Applied Catalysis, 51 (1989) 213-222

Elsevier Science Publishers B.V., Amsterdam -Printed in The Netherlands

New Catalyst for Hydrocracking of Vacuum

Residue

TOSHIO ITOH* and YUKIHIRO TSUCHIDA

Central Research laboratories, Idemitsu Kosan Company, Ltd.," Kamiizumi 1280,
Sodegaura-cho, Chiba 299-02 (Japan)
(Received 2 September 1988, revised manuscript received 31 January 1989)

ABSTRACT

Catalytic hydrocracking using five mineral clay catalysts and five fluid catalytic cracking cat-
alysts was performed in an autoclave. Mineral clay catalysts have higher mid-distillate yields and
lower coke plus gum (coke precursor) yields than fluid cracking catalysts. Allophane is especially
notable for producing the lowest coke plus gum yield. Allophane's functions were investigated by
means of removing iron from allophane and impregnating iron to fluid cracking catalysts. Iron
concentration and macro pore volume were found to be important to suppress coke formation.

INTRODUCTION

Ordinary, petroleum atmospheric residues are usually hydrotreated by fixed

bed reactors which use conventional supported catalysts, e.g. cobalt-molyb-
denum on porous alumina.
As petroleum vacuum residue and tar sands bitumen contain high concen-
trations of asphaltenic materials, metal contaminants and sulfur, hydrotreat-
ing of these feeds with fixed beds is very difficult.
Problems encountered in processing heavy feeds over ordinary supported
catalysts are rapid catalyst deactivation, the deposition of feed metal contam-
inants in the catalyst pores and plugging of fixed bed reactors. As a conse-
quence of these adverse factors, slurry-type processes which can operate with
finely divided catalysts were developed. Such a slurry-type process reduces
diffusion limitations and has no plugging problem attributable to particulate
matter in the feeds.
"As a participant of The Research Association for Petroleum Alternatives Development, Tokyo
bAllophane,clay mineral in volcanic ash soil, has the following features:prominent yellowish brown
to reddish subsoil colors with a smeary feel when the soil is wet; very light and porous profiles with
a low bulk density and high water holding capacity; amorphous to X-rays and has large surface
area and 2.6 wt.-% iron.

0166-9834/89/$03.50 O 1989 Elsevier Science Publishers B.V.

 In slurry-type processes, a few catalysts have already been known to be ef-
fective: VEBA OELYsCombicracking has used iron sulfate, activated lignite
semi-coke and a neutralization agent for the catalysts; and Petro Canada's
CANMET process has used a coal impregnated with ferrous sulfate [1,2].
In this investigation, we attempted to use inexpensive natural clay catalysts
and fluid catalytic cracking catalysts as the catalysts of a slurry-type process.
A natural clay, allophane, has been found to be a very effective catalyst for
hydrocracking of vacuum residues. This paper shows that the allophane cata-
lyst has high mid-distillate yield and suppressing ability for coke plus gum
formation.
This paper also includes a discussion of the nature of allophane in putting
emphasis on the effect of iron, as investigated by the effect of removing iron
from allophane.

EXPERIMENTAL

Materials

The feed used was an Arabian Heavy vacuum residue of which general prop-
erties are shown in Table 1. The commercial fluid catalytic cracking (FCC)
catalysts and the clay minerals (kaolinite, allophane, bentonite, sepiolite and
halloysite) were used for tests as the supports. A commercial hydrodesulfuri-
zation (HDS) catalyst was also used as a reference. The typical specifications
of the supports are shown in Table 2.

Equipment

All hydrocracking tests were carried out in a 300-ml capacity stainless-steel

autoclave. The stirrer shaft was driven magnetically and had a maximum speed
of 1000 rpm. The autoclave was heated by an electrical unit.
TABLE 1

Properties of feedstock

Arabian Heavy VR
- -

Specific gravity (15/4"C) 1.0295

Sulphur (wt.-%) 5.1
Viscosity (Cst, at 100"C) 2680
Conradson Carbon h s i d u e (wt.-%) 11.4
V/Ni ( P P ~ ) 127/41
Nitrogen (wt.-%) 0.32
TABLE 2

Specification of support and of HDS catalyst

Kaolinite Allophane FCC Do FCC Eb HDS catC

SA (m2/g) 27 247 520 350 220
PV (ml/g) - 0.61 - 0.28 0.63
Solid-acid (wt.-% ) - 4.9 - 90.6 -
SiOa (wt.-%) 45 50 60 53 -
A1203 (wt.-%) 39 43 29 33 -
Fe~03 (wt.-%) 0.3 3.6 0.1 0.2 -
CaO (wt.-%) 0.1 1.1 - - -
MgO (wt.-% '0) - - - - -
Na,O (wt.-%) - - 0.4 0.0 -
MOO, (wt.-%) - - - - 10.5
NiO (wt.-%) - - - - 0.7
coo (wt.-%) - - - - 1.2

"FCC catalyst D
bFCC catalyst E
'hydrodesulfurization catalyst.

