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Ind. Eng. Chem. Res. 2005, 44, 9409-9413 9409

Kinetic Model for Moderate Hydrocracking of Heavy Oils


S e r g i o S a n c h e z , t M i g u e l A . R o d r i g u e z , * a n d J o r g e A n c h e yt a * , t *
Instituto Mexican del Petroleo, Eje Central Lerzardecirdenas 152, Mexico, D.F. 07730, Facetted de
Ingenieria, IMAM, Ciudad Universitaria, Mexico D.F. 04510, and Escuela Superior de Ingenieria Quirnica e
Industries Extractives (ESIQIE-1PI\D, UPALM, Zacatenco, Mexico D.F. 07738

In this work, a kinetic model for hydrocracking of heavy oils is proposed. The model includes
five lumps: unconverted resid (538 C+), vacuum gas oil (VGO; 343 -538 C), distillates (204343
C), naphtha (1.13P-204 C), and gases. Kinetic parameters were estimated from the
experimental results obtained in a fixed-bed downflow reactor. The proposed lump kinetic model
fitted the data fbr hydrocracking of Maya heavy crude with a Ni/Mo catalyst at 380 -420 C
reaction temperature, 0.33-1.5 h-_,1 liquid hourly space - velocity, 5000 scf/bbl, and 70 kg/cm 2 .
Only resid cracked to naphtha at 380 C, but all heavier fractions produced some naphtha at
higher temperature. The predicted product composition is in good agreement with experimental
values with an average absolute error of less than 5%. a . y y .,rio
1. Introduction formation, The Mexican Institute of Petroleum (IMP,
Hydrocracking is a process used in the Instituto Mexicano del Petroleo) has developed a process
petroleum refining industry to treat heavy oils, such as for the hydrotreating of heavy petroleum oils, which,
vacuum resid. The main objective of this process is to among several characteristics, operates at moderate
convert heavy molecules into lighter and more valuable reaction conditions and improves the quality of the
products. Various technologies are available for the feed, keeping the conversion level low. 7. 5 These
upgrading of heavy oils., Some processes include suf- conditions change the selectivity of all of the reactions,
ficient large-scale commercial experience to be regarded especially for those of hydrocracking.
as well established, mature processes. There are also There are various kinetic models for the hydrocrack -
processes that are in the early stages of commercial ing of heavy oils reported in the literature and these
application, together with others that have been well were recently summarized elsewhere. 9 Reported models
tested at the demonstration scale.' are commonly developed for severe reaction conditions.
Hydrocracking processes are strongly influenced by Only one modeP makes the differentiation of different
the method of feed introduction, the arrangement of the hydrocracking regimes, namely, low, intermediate, and
catalyst beds, and the mode of operation of the reactors. high hydrocracking, but it does not take into account
Hence, a proper selection and design of reactors are very gas formk-ttion.
important for this. Depending on the nature of the feed, Different approaches have been utilized for kinetic
the reaction is generally carried out infixed-bed, mov- modeling of hydrocracking, varying from the most
ing-bed, or ebullated-bed reactors. Sometimes a combi- common and used lumping technique to more complex
nation of different reactors is preferred. 2 models based on continuous mixtures" or single
The most-known hydrocracking technology is the events:1-2J Govindakanaan and Froment 14 also applied
H-oil process, which is capable of maximizing the the single-event kinetic modeling to the hydrocracking
throughput of heavy fe.olatecks to produce environmen- of vacuum gas oil (VGO) on a Pt zeolite. The authors
tally friendly lighter products. 2 The . H-oil process is recognized that the equations become somewhat more
designed to operate at high severity in an ebul lated - complex because of the multiphase operation of hydro-
bed reactor to produce maximum distillates and mini- crackers. In the case of lumped kinetics, models with
mum fuel oils. 4 The common operating conditions of the only a feW lumps have been proposed in the literature
H-oil process are 170----200 kg/cm 2 pressure, 400-440 (mainly resid, distillates, and naphtha) and other
important lumps, such as VGO (common feed to cata-
C temperature, and 0.1-0.3 h - ' liquid hourly space
lytic cracking units) and gases, are not common in
velocity (LI-ISV). At these conditions, the conversion
hydrocracking lumped models. -
level is higher than 50%. 5
To have a better understanding of the IMP process
The severe hydrocracking conditions cause problems
of coke deposition on the catalyst and sludge formation for the hydrotreating of heavy oils, in this work we
in the product oil, which eventually shorten the life of conducted some experiments in a pilot plant equipped
the catalyst, plug the transfer lines, and deteriorate the with a downflow fixed -bed reactor, with the main
quality of the products. To avoid the problems associ- objective of obtaining information for developing a
kinetic model for the hydrocracking of .heavy oils at
To whom correspondence should be addressed at Instituto moderate reaction conditions. The proposed model,
Mexicano del Petroleo. Fax: (+ 52 -55) 9175 -8429. E-mail:
j a nclleytimp.mx. which is based on the yet acceptable lumping approach,
Instituto Mexican del PetrOleo. can be applied for catalyst screening and basic process
IMAM, Ciudad Universitaria. studies. A inure complex and detailed kinetic model-is
Escuela Superior de Ingenieria Quimica e Industrias under development and will be presented in further
Extractivas (ESIQIE-1PN), UPALM. ated with sediment papers,
10.1021/ie050202+ CCC: $30.25 2005 American Chemical Society
Published on Web 06/15/2005