DOI 10.

1007/s10553-017-0824-4
Chemistry and Technology of Fuels and Oils, Vol. 53, No. 4, September 2017 (Russian Original No.4, July – August, 2017)

PROCESS OF PRODUCING HIGH-OCTANE MOTOR FUEL COMPONENTS

FROM STRAIGHT-RUN GASOLINES ON MODIFIED ZEOLITE CATALYSTS

I. S. Khomyakov, A. M. Gorshkov, and T. A. Gerasina

The effect of micro- and nano-sized CeO 2 powder additives on acidic and catalytic properties
of MFI (mordenite-framework-inverted) type of high-silicon zeolite in the process of production of
high-octane motor fuel components from straight-run gasolines of gas condensate is studied. Addition
of modifying agents to the original zeolite promotes its catalytic activity and concentration of acid
centers. Addition of 1 wt. % of promoting additives of nano-sized CeO 2 powder to zeolite enhances
yield of arenes in the liquid catalyzate by 4-7 wt. % and octane number (ON) of
the obtained catalyzate by 2-3 points in terms of RON. It is shown that zeolite modified by
micro-sized CeO 2 powder possesses similar catalytic and acidic properties as does zeolite modified
by nano-sized CeO 2 powder.
Keywords: straight-run gasoline, gas condensate, high-octane components, zeolite MFI, aromatic
hydrocarbons.

The treatment of natural hydrocarbon material is now becoming particularly important from both the
technical and economic standpoint and the ecological standpoint. The development of ecologically clean and
waste-free catalytic processes takes an important part in the development of alternative sources of hydrocarbon
feedstock and processes based on them [1-4]. The increased demand for motor fuels, toughening of the
requirements imposed on them, and introduction of different types of hydrocarbon feedstock have determined

____________________________________________________________________________________________________
National Research Tomsk Polytechnical University, Tomsk, Russia. E-mail: Khomyakov_i.s@mail.ru.
Translated from Khimiya i Tekhnologiya Topliv i Masel, No. 4, pp. 8 – 11, July – August, 2017.

464 0009-3092/17/5304–0464 2017 Springer Science+Business Media New York

the direction of research on the production of high-octane gasolines. Russia possesses significant reserves
of the various alternative sources of hydrocarbon feedstock: gas condensates; condensates; the natural and
associated petroleum gases that have in recent years been actively introduced into the oil refining industry.
Some of the most promising processes for the production of high-octane components of gasoline
from light hydrocarbon feedstock are processes on catalysts based on high-silica zeolites (HSZ) of
the MFI type [5-8]. Zeolites of this type have high activity and selectivity arising from their unique structural
characteristics and molecular-sieve and acid characteristics [9]. High-silica zeolites of the MFI type belong to
the class of superacids and have various types of active sites, making them active in chemical reactions of
both acid–base and oxidation–reduction type [10-12].
This work presents results on the acidic and catalytic properties of zeolites of the MFI type modified
with micro- and nanosized cerium dioxide powders at rates of 1 and 3 wt. % in the production of high-octane
components of gasoline from light hydrocarbon feedstock.
High-silica zeolites with a silicate ratio (SiO 2 /Al 2 O 3 ) of 50 were obtained by hydrothermal
synthesis from alkaline aluminosilicates at 189°C for six days [13]. After crystallization the zeolites
were washed with water, dried at 110°C, and calcined at 600°C for 6 h. The HSZ was converted into the
active H form by treatment with a 25% solution of HN 4 Cl at 90°C for 2 h followed by drying at 110°C and
calcination at 600°C. (The Na 2 O content of the decationized zeolites was less than 0.01 wt. %.)
It was established that the synthesized zeolites belongs to the MFI class by IR spectroscopy
and x-ray phase analysis. The IR spectra were recorded on a Nicolet 5700 IR Fourier spectrometer in the region
of 450-2000 cm -1 . X-Ray phase analysis was conducted on Dron-3 apparatus (Mo anode, Ni filter). The
diffractograms were interpreted by determining the interplanar separations and line intensities. The results
were then compared with the results obtained for a standard sample. According to the data from x-ray phase
analysis and IR spectroscopy the synthesized zeolite belongs to the MFI type.
The synthesized HSZ was modified with micro- and nanosized cerium dioxide powder (particle
size <5  m and <50 nm respectively) by mechanochemical activation in a KM-1 vibrating ball mill
at 25°C for 12 h. Samples of HSZ modified with micro- and nanosized cerium(IV) oxide powders at rates
of 1 and 3 wt. % were obtained by this method.
The acid characteristics of the initial and modified zeolites were investigated on thermal desorption
apparatus from the adsorption of ammonia in a stream of helium as carrier gas in the range of 50-650°C at a
linear heating rate of 10 deg/min. The adsorption of ammonia on the zeolite was realized with a high carrier gas
flow rate (110 cm 3/min) at 100°C for 1 h in order to exclude diffusion complications and the physical type of
adsorption. After this the reactor with the investigated sample was cooled to 50°C, and the ammonia was
desorbed. A katharometer was used as detector. In the experiments on determination of the acid characteristics
of the zeolite-containing catalysts we used grade A helium (99.995 vol. %) and “pure” grade gaseous ammonia.
The concentration of acid sites in the investigated samples, expressed in  mole/g of catalyst, was determined
from the amount of ammonia in the desorption peaks (forms). The accuracy of determination of the adsorbed
ammonia by gas chromatography was ±2.5 rel. %.
The transformations of the 70–170°C straight-run gasoline fraction (SGF) of the gas condensate at
zeolite-containing catalysts was investigated on flow-type catalytic apparatus with a stationary layer of
catalyst (reactor volume 10 cm 3) in the range of 325-375°C at atmospheric pressure. The volume flow rate of the
feedstock was 2 h -1 , and the experiment took 1 h for each temperature. In hydrocarbon group composition the
initial SGF consisted of 22.7 wt. % of paraffins, 33.2 wt. % of iso-paraffins, 39.9 wt. %of naphthenes,
and 4.2 wt. % of arenes. The octane number of the SGF was 60 points by the research method (RM).