Preparation of catalyst

For catalyst screening, catalysts were prepared by impregnating each com-

mercial FCC catalyst and clay mineral with an aqueous solution of ammonium
metavanadate, nickel nitrate and oxalic acid in such a way that the pore vol-
ume of the support is just filled with the aqueous solution. After drying at 80"C
for 3 h, the materials were calcined at 550 "C for 3 h and sieved to a particle
size between 37 'and 125 pm. The resulting oxide catalysts contained 1.0% V
and 0.5% Ni by weight.
For studying effects of solid acidity and of iron oxide on the catalyst activi-
ties, Fe-impregnated FCC catalyst E, and K-impregnated FCC catalyst E were
prepared by similar method using ferrous nitrate or potassium carbonate, re-
spectively. The resulting oxide catalysts contained the following metal concen-
trations by weight: 1.0% Fe, 2.0% Fe, 2.6% Fe or 4.7% Fe and 0.5% K, 1.0% K,
2.0% K, 2.6% K or 4.0% K. Allophane free from iron was prepared by using
sodium dithionite and sodium citrate in aqueous solution with NaHCO, buffer
131-

Hydrocracking of vacuum residue

For each test, 10 g of catalyst and 80 g of vacuum residue were used. The
autoclave was flushed with hydrogen and was charged to 40 kg/cm2 with hy-
drogen. At the reaction temperature of 450°C, if the reaction pressure was
below 85 kg/cm2, hydrogen was charged to keep the pressure at 85 kg/cm2.
Stirring speed was kept a t 700 rev/min. After reaction had been continued for
1 h, the heating unit was removed and then the autoclave was allowed to cool
to room temperature. The oil and slurry produced, containing used catalyst,
coke and gum, were discharged and bottled.

Analysis of products in the hydrocracking

A portion of the oil produced in each hydrocracking experiment was ana-

lysed by gas chromatography to obtain each yield (naphtha: C,+-171 "C, mid-
distillate: 171-343" C, vacuum gas oil: 343-525" C, and vacuum resi-
due: > 525 " C ) .Coke and gum yields were obtained by dissolving the slurry with
solvents as follows; 5 g of the slurry were mixed with 100 ml of toluene and set
aside for 1.5 h. Undissolved material was separated using a 0.8-pm filter. The
filter cake was washed with toluene followed by n-heptane. After drying and
burning coke, the coke yield was gravimetrically determined. Gum yield was
determined by a similar method using n-heptane as for the coke yield.

Measurement of solid acidity

The amount of solid acidity was indirectly calculated from the catalytic ac-
tivity for cracking reaction of cumene to benzene and propylene. The extent
of cumene cracking was represented by wt.-% of cumene reacted. The cumene
cracking reaction was made with a pulse reactor under the following condi-
tions: 250°C reaction temperature, 60 ml/min helium flow-rate and 0.1 g of
solid sample.

Measurement of XPS

The X-ray photoelectron spectra (XPS) were measured using a Shimazu

ESCA 750 spectrometer with Mg K a (1254 eV) as radiation source. The XPS
spectra were used to determine the surface concentrations of Fe, Si and Al. C,,
(285 eV) was taken as reference for calculating the bond energies. The
intensities of the peaks were referred to the total area of the iron peak
(Fe2p,,,-3,,), with respect to the total area of the aluminum (Al,,) and the
silicon (Si,,) bonds, respectively [4].

RESULTS AND DISCUSSION

Catalyst screening

Ten vanadium and nickel supported catalysts (five mineral clays and five
FCC catalysts) were evaluated. Vanadium-nickel does not consume hydrogen
more than cobalt-molybdenum and other ordinary hydrotreating catalysts,
 50 55 60 65 - 0
50 55 60 65
343'C Conversion (wt?l0) 343°C Conversion (wt%)

Fig. 1. Mid-distillate yields for various catalysts; (1) kaolinite; (2) allophane; (3) bentonite; ( 4 )
sepiolite; ( 5 ) halloysite; (6) FCC catalyst A; (7) FCC catalyst B; (8) FCC catalyst C; (9) FCC
catalyst D; (10) FCC catalyst E.

