 1985.
unidad de hidrotratamiento de gasóleos de vac(o de H DH. Caso 95. GALIASSO, R.; SALAZAR, J. A.; MORALES, A.;
base. El Palito. Technical Report N" INT -O1808.87 .INTEVEP, CARRASQUEL. USA Hydroconversion ofHeavy Crudes with
S.A. Los Teques. 1987. High Metal and AsphaJtene Content in the Presence of Soluble
81. MORALES, A.; SAL~ZAR. J. A.; AGUDELO. M. M.; Metallic Compound and Water. Polen! ~ 4592827. 1986.
MARTlNEZ, N.; CARRASQUEL. A. R. USA Catalyst for 96. GALIASSO, R.; SALAZAR, J. A.; HUSKEY, D.; MORALES,
Hydrocracking of Heavy Vacuum gas Oj)o Patent N' 4600703. A. Canada. Processforthe Conversion of Asphaltene and Resins
1986. in the Presence of Steam Ammonia and HYdrogen, Paten! ~
82. GALIASSO. R.; GARCIA. W.; DE AGUDELO. M. M.; /208590. 1986.
ANDREU, P. Hydrotreatment of Cracked Light Gas Oj), Catal 97. CAPRIOU, L.; KUM,H.; NUÑEZ. A. Desa"ollode un esquema
RevSci Eng. 26 (3-4): 44S-480. 1984. de conversión para e/ procesamiento de cargas residuo/es.
83. GALIASSO. R. Desactivación de catalizadores de parte /. Technical Repon N1IINT-OI066,84. INTEVEP, S.A.
hidrodesulfuración. Plenary Meeting. vrn Encuentro nacional Los Teques, 1984.
de Catálisis IUT Miranda. Marzo loS, 1987. 98. KUM, H.; NUÑEZ, A.Desarrollode un esquemade conversión
84. A YERBE, A.; RAMIREZ, M. M.; MORALES, A. para e/ procesamiento de cargas residuo/es. parte //. Technical
Hidrotratamiento de gasóleos pesados 111. Influencia de la Report N1IINT-O1701, 86.INTEVEP, S.A. Los Teques, 1986.
acidez sobre el hidrocraqueo suave. 2do. Congreso Franco 99. ZERPA, C.; DI MARCO, M.; NUÑEZ, A. Desarrollo de un
Venezolano (Francia),Ruej)Malmaison.124-1~.Abril,1985. esquema de conversión para e/ procesamiento de cargas
8S. GAJARDO, P.; A YERBE. A.; RAMIRFZ, M. M. Correlations residuo/es. TechnicaJ Report N1IINT -O1920,881NTEVEP , S.A.
between surface properties and catalytic activiry of comrnercial Los Teques, 1988.
hyd~ating cataiysts: An XPS and ESR study. In Proceedings 100. ZERPA, C.; DI MARCO, M. P.; GALIASSO, R.; GARCIA, A.;
8th. Int. Congo Catal.. Verlag Chemie. 8th Int. Congo Catal.. ARIAS, B. Hydrodemetallization and Hydroconversion ofTía
Weinhein, Rep. Fed. Germany; 3SI-361. 1984. Juana Heavy Vacuum Residue with Dual Catalysts System.
86. MORALES. A.; RAMIREZ. M. M.; HERNANDEZ, F. Preprints ACS, Div. PetoChern. 32 (2): 464-69. 1987.
Adsorption Mechanism of Phosphorous on Alumina. Applied 101. GONZALEZ. G.; VILERA, M. V.; PARES, G. Desarrollo de
Catalysis.41: 261-271.1988. un esquema de conversión de residlllJ/es. Factibi/idad ticnico-
87. RAMIREZ, M. M.; MORALES, A. Promotor Effect of económica del proceso /NTEVEP HDS. Technical Report NQ
Phosphorous in NiMoP/AIZO) Catalysts on Hydro- INT-01867, 88.INTEVEP, S.A. Los Teques, 1988.
denitrogenation Reactions. In Proceedings IXth International 102. GALIASSO, R.; CAPRIOLI, L.; KUM, H.; GARCIA, J. USA
Congresson Catalysis,Vol. 2. M. J. Phillips y M. Teman (Ed.) Process for the Conversion of Heavy Hydrocarbon Feedstock
IXth Intemational Congress on Catalysis, Calgary; págs. 42-5S. Characterized by High Molecular Weight, Low Reactivity and
Octubre, 24, 1987. High Metal Contento Patent N9 4.62634. 1987.
88. MARTINEZ, N.; VELASQUEZ. J.; REYES. E.; LUJANO. L.;
RODRIGUEZ. E.; SALAZAR. J. A.; CARNA. W.; ZERPA, C.;
GALIASSO, R. Desarrollo de catalizadores ~ hidrocraqueo.
Technical Repon INT -O1217, 84. INTEVEP, S.A. Los Teques,
1984.
89. PRADA, R.; ROMERO, Y.; MUÑOZ, R. Desarrollo del
catalizador INTHHC-2. Technical Report (to be published)
INTEVEP, S.A. Los Teques,1989.
90. GALIASSO. R.; KUM. H.; CAPRIOLI. L. Proceso HH para el
mejoramiento de crudos. Technical Repon N° INT -00660. 83.
INTEVEP, S.A. Los Teques, 1983.

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