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Table 1
Yield of products, wt. %
Composition of liquid phase

Catalyst Temperature, °C RON

gas phase
arenes

liquid phase.
benzene
olefins

paraffins

naphthenes

of the arenes
iso-paraffins

in composition
325 34.8 65.2 21.8 1.0 40.0 19.5 17.1 1.6 88.1
HSZ 350 42.0 58.0 27.6 1.8 40.2 18.2 12.6 1.4 92.2
375 49.0 51.0 33.6 2.9 36.8 17.2 10.8 1.6 92.1
325 33.2 66.8 26.0 1.2 37.0 21.6 13.9 1.5 91.2
1% nano-CeO 2 /99% HSZ
350 41.8 58.2 33.6 2.3 34.1 19.4 11.5 1.4 943
375 46.8 53.2 40.5 3.4 30.4 18.7 9.1 1.3 94.0
325 34.0 66.0 24.4 1.1 36.1 24.5 13.5 1.5 89.1
3% nano-CeO 2 /97% HSZ
350 40.6 59.4 32.6 2.2 34.3 20.0 11.7 1.4 93.2
375 48.1 51.9 39.0 3.3 31.1 18.6 9.9 1.4 93.6
325 34.2 65.8 24.8 1.1 36.9 22.0 14.8 1.5 89.8
1% micro-CeO 2/99% HSZ
350 39.7 60.3 32.6 2.0 35.4 20.3 10.3 1.5 92.7
375 46.7 53.3 40.5 3.2 31.7 17.5 9.1 1.1 93.3
325 35.8 64.2 24.0 1.2 36.9 22.6 15.1 1.4 89.8
3% micro-CeO 2/97% HSZ 350 41.9 58.1 31.4 2.0 34.5 20.5 12.2 1.4 92.7
375 47.2 52.8 38.3 3.1 31.8 18.6 9.9 1.5 93.3
 The gaseous hydrocarbons were analyzed on a packed stainless steel column (length 3 m, internal
diameter 3 mm) filled with a 5% solution of NaOH on Al2O 3 (0.25-0.50 mm fraction). The liquid hydrocarbons
were analyzed on a quartz glass capillary column (100 m  0.25 mm  0.25m) with a deposited ZB-1 stationary
phase. Quantitative analysis of the gaseous and liquid products from transformation of the SGF was performed
by gas chromatography on a hardware programmed setup based on a Khromatek-Kristall 5000 isp. 1 gas
chromatograph with Khromatek-Analitik 2.6 software. The research octane number was determined by
calculation based on the results of gas chromatographic analysis of the hydrocarbon composition of the
feedstock and the liquid products from transformation of the straight-run gasolines on the investigated
zeolite-containing catalysts by means of Khromatik-Gazolin software. The error in the gas-chromatographic
determination of the gaseous and liquid hydrocarbons was ±2.5 rel. %.
The results of the investigations of the catalytic activity of zeolite catalysts in the SGF of gasoline
condensate into high-octane components of motor fuels are presented in Table 1. The arene content in the
obtained catalyzate was used as measure of the catalytic activity. Liquid and gaseous products are formed as
a result of conversion of the SGF at all the investigated samples. If the temperature of the process is raised
from 325 to 375°C there is a tendency for the yield of the liquid catalyzate to decrease on account of increased
degree of transformation of the hydrocarbons in the feedstock. Thus, the yield of gaseous products consisting
largely of propane and butane, the overall yield of which amounts to 90-95 wt. %, is increased.
The yield of liquid catalyzate on the unmodified HSZ decreases from 65.2 wt. % at 325°C
to 51.0 wt. % at 375°C (Table 1). Here, the content of C6-C 12 arenes in the liquid catalyzate increases significantly
with a preponderance of toluene and xylenes. In the investigated temperature range the arene content increases
from 21.8 wt. % to 33.6 wt. % and includes benzene from 1.0 wt. % to 2-9 wt. %. The yield of naphthene
and C 5+ -n- and iso-paraffins decreases with increase of temperature. The research octane number of the liquid
catalyst increases from 88.1 to 92.1 points.
If nanosized cerium dioxide powder is added to the HSZ at the rate of 1 wt. % the yield of arenes in the
liquid reaction products is increased by 4-7 wt. %, and the research ON of the obtained catalyzate is increased
by 2-3 points compared with the reaction products on the original HSZ. In the range of 325-375°C the yield of
the catalyzate is increased by 2.2-3.6 wt. % respectively.
The addition of 1 wt. % of cerium dioxide as modifying additive also increases the yield of
arenes in the reaction products and the octane number of the obtained catalyzate compared with the
initial HSZ (Table 1). We note that the HSZ modified with 1 wt. % of cerium dioxide powder exhibits somewhat
lower activity than the HSZ modified with 1 wt. % of nanosized cerium dioxide powder; the yield of arenes
is 1-1.6 wt. % less, the research ON of the obtained catalyst is 0.9-2.2 points, and the yield of the liquid
catalyst is 0.8-1.3 wt. % lower. Addition of 3 wt. % of the micro- and nanosized cerium dioxide powders leads
to decrease in the catalytic activity of the samples compared with the HSZ modified with 1 wt. % of these
powders.
The acid characteristics of the initial and modified HSZ are presented in Table 2. According to the data
from thermally programmed desorption (TPD) of ammonia all the samples were characterized by the presence
of two peaks on the TPD profile corresponding to two different types of desorption of ammonia: a
low-temperature peak in the region of 120-250°C corresponding largely to desorption of ammonia from the
weak acid sites (a. s.) (type I), which in the zeolite may be coordination-unsaturated aluminum ions; a
high-temperature peak in the region of 300-550°C corresponding to desorption of ammonia from the strong
acid sites (type II), which may be hydrogen ions from the bridging hydroxyl groups [14]. The

