Chemistry and Technology of Fuels and Oils, Vol. 37, No.

1, 2001

REFORMING OF NAPHTHA CUTS IN SMALL PLANTS

S. I. Kollesnikov, Amer Marvan, and I. M. Kolesnikov 665.664.4

It is advantageous to construct small distillation plants and reforming units that operate on oxide catalysts
(zeolite—aluminosilicate, zeolite, etc.) without circulation of hydrogen in the reaction system* for production
of high-octane naphthas from crude oil or gas condensates in the conditions of the Far North, Siberia, and
the Far East.

We p r o p o s e d u s i n g a m e c h a n i c a l m i x t u r e o f t y p e Z - 1 0 z e o l i t e - a l u m i n o s i l i c a t e a n d o x i d e
aluminum—nickel—molybdenum (ANM) catalysts for reforming low-octane naphtha cuts. In the refining industry,
the first one is used as a dehydrogenating, dehydrocyclizing, hydrocracking, and hydrodesulfurizing catalyst,
while the second is used as a cracking and isomerizing catalyst for hydrocarbons or crude oil cuts. Combining
these functions and studying the activity and selectivity of the mixture with optimization of its composition during
reforming of naphtha cuts at atmospheric pressure are of practical and scientific interest.
The aluminum—nickel—molybdenum catalyst produced at Ryazan’ Catalyst Plant had the following

78
76
3
Yield o f reform a te, w t. %

Yield of cok e, w t. %

72

2
68

1
64

60 0
100 80 60 40 20
Z -1 0

0 20 40 60 80 100
ANM
C o m p os itio n o f m ixe d c a ta lysts, v o l. %

Fig. 1. Effect of the composition of the mixture of catalysts on the yield of: 1) reformate;
2, 3) coke respectively in feedstock and in catalyst load.

* S . I . K o l e s n i k o v, I . M . K o l e s n i k o v, F a m Va n B a k , a n d M a r v a n A m e r, i n : P ro c e e d i n g s o f
the III Scientific-Technical Conference “Current Problems of the State and Evolution of the Oil and Gas
Complex in Russia” [in Russian], I. M. Gubkin RSU of Oil and Gas, Moscow (1999), pp. 23 – 24.

____________________________________________________________________________________________________
I. M. Gubkin Russian State University of Oil and Gas. Translated from Khimiya i Tekhnologiya Topliv i
Masel, No. 1, pp. 14 – 16, January – February, 2001.

0009-3092/01/3701–0015$25.00 ©2001Plenum Publishing Corporation 15

physicochemical properties: density of 860 kg/m 3 ; specific surface area of 180 m 2 /g; pore volume of 0.5 cm 3 /g;
composition, wt. %: 3.3 NiO; 15 MoO 3 ; remainder Al2 O 3 .
The Z-10 zeolite—aluminosilicate catalyst was manufactured by Salavat Catalyst Plant with the following
physicochemical properties: bulk density of 620 kg/m3; specific surface area of 420 m2/g; content (wt. %): rare-earth
elements (REM), 1.98; Na 2O, 0.38.
Reforming of the hydrotreated gas condensate 80 – 185°C naphtha cut was conducted** on a continuous
unit with a stationary bed of catalyst. The density of the cut at 20 °C was 741 kg/m 3 and the motor octane number
(MON) was 61.5. The reactor was filled with 40 cm 3 of any of the catalysts or a mixture of them. The load was
heated in a current of air, dried and purified of contaminants, for 1 h at 300 – 550 °C.
The surface of the catalyst was cleaned of moisture and organic contaminants adsorbed from the outside in
an air current at high temperature. After heat treatment ended, the temperature in the catalyst bed was decreased
to 480 °C, the reforming temperature of the naphtha cut.
The reforming process was conducted at a feedstock space velocity of 0.6 h-1 , temperature of 480°C, and
running time of 3 h. The reformate was sampled from the liquid tank every 60 min to determine the density,
refractive index, and octane number (Motor Method: MON). In addition, the yields of reformate, coke, and gas
and the composition (chromatography) of the hydrocarbon gases were determined.
The effect of the composition of the catalyst mixture on the yield of reformate and coke is shown in Fig. 1.
The polyextremal curves obtained reflect the change in the yield of these products, which indicates the complex
mechanism of the interaction of the surfaces of these catalysts on contact with each other and the active sites on
these surfaces.
Ensembles of tetrahedrons of the {AlO 4 ⋅ SiO 4 ⋅ LaO 4 }, {AlO 6 ⋅ SiO 4 ⋅ AlO 4 ⋅ LaO 4 } type and other
compositions are present on the surface of Z-10 catalyst. These ensembles exhibit elevated acceptor strength with
respect to hydrocarbon molecules. Ensembles of tetrahedrons of the {AlO 4 ×NiO 4 ×MoO 4 } type and ensembles of
polyhedrons in which some of the tetrahedrons are replaced by octahedrons of the same metal ions are located on
the surface of ANM catalyst. Ensembles of polyhedrons of this composition already exhibit lower acceptor strength.
As a consequence, the electrons in the upper filled orbital of some polyhedrons interact with the vacant
molecular orbitals of other polyhedrons and the distribution of electrons over energy levels among the polyhedrons
of different catalysts is optimized on contact of two catalysts with a different polyhedral composition and structure.
This affects the activity and selectivity of the combination of polyhedrons on the contiguous phase—catalyst
interface.
As Fig. 1 shows, Z-10 catalyst has higher cracking activity than ANM catalyst: in its presence, the yield of

84 -1
1h
78
2
MON

70
3

62
100 80 60 40 20 0
Z -1 0

0 20 40 60 80 100
ANM
C o m p ositio n o f m ixe d c ata ly sts, vo l. %

Fig. 2. Effect of the composition of a mixture of catalysts on the octane number (ON) of
naphtha-reformate for different durations of continuous work (see figures on curves).

