Hydrotreatmentand Hydrocrackingof Oil Fractions

B. Delmon,G.F. Fromentand P. Grange(Editors)

9 1999ElsevierScienceB.V. All rightsreserved. 377

MODELING OF NATURE AND STRENGTH OF ACID CENTRES IN ULTRASTABLE

ZEOLITES AS A COMPONENT OF HYDROCRACKING CATALYSTS

A.V. Abramova 1, Ye.V. Slivinsky 1, Y.Y. Goldfarb 1, L.Ye. Kitaev 2, A.A. Kubasov z

1 A.V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences,

Leninsky prospect, 29,117912, Moscow, B-71, Russia

2 M.V. Lomonosov Moscow State University, Moscow, Russia

ABSTRACT
The methods of X-ray diffraction, IR-spectroscopy and TPD of ammonia had been used
for investigation of crystal framework structure, nature of surface hydroxyl groups, number and
distribution on strength of ultra stable zeolite Y acid centres and its modification,~: by acid and
alkaline treatment. In the hydrocracking process of vacuum gas oil on catalysts on the basis of
ultra stable zeolite the influence of modifying ways on activity and selectivity of catalysts had been
investigated.

1. INTRODUCTION

Concentration Br6nsted and Lewis acid centres and their distribution on strength are the
determining factors influencing selectivity and stability of the hydroprocesses catalysts. Ways of
control of an acidity: change of Si/A1 ratio, Na20 contents, presence of nonframework inclusions
in zeolite cavities, modifying of zeolites by methods of ion exchange, processing by solutions of
acids and alkalis, and also various ways of calcination.
One of the perspective directions in creation of new hydro cracking catalysts is to use ultra
stable zeolite Y as acid components, having the high Si/A1 ratio, low Na20 contents, and capable
long duration time in conditions of reaction and oxidizing regeneration to save a crystal structure
and acid characteristics.
The conventional dealumination ways - dealumination of the zeolite Y ammonium form by
such organic complexing agents as ethylenldiaminotetraacefic acid or acetylacetone, and mineral
378

acids, frequently result to zeolite amorphization [ 1,2]. Recently in the field of ultra stable zeolites
synthesis have been developed methods based on direct replacement of aluminium with silicon in a
zeolite structure, using such inorganic fluorides and chlorides as SIC14. (NH4)2SiF6 and others as
dealumination agents [3-5].

2. EXPERIMENTAL

In the present paper the water solutions having different concentrations of (NH4)2SiF6have
been used for obtaining of ultra stable zeolite Y as dealumination agent. The necessary effect was
achieved by sequential combination of dealuminated zeolite on air at 500~ and exchange of
residual Na + on NH4 + ions. Next, zeolite with SIO2/A1203 ratio 6,6 (according to chemical
analysis), and residual Na20 contents of 0,02 %, have been further modified by processing with
the diluted water solutions of HCI or sodium hydroxide.
With using of X-ray diffraction and methods the structure of the prepared samples was
investigated. A nature of surface hydroxyl groups, number and distribution on strength of acid
centres are established under the IR-spectroscopy and temperature programmed desorption of
ammonia data.
On the basis of dealuminated or acid and alkaline modified zeolites, NiO and MoO3
containing catalysts of vacuum gasoil hydrocracking were prepared. The process conducted at
temperature 380-420~ pressure 10 MPa, volume feed rate 1 hr1, the H2/feedstock ratio 1000:1.

3. RESULTS AND DISCUSSION

The results of tests of the catalyst are presented in Table 1. As can be seen from the given
data, the feedstock conversion and the gas and gasoline fraction (<180~ yields increase with
increasing reaction temperature. The temperature dependence of the yi eld of diesel fraction (180-
350~ is influenced appreciably by the zeolite modification method. C f note is the higher yield of
gasoline fraction and also the higher content of gas in the hydrocracking products on Cat-3 by
comparison with the remaining catalysts. Taking account of the fact that the catalysts differ only in
the zeolite modification method, an attempt can be made to explain the relationships obtained on
the basis of differences in the structure and properties of zeolites.
As can been seen from X-ray data, dealumination of zeolite and alteration of ion exchange
and calcination stages results to initial reduction of unit cell parameter up to 24,35 A. After acid
and alkaline modifying unit cell parameter grows (up to 24,41-24,48 A) a little.
 379