Fig. 2. Coke plus gum yields for various catalysts: ( 1 ) kaolinite; (2) allophane; (3) bentonite; (4)
sepiolite; (5) halloysite; (6) FCC catalyst A; (7) FCC catalyst B; (8) FCC catalyst C; (9) FCC
catalyst D; (10) FCC catalyst E.

'0 20 40 60 80
Solid Acidity (wt;O/.)
(represented by the cumene conversion)

Fig. 3. Relationship between solid acidity and yield of products. 0=mid-distillate; =coke;
A =gum.

and vanadium and nickel can be supplemented from the vanadium and nickel
that are rejected from the feed in hydrocracking processes. The 343"C conver-
sion (wt.-% ) = 100. (1- (heavy fraction (b.p. > 343 " C ) in products (g) +gum
in products (g) )/charge oil ( g ) ). Fig. 1 shows the results for the percentage
yield of mid-distillate. In spite of low conversion, mineral clay catalysts have
mid-distillate yields higher than FCC catalysts. Fig. 2 shows that mineral clay
catalysts have low coke plus gum yields. Allophane is especially notable for
producing the lowest coke plus gum yield. Table 3 shows the effects of vana-
dium and nickel upon the activities of allophane and FCC catalyst E. AlIo-
TABLE 3

Effect of vanadium and nickel upon catalyst activity

Conversion, 343°C; V,Ni/Allophane, 1.0 wt.-% V-0.5 wt.-% Ni allophane; V.Ni/FCC E, 1.0 wt.-
% V-0.5 wt.-%Ni FCC catalyst E; HDS cat, hydrodesulfurization catalyst.
- - - - - - ---

V,Ni/Allophane Allophane V,Ni/FCC E FCC E HDS cat

Middle
distillate (wt.-%) 28.0 27.3 24.8 25.4 28.6
Gum (wt.-%) 3.2 6.3 5.9 8.0 2.3
Coke (wt.-%) 5.0 8.0 11.0 19.3 5.2
Conversion (wt.-%) 53.0 53.0 51.2 69.4 54.8

phane's activity is the same as that of commercial HDS catalyst. Allophane

seems to suppress overcracking of the vacuum residue.

Catalyst properties and structure

The physical properties and chemical compositions of allophane and the
FCC catalysts are listed in Table 2. Allophane contains iron, and has a larger
pore volume and less solid acidity than the FCC catalyst E.

Influence of solid acidity upon the catalytic reaction

In order to understand the reason for low coke plus gum yield and large mid-
distillate yield of allophane, firstly, the effect of the solid acidity upon mid-
distillate and coke plus gum yield was investigated. Each catalyst was prepared
by impregnating FCC catalyst E with a different amount of K2CO3.Fig. 3 shows
that the yields of the reaction products are entirely independent of the solid
acidity of the catalysts. This result suggests that a large portion of cracking of
the feed oil arises from the thermal reaction and the contribution of catalytic
cracking is negligible.

Effects of iron oxides on the catalyst properties and structure

Secondly, the effect of iron upon mid-distillate and coke plus gum yield was
investigated. Fig. 4 shows the relationship between iron concentration and yield
of the products in the case in which iron impregnated FCC catalyst E has been
used. Coke yields decreased remarkably and mid-distillate yields increased
gradually along with iron concentrations. An iron content of only 3 wt.-% is
enough to decrease coke yield. In contrast gum yields increased slightly.
In the reaction conditions, the iron in allophane should be converted to sul-
fide, which represents the hydrogenation phase. The hydrogenation of free
radicals which are produced by thermal cracking of hydrocarbon should quench
 0 1.0 2.0 3.0 4.0 5.0
Iron Content (wt"1.)
Fig. 4. Relationship between iron content and yield of products. 0= mid-distillate; =coke;
A =gum.