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Table 2

Maximum temperature, °C Concentrated of acid sites, mole/g

Catalyst
I II I II Total
HSZ 185 400 402 224 626
1 % nano -Ñå02/ 99 % HSZ 197 420 538 208 746
3 % nano -Ñå02/ 97 % HSZ 196 420 498 202 700
1 % micro -Ñå02 / 99 % HSZ 193 415 515 202 718
3 % micro -Ñå02/ 97 % HSZ 190 410 480 198 678

concentrations of the weak and strong acid sites for the original HSZ are 402  mole/g and 224  mole/g
respectively (Table 2).
With the introduction of the modifying additives into the original zeolite an increase is observed in
the total concentration of acid sites (c.a.s.) as a result of increase in the concentration of weak acid sites. The
concentration of strong acid sites in the modified samples is reduced by 16-28  mole/g. The largest increase
in the concentration of acid sites occurs in the sample modified with 1% of nanosized cerium dioxide powder
and amounts to 746  mole/g. the increase in the concentration of acid sites in the zeolite as a result of the
introduction of the modifying additives can evidently be explained on the basis of the electronic structure of
the Ce atom [Xe]6s 24f 2. The outer electronic level has two unpaired electrons. In order to form a bond with the
oxygen atoms at the Ce atom electrons are transferred from the 6s2 and 4f2 sublevels to the
unoccupied 5d sublevel, forming a stable 4f 0 configuration. In this state after the formation of cerium dioxide
at the Ce atom there remains one unoccupied orbital at the 5d sublevel, which can act as a weak aprotic acid
site. With the addition of cerium dioxide, probably, partial overlap of the zeolite acid sites occurs as a result of
the larger size of the cerium dioxide particles compared with size of the zeolite pores. However, new active
sites of type I are evidently formed as a result of interaction of the cerium dioxide with the surface of the
zeolite since the oxides of transition metals form with zeolite specific surface complexes in which
the O 2- anions of OH groups of the zeolite itself can act as ligands. This can explain the increase in the
concentration of weak acid sites with the introduction of both nanosized and microsized CeO 2 powders.
Weak acid sites are able to activate the molecules of low alkanes and alkenes, thereby accelerating
their dehydrogenation on account of the electron-withdrawing characteristics of the aprotic center [15]. As a
result the sample exhibits high catalytic activity in relation to the formation of arenes in the reaction products.
The observed decrease of the concentration of acid sites with increase of the concentration of the promoting
additions to 3 wt. % (Table 2) can evidently be explained by a stronger effect from screening of the acid sites
of the zeolite itself. Meanwhile the concentration of the acid sites decreases more strongly as a result of the
introduction of the larger-sized CeO 2 micropowder. However, it is worth mentioning that the samples modified
microsized CeO 2 powder exhibit similar activity with respect to the yield of arenes and the octane number of
the obtained catalyzate, while being a significantly cheaper modifier than cerium dioxide nanopowder.
Thus, all the modified samples exhibit high catalytic activity in the production of high-octane
components of motor fuels and have a higher concentration of weak acid sites than the original HSZ of
the MFI type. The highest concentration of weak acid sites and the highest catalytic activity are exhibited by
the catalyst modified with 1% of nanosized CeO 2 powder. However, it should be noted in particular that the
samples modified with microsized CeO 2 powder have lower but fairly close activity with respect to the yield of

468
arenes in the reaction products and octane number, while being a significantly cheaper modifier than cerium
dioxide nanopowder.

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