Table 1
Results of tests of catalysts based on an ultra stable zeolite in the hydro cracking of vacuum gas
oil.
Catalyst Way of zeolite Temperature of Yield (%) of liquid fractions with different boiling
modifying conversion, ~ temperatures, ~
gas C!-C_4 <180 180-350 ibp-350
Cat-1 380 1.8 7.1 23.6 30,7
400 - 19.4 39.8 59,2
420 7.4 26.9 42.3 69,2
440 11.4 36.2 45.5 81,7
Cat-2 NaOH 380 - 6.1 40.0 46,1
400 1.2 13.0 40.0 53,0
420 10.8 30.0 48.0 78,0
440 20.3 29.6 57.2 86,8
Cat-3 HC1 380 0.7 6.3 34.9 41,3
400 0.8 18.5 35.7 54,2
420 12.3 31.5 33.3 64,8
440 18.4 74.0 14.0 88~

Simultaneously in IR-spectra of a crystal framework the shift of a maximum structural - sensitive

absorption band from 583 cm1 for NH4Y to 610-613 cm1 for dealuminated samples and some
reduction of specified band frequency for samples processed by acid or alkali solution are
observed. The X-ray and IRS data confirm the fact of a zeolite crystal framework dealumination.
At the same time, the unit cell parameter size and value of a structural-sensitive band maximum
can be influenced by A13*in ion exchanged condition. Acid and alkaline processing can partially
extract A13§ from zeolite, thus promoting the marked change of the structural characteristics.
The X-ray and IRS data of a crystal framework are necessary for adding by the
information on a nature of deluminated zeolite hydroxyl groups, as the specific band set of
structural OH-groups is characteristic of the ultra stable form. As have been shown by
measurements of IR-spectra, zeolite samples have well resolved band - 3740 cm1 and broad
absorption in the field of 3500-3700 cm1, for which it is possible to allocate a maximum- 3600
cm1, and also band shoulders at 3560 and 3620 cm1. A similar set of OH-group absorption bands
is close to described in the literature for the ultra stable form of zeolite Y, prepared by
hydrothermal process. Thus, the set of the received data allows to make the conclusion about
formation ultra stable zeolite during dealumination and subsequent treatments; however, the
zeolite structure was imposed by some features of acid or alkaline modifying.
More distinctly influence of modifying is shown by consideration of acid properties of
these samples.
380

The acid properties of zeolites were investigated by the matching of experimental and
computational TPD curves and determination of total of acid centres and function of their
distribution on activation energies of ammonia desorption. The concentration of acid centres has
made 296, 236 and 197 gmol/g for USY-1, USY-2 (processing USY-1 by a solution of alkali) and
USY-3 (processing USY-1 by a solution of an acid) zeolites, accordingly, previously calcinated at
temperature 500~ Thus, the total number of acid centres i.e. number of centres holding
ammonia, at modifying decreases, especially, in case of acid processing. It can be connected with
possible partial amorphization of samples, that is appreciable on weak fall of structural- sensitive
band intensity - 610 cml in a IR-spectrum, and also with additional dealumination, and removal of
ion exchanged aluminium, that results on the one hand in disappearance of a part of centres, and
with another - to appearance of stronger centres. The latter finds the reflection in increase of
values minimum and maximum activation energies of ammonia desorption after acid and alkaline
treatments. Analyzing the TPD data of absorbed ammonia one can conclude, that the initial ultra
stable zeolite modifying results in full removal of weak centres with E < 99 kJ/mole, appreciable
reduction of medium strength centre quantity with 99 <E < 129 and strong centres E > 129
kJ/mole.
The established distinctions in acid properties of zeolite allow to interpete the marked
above differences in behaviour of hydrocracking catalysts, though it is necessary to take into
account, that the deposition of a nickel and molybdenum compounds can influence acid properties
of a zeolite component. The increase in the proportion of medium-strength centres leads at 420~
in growth of an yield of gasoline and gas. Hence, for achievement of a maximum yield of gasoline
the hydro cracking process of vacuum gas oil is expedient for conducting at higher temperatures on
catalyst, which zeolite component contains mainly acid centres of medium strength. In this case
optimum properties has the sample, modified by acid treatment.
For increase of diesel fraction yield at high temperatures it is expedient to use the
zeolite with the greater share of strong centres mainly of electron-acceptor type. In the carried out
research to this requirement satisfies catalyst including zeolite, washed out by alkali solution.

REFERENCES

1. G. Kerr, J. Phys. Chem. 72 (1968) 2594.

2. L.F. Edward, R.V.C. Lovat, J. Chem. Soc. Faraday Trans.1.83. No. 5 (1987) 1531.
3. H.K. Beyer, I.M. Belenykaja, F. Hange, et al., J. Chem. Soc., Faraday Trans.1. 81.No. 11
(1985) 2889.
4. G.W. Skeels, D.W.Breck, Proc. 6th Int.Conf. on Zeolites, Reno, 1984.87.
5. D.W.Breck, G.W. Skeels, A.C.S. Symp. Ser. Washiington.V.218.1983.