TABLE 4

Physical properties and components of iron-removed allophane

Allophane Allophane-A Allophane-B

SA
PV
Solid-Acid
Si02
A1203
Fe20,
CaO
MgO
Na,O
K20

free radical chain reaction or radical polymerization. Rosa-Brussin and co-

workers reported that in a sulfidation process pyrrhotites (Fe,-$3) were formed
from metallic iron coming from reduction of small particles or iron oxides in a
clay, and that there was a relationship between the hydrodemetallization and
the appearance and abundance of pyrrhotites [5,6].
In order to investigate the effect of iron and pore size distributions of allo-
phane, iron free oxides were removed from allophane, using sodium dithionite
and sodium citrate in aqueous solution with sodium bicarbonate buffer [3].
Table 4 shows physical properties and compositions of the iron-free allophane.
Up to 80 wt.-% of iron was removed from allophane by this treatment. The
remainder of iron in allophane could not be removed. Yoshinga reported that
the removal of iron may be achieved almost quantitatively [7].
The IR spectra and silicon NMR were measured to study the allophane
structure. There was no difference through 1130 to 1140 cm-l, which resulted
from the antisymmetric vibration of TO, structure between allophane and the
iron-free allophane.
Silicon NMR spectra also showed there is no structual difference between
allophane and the iron-free allophane. In conclusion, the IR spectra and the
silicon NMR spectra suggest that the structure of allophane is not destroyed.
Table 5 shows the reaction results of the iron-free allophane and the iron-free
allophane in which iron was re-impregnated. The 525°C conversion
(wt.-%)= 100- (1- (heavy fraction (b.p. > 525 "C) in products (g) +gum in
products (g) )/charge oil (g) ) .The iron-free allophane does not show coke plus
gum suppressing ability. These results are the same as those for FCC catalyst
E. The activity of the iron-free allophane being re-impregnated with 2.6 wt.-%
Fe (the same as that of allophane) is practically the same as that of allophane.
In conclusion, it can be said that iron plays a significant role in the suppression
of coke formation.

TABLE 5

Reaction results of modified allophane

Allophane-A FeIAllophane-A Allophane

Gas (&.-%I 6.1 5.2
Naphtha (wt.-%) 17.9 15.9
Middle distillate (wt.-%) 26.9 28.1
Vacuum gas oil (wt.-%) 15.1 21.0
Vacuum residue (wt.-% ) 6.7 13.8
Gum (wt.-%) 8.7 8.2
Coke (wt.-%) 18.6 7.8
Conversiona (wt.-%) 84.6 78.0

Pore Diameter (A)

Fig. 5. Pore size distributions of iron-free allophane. (1) Allophane-A; (2) Allophane-B.
Pore distribution and iron exposed on catalyst surface

Figure 5 shows pore size distribution in two iron-free allophane samples (Al-
lophane-A and Allophane-B ). Allophane-B, which consists of small particles,
has a smaller pore volume and larger apparent bulk density than Allophane-
A. Two iron-free allophanes were re-impregnated with 2.6 wt.-% Fe in similar
manner. Table 6 shows the quantity of iron exposed on the allophanes re-
impregnated with iron, represented by a ratio I (Fe,,,/,_,/,) /I (Si,, Al,,) ob- +
tained by the XPS method. Table 7 shows the catalytic activities of two allo-
phanes re-impregnated with iron. Allophane-A re-impregnated with iron has
coke plus gum suppressing ability higher than Allophane-B re-impregnated
with iron. Rosa-Brussin and coworkers reported that a natural clay catalyst
having iron highly dispersed on the surface was active in hydrodemetallization
and hydroconversion of heavy crudes [ 4 ] .
Since Fe/Allophane-A has a smaller pore volume and less iron exposed on
the catalyst surface than Fe/Allophane-B, the feed can not diffuse properly to
the iron supported on Allophane-A and is not catalyzed by iron sufficiently.
In conclusion macro pore volume and iron exposed on the catalyst surface
also play important parts in suppressing coke formation,

TABLE 6

Surface iron content of catalyst

"Intensity of the iron peak(Fe2,,,,-,/,) measured by XPS

~ ~ )the aluminium (Al,,) measured by XPS.
bTotalintensity of the ~ i l i c o n ( S i and

TABLE 7

Activity of macro-pore allophane

Fe/Allophane B Fe/Allophane A
Gas
Naphtha
Middle distillate
Vacuum gas oil
Vacuum residue
Gum
Coke
Conversiona
ACKNOWLEDGEMENTS

we would like to acknowledge the support of Idemitsu Kosan, Co. Ltd., Cen-
tral Research Laboratories, for allowing this publication. Thanks are also due
to Dr. N. Kawata, for his encouragement and guidance, and to Prof. F. Nozaki,
Chiba University, for his advice on preparation of this paper.

REFERENCES

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C. Zerpa, U.S. Patent 4 568 657 (1986).
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