** With the participation of V. I. Nikonov.

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 TABLE 1

Content (wt. % in feedstock) in gas mixture obtained on catalyst mixture; proportion of

Component ANM component, vol. %
0 10 20 30 50 70 90 100
H2 0.54 1.29 0.29 0.25 0.65 0.87 0.96 1.30
CO – 0.05 0.011 0.014 0.026 0.02 0.017 0.10
CO2 0.003 0.09 0.013 0.007 0.014 0.008 0.004 0.02
CH4 0.081 1.07 0.67 0.47 1.01 1.54 1.81 2.94
C2H6 0.25 0.97 0.64 0.31 0.69 0.87 0.92 0.82
C2H4 0.22 0.13 0.38 0.20 0.32 0.16 0.06 0.01
C3H8 1.86 0.83 4.07 2.20 4.00 3.51 3.00 1.73
C3H6 2.72 3.05 7.63 4.40 8.50 7.31 6.27 3.39
ΣC4H10 0.52 0.23 2.42 0.88 1.80 2.07 1.40 1.09
ΣC4H8 1.14 0.94 3.80 2.90 3.71 3.51 3.02 2.76
ΣC5 – C7 0.53 1.58 1.08 1.17 2.39 2.32 2.48 1.74
Note. Reforming of the naphtha cut was conducted at a temperature of 480°C and feedstock space
velocity of 0.6 h -1 for 3 h.

reformate is ~64 wt. %, versus 76 wt. % in the presence of ANM catalyst. When the volume content of
ANM catalyst in the mixture increases, the yield of reformate changes according to a complex polyextremal curve:
it decreases to the minimum at 10 vol. %, increases to the maximum at 30 vol. %, and again decreases to the
minimum at 50 vol. %.
The same complex dependence on the composition of the catalyst mixture was also obtained for the coke
content on their surface in conversion to the feedstock passed and the mixture load. The yield of coke varied
almost symbatically to the change in the yield of reformate. The increase in it with an increase in the content of
ANM catalyst in the mixture was due to the higher dehydrogenating and dehydrocyclizing selectivity of the latter,
which increases the unsaturated hydrocarbon content in the reformate and the proportion of reactions of their
disproportionation into coke-like products.
The curves of the octane number (ON) of the reformate as a function of the composition of the catalyst
mixture for different lengths of continuous work are shown in Fig. 2. These curves are also polyextremal. The
individual Z-10 and ANM catalysts exhibit almost the same activity in increasing the ON of the reformates in
reforming of the low-octane (ON = 61.5) naphtha cut. The ON of reformates obtained on Z-10 catalyst is equal
to 77, versus 76.5 on ANM catalyst (MON). In continuous work of the catalysts for 1 h, the maximum ON are
83 and 82.2 and the minimum ON are 78.
When the continuous work time of the catalysts is increased to 2 and 3 h, the octane number of the reformate
decreases due to deposition of coke on the surface of the mixture so that its activity and selectivity decrease. It
decreases most significantly in the presence of Z-10 and least significantly in the presence of pure ANM catalyst.
This is due to the lower selectivity of the latter in the reaction of disproportionation of unsaturated and aromatic
hydrocarbons and other reactions that promote coke formation, resulting in production of coke more active in
catalysis.
Mixtures with a 70 – 90 vol. % content of ANM catalyst exhibit the highest activity, indicating reciprocal
promotion of the catalysts.
The composition of the gas mixture changes polyextremally (see Table 1). Propylene and butylenes
predominate in the gas mixture obtained on the mixed catalysts with 90 vol. % ANM, and propane and butanes are
present in a smaller amount. The maximum yield of the latter is attained on mixed catalysts with 20 and
50 vol. % ANM catalyst.
The yield of methane is low for all catalyst compositions. It attains 2.94 wt. % in feedstock only with the

17
individual ANM catalyst. These data are required for calculations of reformate stabilization and fractionation
towers.
It follows from the data reported that reforming of the naphtha cut on mixed catalysts is conducted in
conditions that ensure the highest yield of C 3 – C 4 hydrocarbons with predominance of unsaturated structures.
The hydrogen content in the gas increases from 0.29 to 1.3 wt. % with an increase in the content of ANM catalyst
in the mixture.
The polyextremal curve of the yield of hydrocarbon components of the gas as a function of the ANM content
reflects the complex mechanism of the reaction of the surfaces of the different catalysts and the participation of a
complex group of catalytic sites in conversion of the naphtha cut. Based on the experimental data, a mixture
of 20 – 30 vol. % of Z-10 catalyst with 80 – 70 vol. % ANM catalyst is optimum for industrial use.

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